description stringlengths 2.98k 3.35M | abstract stringlengths 94 10.6k | cpc int64 0 8 |
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BACKGROUND
[0001] Thin-film-transistor (TFT) technology is important for fabrication of circuitry that requires the ability to flex and in large area devices such as flat panel displays, imagers, and detectors that require active areas that are large compared to the current size of semiconductor wafers. However, a significant limitation of the TFT technology results from the difficulty in fabricating useful PMOS devices in a-Si Amorphous silicon (a-Si) or other thin film semiconductor materials such as Zinc Oxide and thin-film polysilicon. As a result of this difficulty, many TFT circuits only use NMOS transistors, which can cause problems when trying to implement logic with full rail-to-rail output voltage levels, i.e., signals ranging from ground to the power supply voltage. In particular, TFT logic circuits generally lose signal level from the dynamic voltage range and therefore cannot be easily cascaded in the way that conventional CMOS circuits can.
[0002] FIG. 1 shows a circuit diagram for a conventional NMOS inverter 100 that can be fabricated using thin-film transistors in a-Si or other material. Inverter 100 includes two NMOS transistors 110 and 120 . Transistor 110 has a gate and a drain connected to supply voltage Vdd and a source connected to an output node 115 . Transistor 120 has a drain connected to output node 115 , a gate connected to receive an input signal IN, and a source connected to ground.
[0003] In operation, when an input signal IN is high, ideally at supply voltage Vdd, transistor 120 carries a saturation current which also flows from supply voltage Vdd through transistor 110 . Accordingly, when input signal IN is high, inverter 100 acts as a voltage divider, and output signal OUT is pulled to a voltage that will not be the ground voltage but instead depends on the sizes of transistors 110 and 120 . When input signal IN is low (ideally at the ground voltage), transistor 120 will be off, and transistor 110 will pull up output node 115 to a voltage that is lower than supply voltage Vdd by at least the threshold voltage of transistor 110 . Accordingly, the output signal OUT from inverter 100 does not have the full rail-to-rail voltage range from ground to supply voltage Vdd.
[0004] The problem of being unable to provide output signals with the full rail-to-rail voltage swings limits the number of such logic gates that may be serially connected or cascaded without additional signal correction or conditioning. Accordingly, systems and methods that are able to provide rail-to-rail signal range in TFT circuits and NMOS circuits are desired.
SUMMARY
[0005] In accordance with an aspect of the invention, a logic circuit includes a logic stage connected to a supply voltage and a level shifter connected to a voltage higher than the supply voltage. In one embodiment, the level shifter includes: a first NMOS transistor having a gate and drain connected to the higher voltage and a source connected to a first node; and a second NMOS transistor connected between the first node and a reference voltage and having a gate to which a first input signal of the logic circuit is applied. The logic stage includes: a third NMOS transistor coupled between the supply voltage and a second node and having a gate connected to the first node; and a fourth NMOS transistor coupled between the second node and the reference voltage and having a gate to which the first input signal of the logic circuit is applied. An output signal of the logic circuit that is provided at the second node has full rail-to-rail voltage swings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] FIG. 1 is a circuit diagram of a conventional NMOS inverter.
[0007] FIG. 2 is a circuit diagram of an inverter in accordance with an embodiment of the invention.
[0008] FIG. 3 is a circuit diagram of a NAND gate in accordance with an embodiment of the invention.
[0009] FIG. 4 is a circuit diagram of a NOR gate in accordance with an embodiment of the invention.
[0010] FIG. 5 illustrates a branch of a decoder circuit that can be constructed using inverters, NAND gates, and NOR gates in accordance with embodiments of the invention.
[0011] FIG. 6 illustrates a circuit in accordance with an embodiment of the invention integrating decoder circuits and a TFT array in the same thin film.
[0012] Use of the same reference symbols in different figures indicates similar or identical items.
DETAILED DESCRIPTION
[0013] In accordance with an aspect of the present invention, dual rail logic using a supply voltage and a higher voltage can provide full rail-to-rail (e.g., the supply voltage to a reference voltage or ground) swings and maintain the constant levels when required. The dual rail a-Si logic can be used to build in basic logic circuit blocks such as inverters, NAND gates, and NOR gates and therefore can construct virtually all the logic circuits commonly built using CMOS technology. One particular application of the invention is in a flat panel display where the NMOS a-Si logic described herein can be used to build edge electronics to drive the gate lines. In contrast, a conventional manufacturing process fabricates edge electronics for flat panel displays in silicon chips that must be attached to the panels.
[0014] FIG. 2 illustrates an inverter 200 in accordance with an embodiment of the invention employing a level shifter 210 and an inverting stage 220 . Level shifter 210 operates at a voltage VddH that is higher than the supply voltage Vdd of inverter 200 , but level shifter 210 is otherwise similar to the conventional NMOS inverter of FIG. 1 . In particular, level shifter 210 includes a loading TFT 212 and a driving TFT 214 connected in series between voltage VddH and ground. Both TFTs 212 and 214 are N-type. Loading TFT 212 has a gate and a drain coupled to higher voltage VddH and a source coupled to an internal node 216 . Driving TFT 214 has a drain connected to node 216 , a source connected to ground, and a gate connected to the input signal IN.
[0015] Inverting stage 220 includes a loading TFT 222 and a driving TFT 224 connected in series between supply voltage Vdd and ground. Both TFTs 222 and 224 are N-type. Loading TFT 222 has a drain connected to power supply Vdd, a source connected to an output node 226 , and a gate driven by level shifter 210 . Driving TFT 224 has a drain connected to output node 226 , a source connected to ground, and a gate connected to receive an input signal IN.
[0016] When the input signal IN is low, preferably near ground voltage, driving TFT 214 in level shifter 210 is non-conductive, and loading TFT 212 pulls node 216 , and therefore an internal signal IN applied to the gate of TFT 222 , up to a voltage that is lower than voltage VddH by the threshold voltage Vt of TFT 212 . In accordance with an aspect of the invention, voltage VddH is selected to be higher than supply voltage Vdd by at least the sum of the threshold voltages of TFTs 212 and 222 , e.g., VddH≧Vdd+2Vt if TFTs 212 and 222 have the same threshold voltage Vt. As a result, the voltage of internal signal IN is greater than supply voltage Vdd by at least the threshold voltage Vt of TFT 222 . TFT 222 can then pull the output signal OUT to supply voltage Vdd because the gate-to-source V GS of TFT 222 is greater than or equal to the threshold voltage Vt of TFT 222 even when the source (output node 226 ) of TFT 222 is at supply voltage Vdd. Also, input signal IN being low makes TFT 224 non-conductive, so that TFT 224 does not prevent TFT 222 from pulling output signal OUT to voltage Vdd. Inverter 200 thus inverts the low input signal IN to produce output signal OUT fully at supply voltage level Vdd.
[0017] When input signal IN is high, preferably near supply voltage Vdd, driving TFT 214 in level shifter 210 is conductive. The sizes of TFTs 212 and 214 in level shifter 210 are selected so that TFT 214 pulls internal signal IN , which is applied to the gate of loading TFT 222 in inverting stage 220 , low enough that TFT 222 is in non-conductive. The high input signal IN also puts driving transistor 224 in inverting stage 220 in the conductive mode, and with loading TFT 222 being non-conductive, driving TFT 224 pulls output signal OUT to the ground voltage. Inverter 200 thus inverts the high input signal IN to produce output signal OUT fully at ground voltage.
[0018] The level of output signal OUT of inverter 200 can thus change from ground to supply voltage Vdd when input signal IN changes from supply voltage Vdd to ground. Inverter 200 thus has rail-to-rail output capability, and one or more additional inverters of the same type as inverter 200 can be cascaded with inverter 200 without worrying about a signal losing dynamic range. Additionally, all of TFTs 222 , 224 , 212 , and 214 are NMOS devices that can be fabricated in a-Si or other thin-film semiconductors using processes well known in the art.
[0019] Other logic gates such as NAND gates and NOR gates can be built in thin films using similar techniques. FIG. 3 , for example, shows a NAND gate 300 in accordance with an embodiment of the invention. NAND gate 300 includes two level shifters 310 and 320 and a logic stage 330 . The level shifters 310 and 320 receive the input signals A and B of NAND gate 300 , and logic stage 330 produces the output signal OUT.
[0020] Level shifter 310 , which operates at higher voltage VddH, receives input signal A and produces an internal signal Ā that is applied to the gate of a TFT 332 in logic stage 330 . Level shifter 310 includes a loading TFT 312 and a driving TFT 314 that are connected in the same manner as TFTs in level shifter 210 of FIG. 2 . In the same manner as the operation of level shifter 210 described above in regard to FIG. 2 , internal signal Ā from level shifter is in a high state or a voltage about VddH−Vt when input signal A is low and is in a low state or a voltage that keeps a connected transistor 332 non-conductive when input signal A is high.
[0021] Level shifter 320 , which operates at higher voltage VddH, similarly includes a loading TFT 322 and a driving TFT 324 that are connected in the same manner as the TFTs in level shifter 210 of FIG. 2 . TFT 324 receives input signal B and produces an internal signal B . In the same manner as described above, internal signal B from level shifter 320 is in a high state or a voltage of about VddH−Vt when input signal B is low and is in a low state or a voltage that keeps a connected transistor 334 non-conductive when input signal B is high.
[0022] Logic stage 330 includes the pair of TFTs 332 and 334 connected in parallel between supply voltage Vdd and an output node 335 and a pair of TFTs 336 and 338 that are connected in series between output node 335 and ground. TFTs 332 and 334 have gates connected to respectively receive internal signals Ā and B from respective level shifters 310 and 320 . Input signals A and B are respectively applied to the gates of TFTs 336 and 338 .
[0023] In operation, when at least one of input signals A and B is low, at least one of transistors 336 and 338 is non-conductive, and at least one of internal signals Ā and B is in a high state, i.e., at least voltage VddH−Vt. Voltage VddH is greater than supply voltage Vdd by at least 2Vt, so that at least one of TFTs 332 and 334 is conductive and able to pull output signal OUT fully to supply voltage Vdd. Accordingly, if either or both of input signals A and B are in the low state, output signal OUT of NAND gate 300 is a high state that is fully up to supply voltage Vdd.
[0024] When both input signals A and B are high (preferably near supply voltage Vdd), internal signals Ā and B are both in a sufficiently low state that both TFTs 332 and 334 are non-conductive. The high input signals A and B also make both TFTs 336 and 338 conductive, so that the series connected TFTs 336 and 338 pull output signal OUT fully to ground. Accordingly, when both input signals A and B are high, NAND gate 300 drives output signal OUT to a low state that is fully ground. NAND gate 300 thus provides the desired logical operation and a full rail-to-rail voltage swing.
[0025] FIG. 4 shows a NOR gate 400 in accordance with an embodiment of the invention. NOR gate 400 includes level shifters 310 and 320 that are connected to receive input signals A and B and that generate respective internal signals Ā and B as described above in regard to FIG. 3 . NOR gate 400 also includes a logic stage 430 including TFTs 432 , 434 , 436 , and 438 . TFTs 432 and 434 are connected in series between supply voltage Vdd and an output node 435 . Internal signals Ā and B from level shifters 310 and 320 are respectively applied to the gates of TFTs 432 and 434 . TFTs 436 and 438 are connected in parallel between output node 435 and ground, and input signals A and B are respectively applied to the gates of TFTs 436 and 438 .
[0026] When at least one of the input signals A and B applied to NOR gate 400 is high, at least one of transistors 436 and 438 is conductive, and at least one of internal signals Ā and B is in a low state, i.e., a voltage such that the corresponding TFT 432 or 434 is non-conductive. As a result, no current flows from supply voltage through transistors 432 and 434 to node 435 , and one or both of transistors 436 and 438 are conductive and pull the output signal OUT on output node 435 to ground. Accordingly, if either or both of input signals A and B are in the high state, output signal OUT of NOR gate 300 in is a low state that is fully at the ground or reference voltage.
[0027] When both input signals A and B are low (preferably near ground), both transistors 436 and 438 are non-conductive. Internal signals Ā and B are both in a high state, i.e., at least voltage Vdd+Vt, so that series connected TFTs 432 and 434 pull the output signal on node 435 up to supply voltage Vdd. Accordingly, when both input signals A and B are low, NOR gate 400 drives output signal OUT to a high state that is fully the supply voltage Vdd. NOR gate 400 thus provides the desired logical operation and a full rail-to-rail voltage swing.
[0028] The embodiments of this invention described above enable rail-to-rail output capability in a TFT circuit containing only NMOS transistors fabricated in a-Si or other thin film semiconductor materials such as Zinc Oxide and polysilicon. As a result, TFT logic can cascade many functional blocks to produce more complicated functions. In contrast, fabrication of such complex circuits with other thin-film technologies that suffer from loss of dynamic signal range would be difficult or impossible. The TFT circuitry can further include charge pumps or other circuits to generate the higher voltage VddH from the supply voltage Vdd, so that the existence or use of voltage VddH is transparent or unknown to the user of the TFT circuit.
[0029] One example of complex logic that can be fabricated using the logic gates described above is a decoder circuit. FIG. 5 shows the example of one branch 500 of a 4-bit decoder. Decoder branch 500 includes a NOR gate 400 having input terminals connected to the output terminals of two NAND gates 300 , and each NAND gate 300 has an inverter 200 connected to one of its input terminals. The logic gates in decoder branch 500 are thus cascaded in three levels. With the illustrated connections, decoder branch 500 asserts and output signal ĀB C D high only when the four input signals A, B, C, and D meet the conditions of signal A being low, signal B being high, signal C being low, and signal D being high, e.g., when the input signals represent the 4-bit binary value 0101. Techniques for combining inverters, NAND gates, and NOR gates to design decoder branches decoding other binary value are well known in the art and generally require more levels of logic gates when the number of input bits increases. For complex decoders, more levels of logic gates would be a problem if each level lost more of the dynamic signal range. Since each of gates 200 , 300 , and 400 has rail-to-rail output capability the gates can be easily cascaded as needed and complex logic such as decoder circuits can be implemented.
[0030] TFT decoders can be used in large TFT array applications, such as flat panel displays. FIG. 6 , for example, illustrates a thin-film circuit 600 including row decoder logic 610 , column logic 620 , and a TFT array 630 that can all be fabricated using techniques described herein in a thin film of a flat panel display. With a conventional architecture, array 630 has gate lines 632 that need to be driven to high one by one sequentially, for example, to refresh of pixels in the flat panel display. Row decoder 610 , which is constructed from inverters 200 , NAND gates 300 , and NOR gates 400 of the types described above, can perform this function and provides full rail-to-rail signal range even though decoder 610 includes only NMOS transistors. In contrast, some current systems require silicon chips to be bonded on the edge of a panel to provide address decoding for a TFT array fabricated on the panel. The embodiment of this invention illustrated in FIG. 6 can integrate decoder 610 and column logic 620 directly on the panel edge using the same TFT fabrication process as used for array 630 .
[0031] Although the invention has been described with reference to particular embodiments, the description is only an example of the invention's application and should not be taken as a limitation. For example, although the above described embodiments of the invention use only NMOS transistors in a thin-film where useful PMOS transistors are difficult fabricate, some alternative embodiments of the invention use only PMOS transistors in a thin film such as some organic semiconductors where NMOS devices are difficult to fabricate. A purely PMOS embodiment, for example, can include a logic stage made solely of PMOS transistors and PMOS level shifters that are driven by the supply voltage and a negative voltage. The level shifters in the PMOS implementation apply gate voltages to PMOS pull-down TFT in the logic stage, so that the gate voltages are either sufficiently positive to make the PMOS transistors non-conductive or negative enough that PMOS pull-down TFTs can pull an output signal to ground giving the logic stage a full rail-to-rail dynamic signal range for the output signal or signals. Various other adaptations and combinations of the features of the embodiments disclosed are within the scope of the invention as defined by the following claims. | A thin-film logic circuit, which can be fabricated entirely of TFTs of the same conductivity type, includes a logic stage connected to a supply voltage and a level shifter connected to a wider voltage range provided by the supply voltage and ground. The logic circuit produces output signals with full rail-to-rail signal range from ground to the supply voltage and can implement or include a basic logic component such as an inverter, a NAND gate, or a NOR gate or more complicated circuits in which many basic logic components are cascaded together. Such logic circuits can be fabricated directly on flexible structures or large areas such as in flat panel displays. | 7 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates generally to an automotive body structure. More specifically, the present invention relates to the structure of a front pillar section of an automobile body that includes a reinforcement/structural deformation resistance control arrangement that achieves impact force re-direction and improvement in frontal impact safety.
[0003] 2. Description of the Related Art
[0004] Japanese Unexamined Patent Publication (kokai) No. 10-7020 discloses an automotive body structure that is equipped with an arrangement for absorbing collision/impact energy. In this structure, the energy absorbing arrangement is located at the lower ends of each front pillar and at a level that is opposite each of the front wheels. With the arrangement, energy is absorbed in the event that the forward wheels are forced back under the impact to the degree that they deformingly engage the forward surfaces of the lower ends of the front pillars.
[0005] In the above-mentioned structure, while it will be expected that this energy absorbing arrangement would contribute to impact energy absorption at the time of the interference with the front wheels and the other automotive front members. However, it may not contribute to the absorption of the impact energy before the front wheel contacts the lower pillar. Accordingly, there still exists a need for a structure that can improve the impact energy provided by the vehicle cabin in the event of a severe head-on collision or the like.
SUMMARY OF THE INVENTION
[0006] It is an object of the present invention to provide a body structure for a vehicle that is capable of effectively inducing predetermined amounts of buckling (structural) deformation of the structural member(s) located immediately in front of the passenger compartment and which redirects the impact force through an upper portion of the front pillar in a manner that improves collision energy absorbing characteristics of the automotive vehicle.
[0007] These and other objects of the invention are satisfied by an embodiment of the invention, which provides a body structure for a vehicle, comprising: a front pillar having a lower pillar portion and an upper pillar portion, the upper pillar portion merging with an upper end of the lower pillar, the upper pillar portion being angled toward a rear of the vehicle with respect to the lower pillar portion; a hood ridge member extending longitudinally along a side of the vehicle structure, the hood ridge member having a rear end portion joined to an upper end of the lower pillar portion; and a load-converting and force transmitting arrangement comprising: a first structural feature which forms part of the front pillar, the first structural feature being arranged to induce structural deformation of a predetermined portion of the lower front pillar portion upon a predetermined amount of force being transmitted thereto through the hood ridge member as a result of a frontal collision of the vehicle, the first structural feature re-orienting at least a rear end portion of the hood ridge member, with respect to the front pillar, to an orientation where the rear end portion of the hood ridge member is at least partially aligned with the angled upper pillar portion and so that force is transmitted from the hood ridge member toward the upper front pillar portion, and a second structural feature which forms part of at least one of the upper and lower pillar portions and which is arranged to receive force from the hood ridge member and to direct the received force along the upper front pillar portion.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] The various features and advantages of the embodiments of the present invention will become more clearly appreciated as a detailed description thereof is given with reference to the appended drawings wherein:
[0009] [0009]FIG. 1 is a perspective view of a body structure for a vehicle to which the embodiments of the present invention are applicable;
[0010] [0010]FIG. 2 is a perspective view depicting the essential body structural elements according to a first embodiment of the invention;
[0011] [0011]FIG. 3 is a schematic side view of body structure, which demonstrates various aspects of the first embodiment of the invention;
[0012] [0012]FIG. 4 is a sectional view taken along section line 4 - 4 of FIG. 3 showing structural deformation which occurs in accordance with the first embodiment;
[0013] [0013]FIG. 5 is a perspective view of vehicular body structure showing the effect of the first embodiment and the initial type of deformation, which occurs as a result of a severe head-on type collision:
[0014] [0014]FIG. 6 is a perspective view showing the deformation, which develops in accordance with the first embodiment during subsequent stages of vehicle deformation;
[0015] [0015]FIG. 7 is a perspective view of a door hinge employed in the first embodiment of the invention;
[0016] [0016]FIG. 8 is a perspective view showing a second embodiment of the invention;
[0017] [0017]FIG. 9 is a schematic side view of the body structure showing zones of localized reduced structural strength and the provision of reinforcement member in accordance with a third embodiment of the invention;
[0018] [0018]FIG. 10 is a perspective view of a reinforcement member used in the third embodiment of the invention; and
[0019] [0019]FIG. 11 is a perspective view showing a further embodiment of the invention wherein a reinforcing portion is secured to one or both of the upper side of the hood ridge and upper pillar.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
First Embodiment
[0020] In FIG. 1, reference numerals 1 designate left and right front pillars each of which comprises of a substantially-upright lower pillar portion 1 A and rearwardly obliquely angled upper pillar portion 1 B which merges with and upper end of the lower pillar portion 1 A.
[0021] Hood ridge members 2 are provided on each lateral side of the illustrated automotive body. In this arrangement, the rear or inboard ends of each hood ridge member 2 is abutted against and welded to a front face of an upper end of a lower pillar portion 1 A.
[0022] Reference numeral 3 denotes a dash cross member while 4 designates front side members which are respectively coupled a side of the dash cross member 3 . In order to strengthen the hood ridge members 2 , the dash cross member 3 and the front side members 4 , strut tower members 5 are respectively combined with these elements.
[0023] The front ends of the left and right front side members 4 are connected with each other through a first cross member 6 and a bumper armature 7 . The front side members 4 , the first cross member 6 , the bumper armature 7 , the hood ridge members 2 , and the strut tower members 5 constitute the framework of a front compartment FC.
[0024] The respective lower ends of the left and right lower pillars 1 A are joined to left and right side sills 9 , respectively. These side sills 9 constitute a floor framework and extend down both sides of a floor member 8 . The respective upper ends of the left and right upper pillars 1 B are joined to left and right side roof rails 12 and a front roof rail 13 . These elements 12 , 13 constitute a roof framework of a roof panel 11 .
[0025] In FIG. 1, reference numerals 14 denote center pillars, 15 one of the two rear pillars, and 16 one of the two rear fenders of the automotive body.
[0026] In this embodiment, each front pillar 1 is, as best seen in FIG. 4, formed of a substantive outer member 1 OUT and an inner member lIN shown in two dot phantom. Both members of the pillar are each formed as single integral or unitary body via casting of a corrosion resistant lightweight material, such as an aluminum alloy. In FIG. 1, the front end of the side sill 9 , the front end of the side roof rail 12 and the lateral end of the front roof rail 13 , are hatched for ready identification.
[0027] Additionally, as shown in FIGS. 2 and 3, each lower pillar 1 A is provided with a load-converting and transmitting member 21 which converts and transmits a front and rear direction's force that the hood ridge member 2 has been subjected at the vehicle's collision, into a force in the axial direction of the upper pillar 1 B.
[0028] The load-converting and transmitting member 21 includes a load-receiving part 22 which is arranged to extend from a site where the upper end of the lower pillar 1 A to the hood ridge member 2 join, and which is inclined with respect to the lower pillar 1 A for receiving a longitudinally acting collision force in a manner which will be described in more detail hereinafter.
[0029] A “weakened part” (viz., a portion or zone of relatively reduced structural deformation resistance) 23 (or first structural member) is provided forward and below the load-receiving part 22 , and a reinforcement part 24 which supports the load-receiving part 22 .
[0030] The load-receiving part 22 in this embodiment includes a slanted or angled rib 22 a that is integrally or unitarily formed with the lower pillar 1 A. The slanted or angled rib 22 a has its upper edge joined to an upper wall of the hood ridge member 2 that is connected to the front pillar 1 . On the other hand, the reinforcement part 24 has a reinforcement rib 24 a, which is unitarily formed with both sidewalls of lower pillar 1 A and upper pillar 1 B. Additionally, the reinforcement rib 24 a is continuously formed so as to extend from the center of the back face of the slanted rib 22 a into the interior of the upper pillar portion 1 B. In this way, the load-receiving part 22 and the reinforcement part 24 are respectively provided in the form of “rib” structures.
[0031] As shown in FIG. 4, the weakened part 23 is provided by the local control of the wall thickness of the lower pillar 1 A. That is, according to this embodiment, the portion of the lower pillar which is located in front of the slanted rib 22 a is formed so as to have a wall thickness which is less than that of the remaining upper portion of the lower pillar 1 A. In this manner the area of relatively reduced structural deformation resistance is provided through the reduced structural strength inherent with the reduced wall thickness. Further, at the lower end of the lower pillar 1 A, another (second) “weakened” part 31 is provided on the front or forward side of the pillar at a location opposite the front wheel 17 . Behind this weakened part 31 , another (second) load-receiving member 32 is formed for receiving the longitudinally acting collision force, while another (second) reinforcement part 33 is formed there behind for supporting the load-receiving part 32 . Note, these additional parts 31 , 32 , 33 are referred to the second weakened part 31 , the load-receiving part 32 and the reinforcement part 33 to distinguish the same from the corresponding parts 23 , 22 , 24 , located above.
[0032] Similarly to the load-receiving part 22 (or second structural feature) and the reinforcement part 24 of the load-converting and transmitting member 21 , the load-receiving part 32 and the reinforcement part 33 which are located in the lower portion of the lower pillar 1 A, has “rib” structures unitarily formed with the lower pillar 1 A. For example, in the embodiment, the load-receiving part 32 has a vertical rib 32 a that is formed integrally with the lower pillar 1 A and merges with the lateral and bottom wall surfaces (faces) thereof. Similarly, the reinforcement part 33 is also constituted by a reinforcement rib 33 a that is formed integrally with the lower pillar 1 A and the side sill 9 . The reinforcement rib 33 a is, as will become more evident hereinbelow, also configured span the respective side faces of the lower pillar 1 A and the side sill 9 , and to extend from the substantial center of the back face of the vertical rib 32 a into the interior of the side sill 9 . The vertical rib 32 a is, in this embodiment, arc-shaped so as to facilitate its surface-acceptance for the front wheel 17 .
[0033] The reinforcement rib 33 a comprises a first rib member 33 a, which substantially horizontally connects the back face of the vertical rib 32 a with a stepped shelf 9 a formed on the side face of the side sill 9 , and a second obliquely angled rib 33 a 2 which intersects with the first rib 33 a 1 and also connects the back face of the vertical rib 32 a with the bottom face of the side sill 9 .
[0034] Although not shown in detail, the second weakened part 31 at the lower end of the lower pillar 1 A can be also be provided by controlling a localized portion of the wall thickness of the lower pillar 1 A, as similar to the previous weakened part 23 . For example, the forward wall of the portion of the lower pillar which is located in front of the vertical rib 32 a is formed so as to have a wall thickness which less than that of adjacent wall portions and thus establish the so called weakened part 31 .
[0035] The lowermost end of the slanted rib 22 a of the load-converting and transmitting member 21 is continuously integrated with the uppermost end of the vertical rib 32 a of the lower pillar 1 A through the intermediary of a vertically extending connecting rib 34 formed unitarily with the inner face of the lower pillar 1 A.
[0036] Note, although the above ribs 22 a, 24 a, 32 a, 33 a, 34 have been described as being unitarily formed with the outer member 1 OUT, it will be noted that, as an alternative, the ribs can be unitarily formed with the inner member 1 IN if so desired.
[0037] According to the above-mentioned embodiment, when the collision force which acts in the longitudinal fore-and-aft direction of the vehicle, acts on the hood ridge member 2 during a vehicular collision, the collision force is effectively re-oriented and transmitted from the lower pillar 1 A of the front pillar 1 to the inclined upper pillar 1 B by the load-converting and transmitting member 21 . The thus transmitted force is then dissipated into the roof framework members, i.e., the side roof rail 12 and the front roof rail 13 .
[0038] Consequently, while maintaining the reactive force of the hood ridge member 2 against compressive crushing at a higher level, the hood ridge member 2 can be positively deformed in it buckling mode to accomplish the effective buckling deformation of the front compartment FC, thereby improving the collision energy absorbing characteristics of the vehicle.
[0039] In more detail, when the longitudinally acting collision force acts on the hood ridge member 2 , the slanted or angled rib 22 a having the load-receiving part 22 of the load-converting and transmitting member 21 , receives the collision force and, due to the disposition of the weakened part or zone 23 in front of the slanted rib 22 a, induces deformation of this zone with the attendant reduction in resistance to forward motion of the lower portion of the hood ridge member 2 . Accordingly, in response the bucking of the weakened part 23 , the relative high structural deformation resistance which exist at the upper level of the hood ridge member 2 causes the hood ridge member 2 to pivot downwardly so that it becomes re-oriented and tends to become aligned with the upper pillar 1 B in the manner illustrated in FIG. 5. In this way, it is possible to achieve load transmission to the upper pillar 1 B effectively.
[0040] Again, as shown in FIG. 6, even if the buckling deformation of the weakened part 23 permits the rear end of the member 2 to butt against the bottom of the slanted rib 22 a, the load transmission to the side of the upper pillar 1 B is still maintained during the latter stages of hood ridge buckling deformation since the slanted or angled rib 22 a is reinforced by the reinforcement rib 24 a. Therefore, due to the controlled buckling deformation induced in the lower pillar 1 A through the provision of the weakened part 23 , it is possible to improve the collision energy absorbing characteristics of the vehicle due to the buckling deformation of the front compartment FC including the hood ridge member 2 and thus increase the amount of collision energy absorbed.
[0041] Above all, since the reinforcement rib 24 a is formed integrally with the upper pillar 1 B from the back face of the slanted rib 22 a to the inside of the upper pillar 1 B in addition to the integral casting of the lower pillar 1 A with the upper pillar 1 B, it is possible to remarkably enhance the efficiency of load transmission in the axial direction of the upper pillar 1 B.
[0042] Additionally, the slanted or angled rib 22 a has an upper end or edge joined to the upper wall of the hood ridge member 2 . Thus, if the strut tower 5 is subjected to an upwardly acting thrust or force, it is possible to maintain the resistance of the strut tower 5 to such a force due to the tensile strength of the slanted rib 22 a.
[0043] With the provision of the second lower weakened part 31 , wherein the vertical rib 32 a acts in the same manner as the load-receiving part 32 and the reinforcement rib 33 a acts in the same manner as the reinforcement part 33 , when the buckling deformation of the front compartment FC progress to the degree that the front wheel 17 engages and interferes with the lower end of the lower pillar 1 A, collision energy can be further absorbed by the buckling deformation thereof, in the manner depicted in FIGS. 5 and 6.
[0044] It is to be furthermore noted that the buckling deformation of the weakened part 31 is restricted by the vertical rib 32 a, as shown in FIG. 6. That is to say, when the wall structure which defines the weakened part 31 is forced back into contact with the vertical rib 32 a by tire impact, the longitudinally acting force is received by the rib 32 a and is then transmitted into the side sill 9 thus reducing the load bearing burden on the lower pillar 1 A.
[0045] Since the reinforcement rib 33 a is formed integrally with the lower pillar 1 A and extends from the back face of the vertical rib 32 a into the interior of the side sill 9 , in addition to integral casting of the lower pillar 1 A and the side sill 9 as a single body, the connecting rigidity between the lower pillar 1 A with the side sill 9 is enhanced.
[0046] Additionally, the reinforcement rib 33 a comprises a first substantially horizontal rib 33 a 1 which is connected with a shelf section 9 a formed on the side face of the side sill 9 , and thus exhibits a high surface rigidity, and the second rib 33 a 2 which is connected with the back face of the side sill 9 while obliquely intersecting with the first rib 33 a 1 in order to distribute the load into the side face and the bottom face of the side sill 9 . Accordingly, it is possible to remarkably enhance the load transmissibility from the lower pillar 1 B to the side sill 9 .
[0047] Further, since the slanted/angled rib 22 a located at the upper end of the lower pillar 1 A is connected with the vertical rib 32 a at the lower end of the lower pillar 1 A through the connecting rib 34 formed integrally with the lower pillar 1 A, the load transmissibility in the vertical direction of the lower pillar 1 A is improved to enhance the load transmissibility to the upper pillar 1 B and the side sill 9 even further.
[0048] The above-mentioned lower pillar 1 A is equipped with door hinges of the type illustrated in FIG. 7. These door hinges 35 are fastened to upper and lower points on an outboard side face of the lower pillar 1 A through respective mounts or seat parts 36 . However, if the door hinges 35 are fastened in a manner wherein their seat parts 36 are located at the same level as, and/or overlap either of the weakened parts or zones 23 , 31 , a problem may arise in that the “positive” (viz., controlled) requisite buckling deformation of the parts 23 , 31 is modified by the existence of the seat parts 36 . In this embodiment however, each door hinge 35 is provided, between front and rear fastening holes 37 , 37 , with an elongate hole 38 or the like. This feature reduces the structural reinforcing effect of the portion of the door hinge 35 (viz., the seat 38 ), and obviates the problem wherein the desired deformation of the “weakened” parts 23 , 31 is inhibited.
[0049] Further, the weakened parts 23 , 31 of this embodiment are respectively established by controlling the wall thickness of the lower pillar 1 A and the load-receiving parts 22 , 32 and the reinforcement parts 24 , 33 are together provided in the form of “rib” structures. Therefore, these elements can be easily formed by means of casting and additionally, the distribution of plate/wall thickness and the rigidity of ribs can be adjusted to exhibit optimum characteristics through the control of wall thickness while taking advantage of the ease with which the products are cast.
[0050] Since the lower pillar 1 A and the upper pillar 1 B are cast into one body including the load-receiving parts 22 , 32 , the reinforcement parts 24 , 33 and so on, it is possible to reduce the number of components, realizing the rationalization of vehicle body.
Second Embodiment
[0051] [0051]FIG. 8 shows the second embodiment of the present invention. According to this embodiment, the reinforcement part 24 of the load-converting and transmitting member 21 is formed as a separate a reinforcement plate 24 b which is connected to essentially the center of the rear face of the slanted or angled rib 22 a, and arranged to extend back through the interior of the upper pillar 1 B. The reinforcement plate 24 b is secured in place by means of welding, bonding, etc.
[0052] Therefore, according to the second embodiment, it is possible to achieve essentially the same collision energy absorbing characteristics as the first embodiment. Additionally, owing to the provision of the reinforcement plate 24 b which is separate (viz., not unitarily formed) from the upper pillar 1 B, it is possible to achieve an increase in the freedom of design with respect to the front pillar 1 and the reinforcement part 24 . Of course, by controlling both profile and thickness of flanges 24 c and a bead 24 d of the plate 24 b in a suitable manner, it is also possible to control the characteristics of the reinforcement part 24 in terms of its reaction generating effect (viz., its force resisting/directing effect).
Third Embodiment
[0053] [0053]FIGS. 9 and 10 show a third embodiment of the invention. According to this embodiment, the angled rib 22 a of the load-converting and transmitting member 21 is arranged so as to extend from a junction of the upper wall of the hood ridge member 2 and the front pillar 1 to the rear face or wall of the lower pillar 1 A. A reinforcement part or portion 24 is defined by a thickened wall portion 24 c which is either integrally formed on, or secured to, a portion of the rear wall of the lower pillar 1 A to which the slanted rib 22 a is integrated.
[0054] According to this embodiment of the invention, a reinforcement member 39 is additionally disposed in the lower pillar intermediate of the upper end which is connected to the hood ridge member 2 and the lower end which is connected to the side sill 9 . The provision of the reinforcement member 39 , renders it possible to provide both areas of the lower pillar portion which are faced by the slanted or angled rib 22 a and the vertical rib 32 a (shown by vertical hatching in FIG. 9), with lower relative levels of structural rigidity as compared with that portion which exhibits enhanced structural rigidity due to the provision of the reinforcement member 39 . This, in effect, allows these portions to undergo initial deformation and thus provides the weakened parts 23 , 31 of the previous embodiments without actually reducing the structural strength of the two zones.
[0055] As shown in FIG. 10, the reinforcement member 39 is shaped so as to have a substantially V-shaped configuration. The member 39 has an abutment surface 39 a formed at the apex of the V-shaped member and flanges 39 b, 39 c formed on the upper and lower terminal ends. The abutment surface 39 a is welded to the front face of the lower pillar 1 A. The upper flange 39 b of the member 39 is welded to the base of the thickened part 24 c connected to the slanted rib 22 a, while the lower flange 39 c is welded to the upper end of the vertical rib 32 a.
[0056] Therefore, also in this embodiment, it is possible to effect the similar characteristics of absorbing the collision energy to that of the first embodiment. Furthermore, since the slanted or angled rib 22 a is arranged so as to extend from the upper wall of the hood ridge member 2 to the rear face of the lower pillar 1 A in the junction zone between the lower pillar 1 A and the upper pillar 1 B, the rigidity of integration therebetween can be enhanced to improve the transmissibility of load from the hood ridge member 2 to the upper pillar 1 B.
[0057] In addition, since the reinforcement part 24 is constituted by the thickened part 24 c on the rear face of the lower pillar 1 A, it is possible to establish the appropriate distribution of plate thickness owing to the characteristics of casting products.
[0058] Further, since the weakened parts (viz., the areas of relatively lower structural deformation resistance) 23 , 31 are established by the addition of the reinforcement member 39 , the overall rigidity of the pillar can be enhanced as compared with the previously described embodiments wherein both weakened parts are provided through the use of wall structures wherein the thickness of the walls are deliberately reduced to lower the strength thereof.
[0059] Additionally, since the reinforcement member 39 connects the slanted rib 22 a with the vertical rib 32 a in this embodiment, the reinforcement member 39 provides the same function as the connecting rib 34 of the first embodiment, whereby it is possible to enhance the load-transmission performance of the lower pillar 1 A in the vertical direction of the vehicle.
Fourth Embodiment
[0060] [0060]FIG. 11 shows a fourth embodiment of the invention. This arrangement, similar to the third embodiment, establishes a location of increased structural strength which automatically renders other portions relatively lower in resistance to structural deformation and thus achieves the same effect as the previously described embodiments. To increase the strength of the lower portion of the upper pillar portion 1 B and/or an upper end portion of the hood ridge member 2 , a reinforcement member or gusset 40 is welded or otherwise secured to an inboard edge of these two members in the manner shown in FIG. 11. This gusset 40 in this embodiment is located along and edge of the upper pillar 1 B. In addition, another reinforcement member or gusset 41 is secured to an inboard edge of the lower pillar 1 A.
[0061] The gusset 41 is attached to the upper part of the front pillar and gusset 41 is attached to the lower part of the front pillar. The gussets 40 , 41 form more rigid portions, which have a relatively higher rigidity, in the front pillar and center part C. A weakened portion is thus formed between the high rigidity portions. Because gussets 40 , 41 are attached to the outer panel of the front pillar, the body structure is constructed rather easily. Moreover, the rigidity is readily adjustable due to the gussets 40 , 41 being attached to the outer panel of the front pillar.
[0062] Japanese Patent Application No. 2000-66478 upon which this application is based and on which the claim to priority is founded, is incorporated herein by reference thereto.
[0063] Although the invention has been described above with reference to only a limited number of embodiments, the invention is not limited thereto and the various modifications and changes which can be made without departing from the scope of the invention will be self-evident to those skilled in the art to which the invention pertains. | The pillar structure to which the passenger cabin end of the hood ridge panel is connected, is arranged have different localized structural deformation resistances which buckle/deform in a manner which causes the hood ridge panel to reorient in response to a vehicle structure deforming force being applied to the front of the vehicle during a collision, and results in the force, which passes through the hood ridge panel, being redirected by a load-converting and transmitting member included in the pillar, up and along an upper rearwardly angled upper portion of the pillar. This force redirection produces sufficient resistance to induce compressive bucking in the structure forward of the passenger cabin and thus attenuate damage to the cabin structure. | 1 |
BACKGROUND
1. Field of the Invention
The present invention relates to an improved piston adapted to be used in a pneumatic, hydraulic, or hydropneumatic installation.
2. The Prior Art
Installations of the type referred to typically include a cylinder, a piston slidably housed within the cylinder and being provided with damping means and being connected to a piston rod, the cavity of the cylinder being filled with gas and/or liquid and being separated by the piston into two working chambers, the piston rod extending through guiding and sealing means provided at one end of the cylinder, and the damping means comprising a constantly open throttled passage between said working chambers.
German Gebrauchmuster No. 7,833,144 describes, for example, a gas spring having a constantly open passage between the working chambers, the passage being defined by a throttled bore through the piston extending parallel to the axis of the piston. This throttled bore is effective only when the piston rod moves out of the cylinder and is adapted to limit the rate of movement of the piston rod out of the cylinder to a predetermined measure. Especially in gas springs having a high internal pressure, these throttled bores have a cross-section of about from 0.3 to 0.4 mm φ to achieve the desired damping effect. Due to this narrow cross-section, the bores are susceptible to clogging, as even extremely small impurities can occlude this cross-section. Furthermore, these bores must be made very precisely to maintain the damping effect within the required tolerance.
SUMMARY
It is the object of the present invention to overcome the disadvantages of the conventional constructions and to provide a damping means for a piston movable within a cylinder, which damping means is simple to manufacture and moreover is very reliable in operation. Furthermore, it is desired to hold the damping effect of the damping means within the required tolerance.
According to the present invention this and other objects are accomplished in that the constantly open throttled passage comprises at least one spiral throttled channel extending in a plane perpendicular to the axis of the piston. The spiral design of the throttled channel allows the channel to be relatively long and to have a correspondingly large cross-section, so that clogging caused by impurities entrained by the damping medium is prevented. The desired damping effect can be achieved in a simple manner by modifying, as needed, the length and the cross-section of the channel. Such a relatively large cross-section of the channel has the advantage that impurities which might be entrained in the damping medium cannot deposit, but are instead removed from the throttled channel by the damping medium.
In accordance with a further feature of the present invention, the throttled channel extends in the plane perpendicular to the axis of the piston along an angle or more than 360°. Due to the spiral design, it is thus easy to provide a throttled passage of great length at one front end of the piston. In order to achieve a predetermined flow resistance, the cross-section of said throttled channel can, therefore, be correspondingly large. For this reason, the pitch selected for the spiral is decisive for the length of the channel and can be readily adapted to the required damping effect.
According to a further feature of the present invention, at least one axial bore provided within the piston body terminates in the throttled channel in the region of its radially inner end, to make sure that damping fluid flows through the throttled channel over its entire length. It is of advantage to provide the axial bores with larger cross-sections than the throttled channel so that merely the throttled channel acts as a damping means and no special requirements of the axial bore itself must be fulfilled. Hence the axial bore need not be provided after the piston has been manufactured, but can be made at the same time as the piston is sintered, die-cast or injection-molded. The making of the throttled channel as such is very simple because, according to a further feature of the present invention, this throttled channel extends at the front end of the piston body and is covered by a piston plate. The piston body including the throttled channel thus is simple and inexpensive to manufacture. Moreover, the present die-casting, sintering, and injection-molding techniques allow for high precision manufacture of the groove-shaped channel within the piston body.
In the front face of the piston body, the throttled channel is preferably covered by a piston plate which can be a planar member made of plastic material or of a composite material. It is also possible to provide this throttled channel in a piston plate. In either case, the radially outer end of the throttled channel terminates in one of the working chambers.
If great damping forces are required or if a relatively large cross-section of the channel is desired, it is possible according to the present invention to arrange a spiral throttled channel on both sides of the piston body and to connect the radially inner ends of the channel by means of an axial bore. According to a further feature of the invention, it is advantageous to provide the outlet slot or the inlet slot, respectively, of the throttled channel approximately tangentially to the peripheral surface of the piston.
Details of the invention follow from the description of the illustrated embodiments.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a longitudinal section of a gas spring;
FIG. 2 is an end view of the piston body according to line V--V of FIG. 1;
FIG. 3 shows a spiral throttled channel extending in the piston plate;
FIG. 4 is a top view of the piston unit on the line IV--IV of FIG. 3; and
FIG. 5 shows a piston having spiral throttled channels extending in both front faces of the piston body.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The preferred embodiment of the present invention is a gas spring which presents a pneumatic installation, and which produces an outward force acting on the piston rod which corresponds to the product of the cross-sectional area of the piston rod and the pressure within the cylinder. The invention can of course be used for any other pneumatic, hydraulic, or hydropneumatic installations in which a dampened movement of the piston rod is to be provided. In particular, in gas springs which are installed, for example, as operating aids for opening a flap swinging about a horizontal axis, damping means are used to prevent rapid movement of the piston rod.
The gas spring shown in FIG. 1 has a cylinder 1 in which slides a piston 5 connected to a piston rod 4. Guide means 2 for the piston rod 4 and the piston rod sealing means 3 are positioned at one end of the cylinder. The piston 5 mounted on the extension 13 of the piston rod 4 separates the cavity of the cylinder 1 into a working chamber 14 above the piston and into a working chamber 15 below the piston. These working chambers 14 and 15 are filled with pressurized gas. The piston 5 includes the piston body 6 disposed between the piston plate 9 and the piston disc 10. An annular recess within the piston body 6, together with the piston disc 10, define an annular groove 11 in the piston which is larger than a piston ring 12 both in axial and in radial direction. Thus the piston ring 12 which is in sealing engagement with the inner peripheral face of the cylinder 1 can be moved in the axial direction in the annular groove 11. The piston body 6 further comprises an axial bore 7 connected to the throttled channel 8. This axial bore 7 and the throttled channel 8 define the constantly open passage between the working chamber 14 and the working chamber 15. FIG. 2 shows the throttled channel 8 positioned within the piston body 6, and it can be seen that the axial bore 7 ends in the channel 8 in the region of the radially inner end thereof and that this channel 8 extends spirally on the lower front side of the piston body 6. The exit of the throttled channel 8 into the working chamber 15 extends approximately tangentially to the peripheral surface of the piston body 6. In order to achieve an undisturbed flow of the fluid into the working chamber 15, it is of advantage to provide the piston plate 9 with a diameter which is less than the diameter of the piston body 6.
The mode of operation of the gas spring shown in FIGS. 1 and 2 will be explained below. Due to the internal pressure of the gas spring, the outward thrust on the piston rod corresponds to the product of the pressure and the cross-sectional area of the piston rod. The rate at which the piston rod 4 moves out of the cylinder 1 is determined by the throttle means within the piston 5. During the movement of the piston rod 4 out of the cylinder 1, the damping medium flows through an opening 25 in the piston plate 10 and through the axial bore 7 into the throttled channel 8. The damping effect on the movement of the piston rod is substantially determined by the length and the cross-section of the spiral throttled channel 8 through which the damping medium flows into the working chamber 15. During this movement, the piston ring 12 engages the lower side face of the annular groove 11 of the piston (as shown in FIG. 1) due to the friction caused between the piston ring 12 and the inner peripheral face of the cylinder 1, so that the annular gap 26 between the piston 5 and the cylinder 1 is closed, with the result that the damping medium can flow from the working chamber 14 to the working chamber 15 only through the axial bore 7 and the throttled channel 8. Due to the spiral shape of the throttled channel 8, the length of the throttled channel can be relatively great, i.e. substantially greater than 360°. FIG. 1 clearly shows that the throttled channel is defined by the piston body 6 and the piston plate 9. This arrangement of the throttled channel allows a very simple manufacture.
When the piston rod 4 moves into the cylinder 1 under an externally applied force acting on the piston rod, the movement of the piston rod into the cylinder has the effect that the piston ring 12 in the annular groove 11 of the piston makes engagement with the inner side of the piston disc 10. Thus an additional flow cross-section is provided and the damping medium sequentially flows through the annular gap 26 between the piston body 6 and the cylinder 1 through the annular groove 11 of the piston and through the opening in the piston disc 10 from the working chamber 15 to the working chamber 14 without substantially damping the movement of the piston rod 4 into the cylinder 1.
The embodiment shown in FIGS. 3 and 4 differs from that shown in FIGS. 1 and 2 principally in that a plurality of axial bores 7 are provided in the piston body 6 which terminate in an annular channel 16 extending in the piston body 6. In this embodiment, the piston 5 also includes the piston body 6 mounted on the extension 13 of the piston rod 4 between the piston disc 10 and the piston plate 9. A further difference resides in that the spiral throttled channel 17 extends in the piston plate 9 and is covered by the piston body 6. The annular channel 15 of the piston body 6 communicates with the throttled channel 17 in the region of the radially inner end of the throttled channel 17. When the piston rod 4 moves out of the cylinder 1, the damping medium flows from the working chamber 14 through the opening 25 in the piston disc 10 into the axial bores 7 and through the annular channel 16 into the throttled channel 17 and from there into the working chamber 15.
In the embodiment shown in FIG. 5, the piston body 6 is provided with spiral throttled channels on both sides thereof. The throttled channel 20 covered by the piston disc 18 has an inlet slot 21 at its radially outer end, and terminates at its radially inner end in the axial bore 7. This axial bore 7 connects the throttled channel 20 to the throttled channel 8, which is covered by the piston plate 9 and has an outlet slot at its radially outer end. Thus, the throttled channels 8 and 20 are connected in series. In order to provide a substantially unrestricted flow passage defined by the piston and the inner wall of the cylinder 1 when the piston 4 and thus the piston move into the cylinder 1, the piston disc 18 is provided with recesses 19. At this stage of the movement of the piston rod into the cylinder, the piston ring 12 engages the contact face defined by the piston disc 18 due to the friction caused on the inner peripheral face of the cylinder 1. The recesses 19 and the annular groove 11 of the piston as well as the annular gap 26 defined between the piston body 6 and the cylinder 1 permit the unrestricted flow of the damping medium from the working chamber positioned below the piston into the working chamber positioned above the piston. Such a design is suited in particular for use in installations in which a great damping effect is needed when the piston rod moves out of the cylinder or when throttled channels having a relatively large cross-section are desired.
Although the invention has been described herein by reference to specific embodiments thereof, it will be understood that such embodiments are susceptible of variation and modification without departing from the inventive concepts disclosed. All such variations and modifications, therefore, are intended to be encompassed within the spirit and scope of the appended claims. | A piston for a pneumatic, hydraulic or hydropneumatic fluid-filled cylinder includes a constantly open throttled passage therethrough comprised by at least one spiral-shaped throttled channel extending in a plane perpendicular to the piston axis. The spiral configuration of the throttled channel permits the use of a relatively large flow cross section in the channel, thereby preventing clogging of the throttling passage by contaminants entrained in the damping medium, while still providing the desired damping effect. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a cage, more particularly to a modularized cage, typically a birdcage.
2. Description of the Related Art
A cage, such as a birdcage, is a necessary tool for breeding or selling pets like birds, and the size of the birdcage should be made according to the size and quantity of birds. Therefore, a breeder may provide an appropriate size of the cage to a cage manufacturer. If a manufactured cage is transported as is, it will occupy lots of space. Therefore, the structure of the birdcage designed in detachable modules for the purpose of easy transportation and assembling upon its arrival at the destination can effectively reduce transportation cost. Easy assembling and firm structure, and even more flexibility for changes and additional functions should be taken into consideration for the module design of the birdcage.
SUMMARY OF THE INVENTION
The primary objective of the present invention is to provide a sectional birdcage, designed in detachable modules for reducing accommodation space and lowering transportation cost. The birdcage of the present invention features easy assembly as well as stable and firm structure, and the birdcage adapts to different specifications and provides more choices for configuration under limitations of cost.
Technical measures taken to achieve the above stated objectives of the present invention, comprises:
a plurality of aluminum pressed pipes; the cross-sectional structure of each pipe having a hollow main pipe; a grid groove being disposed along the direction of the long axis on both sides of the exterior adjacent to the main pipe, and both ends of the grid groove being open; and an opening being disposed at the center of the exterior;
a plurality of three-way connectors made of a plastic material, each three-way connector having a main body, with an insert post being protruded from each of three sides adjacent to said main body for allowing an end of the main body of the pipe to be tightly pressed and pass through; and
a plurality of metal grid plates, having a metal bar at its periphery slidably embedded into a groove of the grid plate of the pipe.
BRIEF DESCRIPTION OF THE DRAWINGS
Other features and advantages of the present invention will become apparent in the following detailed description of preferred embodiments with reference to the accompanying drawings, in which:
FIG. 1 is an exploded perspective view showing dissembled parts of the birdcage according to a first preferred embodiment of the present invention.
FIG. 2 is a perspective view showing the parts according to FIG. 1 assembled.
FIG. 3 is a cross-sectional view of the birdcage through cross-section 3 — 3 in a direction of arrows indicated in FIG. 2 .
FIG. 4 is a cross-sectional view through cross-section 4 — 4 indicated in FIG. 2 .
FIG. 5 is an enlarged exploded perspective view of a region enclosed in a circle in FIG. 2 .
FIG. 6 is a perspective view showing disassembled parts of the birdcage according to a second preferred embodiment of the present invention.
FIG. 7 is a cross-sectional view of the birdcage through cross section 7 — 7 in a direction of arrows indicated in FIG. 6 .
FIG. 8 is an exploded perspective view showing disassembled parts of the birdcage according to a third preferred embodiment of the present invention.
FIG. 9 is a perspective view showing the parts assembled according to FIG. 8 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The modularized birdcage according to the present invention comprises:
a plurality of frame pipes generally designated 10 as shown in FIGS. 3 and 5, each preferably being an aluminum pressed pipe and having a cubic main pipe body 11 , and said main pipe body 11 at each of its two externally adjacent sides having a grid plate groove 12 along the direction of the long axis of the main pipe body 11 , and both ends of said grid plate groove 12 being open, and an opening being disposed at the center of an external wall;
a plurality of three-way connectors 20 as shown in FIGS. 1 and 5, made of a plastic material and having a cubic main body 21 , and said main body 21 at each of its three adjacent sides having an outwardly protruded insert post 22 for allowing an end of the main pipe body 11 of the frame pipe 10 to pass through, and a slippery-proof threaded section being disposed on the surface of the insert post 22 such that the inner wall of the main pipe body 11 producing a slippery-proof effect to prevent the insert post 22 from falling apart from the main pipe body 11 ; a roller through hole 23 being disposed on said main body 21 for allowing an insert rod 241 on a roller 24 to pass through, and said roller 24 being disposed on the bottom of the three-way connection 20 ;
a plurality of grid plates 30 as show in FIGS. 1, 2 , and 3 , each grid plate each 30 comprising a plurality of longitudinal and transversal metal bars, 301 , 302 and all longitudinal metal bars 301 being soldered with the transversal metal bars 302 on the same side; the metal bar at the periphery of said grip plate 30 being slidably embedded into the groove of grid plate of said frame pipe 10 , thereby a metal bar 301 , 302 being embedded into the inner side of the grid plate groove 12 , and the end of its perpendicularly intersected metal bar 301 , 302 passing through an opening 121 of the grid plate groove 12 ;
a plurality of grid plate reinforced rod 40 as shown in FIGS. 1 , 2 , and 4 , each being a pressed aluminum rod with a length slightly shorter than the width of the grid plate 30 ; the cross-sectional structure having an upper and a lower grid plate groove 41 , and an opening 411 at the center of the cross-sectional structure along the direction of the long axis; the metal bars at the bottom and top of the two upper and lower grid plates 41 and the grid plate groove 41 of the reinforced rod 40 being intersected and slidably embedded at their ends; the transversal metal bar 302 being embedded into the inner side of the grid plate groove 41 , and the longitudinal metal bar 301 passing through the opening 411 of the grid plate groove 41 ; the way of using said grid plate reinforced rod 40 for the connection increasing the area of the grid plate 30 and providing an excellent support to said grid plate 30 .
By means of the foregoing modules, a birdcage 50 of different configurations and variations can be made. As shown in FIGS. 1 and 2, the metal bars at the periphery of the grid plate 30 and the grid plate groove 12 of the frame pipe 10 are intersected and slidably embedded at their ends, and the frame pipes 10 are mutually coupled with a three-way connector 20 to constitute a cage bottom 51 , a cage body 53 , and a cage top 52 of the birdcage 50 . A plurality of rollers 24 can be installed onto the bottom of the three-way connector 20 at the cage bottom 51 as needed. Accessory resting bars, feeding boxes, drinking devices and the like (not shown in the figure) can be installed inside the birdcage. Because such accessories are not key features of this invention, they will not be described here. The grid plate 30 for the cage body 53 may include a door 54 according to the prior art technology.
The above embodiment may use several grid plate reinforced rods 40 and a required number of grid plates 40 depending on the area of the grid plate 30 and the required support. If grid plate reinforced rods are used, the bottom and the top of the upper and lower grid plates 30 should be coupled to the grid plate groove 11 of the reinforced rod first, and then the metal rod at the periphery of the grid plate 30 with the combined grid plate rod 40 are slidably embedded into the grid plate groove 12 of the frame pipe 10 . Because the length of the grid plate reinforced rod 40 is shorter than the width of the grid plate 30 , both ends of the grid plate reinforced rod 40 will not be embedded into the grid plate groove 12 of the frame pipe 10 .
Further, in FIGS. 1 and 2, various measures may be used to support the bottom of the grid plate 30 of the cage body 53 to an appropriate height, and its purpose is to create an accommodating space between the bottom of the cage body 53 and the cage bottom 51 for placing a dirt tray 56 . In the embodiment of this invention, a supporting frame 57 is slidably embedded into the grid plate groove 12 of the frame pipe 10 at the cage bottom 51 and the bottom of the cage body 53 first, and then the grid plate 30 of the cage body 53 is disposed; such supporting frame 57 upwardly supports the grid plate 30 of the cage body 53 at a predetermined height, and then the bottom of the grid plate 30 of the cage body 53 is hooked to a bottom grid 58 , and a dirt tray 56 can be placed in the space between the bottom grid 58 and the cage bottom 51 , and the dirt tray 56 can be drawn out from the reserved opening in the supporting frame 57 .
Refer to FIGS. 6 and 7 for the second preferred embodiment of this invention, which has a panel groove 13 disposed at the outer edge of the frame pipe 10 ′ of the cage body 53 and the cage bottom 51 , a panel 55 is slidably embedded into the corresponding panel groove 13 of the cage body 53 , such that the bottom of the panel 55 can be supported by the panel groove 13 of the cage bottom 51 . By the means of the panels surrounding the cage body 53 , the bird inside the birdcage can be protected from strong winds or achieve the purpose of keeping the bird warm. A viewing hole 551 is added onto the panel 55 for gripping or viewing.
Refer to FIGS. 8 and 9 for the birdcage 60 according to the third preferred embodiment of this invention. By means of the aforementioned modules and assembling principle, a cage bottom 62 , a cage body 65 , and a cage top 63 of a birdcage 60 are constructed. However, the grid plate of the cage bottom 62 is replaced by a bottom plate 61 , and the cage body 65 is made of transparent side panels 64 , grid plate reinforced rods 40 , and grid plates 30 . The bottom plate 61 and side plate 64 at the cage bottom 62 according to this embodiment constitute another feeding area 66 , and such feeding area 66 may be covered with other basic materials such as soil, said, and saw dust for breeding small pets other than birds such as mice, rabbits, etc. As to the way of assembling the cage body 65 , four pieces of transparent side panels 64 are embedded downward into the bottom of the frame pipe 10 of the cage body 65 and the frame pipe 10 of the cage bottom 62 , and then the bottom of grid plate 30 is slidably embedded into a grid plate reinforced rod 40 , and the metal bars at the periphery of the grid plate 30 is slidably embedded downwardly into the grid plate groove 12 of the frame pipe 10 of the cage body 65 . The grid groove 41 at the bottom of the grid plate reinforced rod 40 is embedded into the top of the side panel 64 .
The birdcage of the present invention can be designed as a combination of several modules, and each module facilitates the reduction of accommodating space and transportation cost. The birdcage of this invention does not require any special tools or special skills for its assembling; the assembling is simple and easy, yet the structure is very stable and reliable. The frame pipe of this invention preferably is made of aluminum (or equal) by pressing, and thus it is not limited to any particular predetermined length. Therefore, such birdcage can adapt different specifications or provide more choices for its shape.
While the present invention has been described by two most practical and preferred embodiments, it is understood that this invention is not limited to the disclosed embodiments but is intended to cover various arrangements included within the spirt and scope of the broadest interpretations and equivalent arrangements. | The present invention discloses a sectional cage, typically a birdcage designed as a combination of several modules, each module facilitating the reduction of the accommodating space and transportation cost. The cage of the present invention features an easy assembling and a stable and firm structure, and adapts different specifications and provides more choices for economical variation of its shape, assembly and disassembly. | 0 |
BACKGROUND
1. Technical Field
An embodiment of the invention relates generally to the detection of electromagnetic energy, and in particular relates to a detector to detect extreme ultraviolet radiation.
2. Description of the Related Art
Photo-lithography processes are used to create the very small features that make up integrated circuits, by projecting high-density patterns of electromagnetic radiation onto a wafer during manufacture. Higher density integrated circuits require smaller feature sizes. However, a limiting factor in how small the features can be produced is the wavelength of the radiation used to project the pattern. Current photo-lithography techniques may use radiation in the vacuum ultraviolet (VUV) range, with a wavelength approximately in the 100–200 nanometer (nm) range, but significant increases in feature density may require the use of extreme ultraviolet (EUV) radiation, which may have a wavelength approximately in the 10–14 nm range. However, EUV radiation is highly absorbed by most materials, so EUV-based lithography may require different techniques than are used with longer wavelengths of radiation.
Controlling the amount of energy projected during the lithography operation is important, and requires determining the amount of energy in the EUV beam. Diode based sensors may be used to measure EUV intensity. Unfortunately, directing a controlled portion of the beam to a diode sensor with a beam splitter, which works well with longer wavelengths of radiation, is impractical with the high-energy EUV radiation. Conventional forms of detecting the electromagnetic energy off-axis in the lithography tool have proven to produce significant errors, since the actual dose within the path must be inferred, and controlling the percentage of energy off-axis is difficult.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention may be understood by referring to the following description and accompanying drawings that are used to illustrate embodiments of the invention. In the drawings:
FIG. 1 shows a cross section of a grazing-incidence detector comprising a sensor coated with a reflective material, according to one embodiment of the invention.
FIG. 2 shows a chart of the amount of reflectivity of a ruthenium layer based on surface roughness, according to one embodiment of the invention.
FIG. 3 shows a flow chart of a process for fabricating a detector, according to one embodiment of the invention.
FIG. 4 shows a cross section of a detector comprising a multi-layer reflector, according to one embodiment of the invention.
FIG. 5 shows a schematic of the effects of a multi-layer reflector, according to one embodiment of the invention.
FIG. 6 shows an example graph of reflectivity vs. the number of bilayers, according to one embodiment of the invention.
FIG. 7 shows a flow chart of a method of fabricating a detector, according to one embodiment of the invention.
FIGS. 8A through 8I show a cross section of elements of a detector during fabrication, according to one embodiment of the invention.
FIG. 9 shows portions of an EUV lithography system, according to one embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
In the following description, numerous specific details are set forth. However, it is understood that embodiments of the invention may be practiced without these specific details. In other instances, well-known structures and techniques have not been shown in detail in order not to obscure an understanding of this description.
References to “one embodiment”, “an embodiment”, “example embodiment”, “various embodiments”, etc., indicate that the embodiment(s) of the invention so described may include a particular feature, structure, or characteristic, but not every embodiment necessarily includes the particular feature, structure, or characteristic. Further, repeated use of the phrase “in one embodiment” does not necessarily refer to the same embodiment, although it may.
Some of the drawings show physical devices. The drawings are not drawn to scale, and the relative dimensions shown in the drawings should not be interpreted as a limitation on the relative dimensions of physical devices. Any references to “up”, “down”, “above”, “below”, or similar directional terms, refer to the orientation as shown in the drawings, and not necessarily to the orientation of an actual physical device with respect to gravity.
Various embodiments of the invention pertain to an EUV detector with a reflective structure disposed on a sensor. The reflective structure permits a small portion of incident EUV energy to be captured and detected by the sensor, while reflecting a substantial portion of the energy to the intended target. One embodiment uses for the reflective structure a layer of material that is reflective at the EUV wavelengths at a grazing incidence angle. Another embodiment uses a multi-layer reflector as the reflective structure.
Coated Detector
FIG. 1 shows a cross section of a detector comprising a sensor coated with a reflective material, according to one embodiment of the invention. The detector 100 may comprise a substrate 110 , a sensor 120 , and a reflective structure in the form of a reflective layer 130 . In one embodiment reflective layer 130 comprises a material that reflects a substantial amount of EUV radiation striking the surface of reflective layer 130 at a shallow angle (e.g., an angle of incidence of less than 20 degrees), while absorbing a sufficient portion of the EUV radiation to be detectable by the sensor 120 .
In one embodiment, sensor 120 may comprise a pyroelectric sensor that detects thermally induced distortion of a crystal lattice at or near the surface of the sensor 120 , and is sensitive to rates of change in temperature. Commercially available pyroelectric sensors may be sensitive to wavelengths from infrared through x-ray, may be able to resolve pulses of less than 1 nanosecond (ns), and may have threshold sensitivities of approximately 0.2 micro joules. In a particular embodiment the sensor 120 is comprised of lithium tantalate and is 1–2 millimeters (mm) across, but other embodiments may use other materials and/or sizes.
The substrate 110 may comprise any suitable substance that provides physical support for the sensor 120 and the reflective layer 130 , and may also provide electrical connections (not shown) to the sensor 120 so that the amount of energy detected by sensor 120 may be converted into usable electrical signals.
In one embodiment the reflective layer 130 has a thickness in the range of approximately 100–200 nanometers (nm), but other embodiments may have other thicknesses. While in one embodiment reflective layer 130 comprises ruthenium, in an alternate embodiment reflective layer 130 may comprise other materials (e.g., gold).
In one embodiment substrate 110 and reflective layer 130 are circular with a diameter of approximately 3 inches, while sensor 120 is circular with a diameter of approximately 1–2 mm, but other embodiments may have other sizes and shapes. (Note: the figures show the various elements in cross section, so that the overall shape of those elements cannot be determined from the figures.)
FIG. 1 also shows a ray of EUV radiation 140 striking reflective layer 130 at an angle of incidence θ 1 , and reflecting off reflective layer 130 as ray 143 at an equal angle of reflection θ 2 , from where the ray 143 may travel to a target area, such as a focusing reflector. The focusing reflector may redirect the ray through a patterning mask to a wafer for lithographic patterning. A portion 145 of the ray may penetrate into the reflective layer 130 , where it may be partially or fully absorbed to create the thermal effects that permit detection. In one embodiment, angle of incidence θ 1 is a grazing angle of approximately 2 degrees, but other grazing angles may also be used.
Although a single ray 140 is shown striking the reflective layer 130 at a single point, this is a simplification that is intended to illustrate the effects of the reflective layer on incoming radiation. In actual usage, many parallel rays 140 may strike throughout a larger portion of the surface area of the reflective layer 130 , including areas not over the sensor 120 .
The surface roughness of the reflective layer 130 may have a significant effect on the amount of light reflected to the target area. Because surface roughness may cause any single point on the surface of reflective layer 130 to vary from the overall plane of that surface, the angle of incidence and angle of reflection may vary from θ 1 and θ 2 at that point, causing reflected ray 143 to be scattered and miss the target area.
FIG. 2 shows a chart of the amount of reflectivity of a ruthenium layer based on surface roughness, according to one embodiment of the invention. The surface roughness may be measured in statistical units of vertical variation, e.g., in this case expressed in nanometers root-mean-squared (nm rms). Surface roughness of the untreated reflective layer 130 (as the layer exists after being deposited but before further treatment) may be improved through various means (e.g., chemical mechanical polishing, magneto-rheological polishing, ion milling, etc.) One embodiment has a surface roughness of between approximately 0.2 nm rms and approximately 2.0 nm rms, but other embodiments may have other values.
In the chart of FIG. 2 , the EUV radiation has a wavelength of 13.5 mn, and the angle of incidence is approximately 15 degrees. Other values for these parameters may produce somewhat different reflectivity.
Incoming radiation that is not reflected or scattered may penetrate into the reflective layer 130 , where it may be absorbed and converted into thermal energy that is conducted into sensor 120 , where the energy is detected. In one embodiment, approximately 16 percent of the incident radiation penetrates into the reflective layer 130 in this manner, but other embodiments may have other percentages.
FIG. 3 shows a flow chart of a process for fabricating a detector, according to one embodiment of the invention. In flow chart 300 , at 310 a pyroelectric sensor is provided. At 320 , a reflective layer is deposited on the sensor. In one embodiment, this deposition is accomplished through sputtering, but other embodiments may use other techniques, such as physical vapor deposition (PVD). In the illustrated example the reflective layer comprises ruthenium, but other embodiments may comprise other materials (e.g., gold, etc.)
At 330 the surface of the reflective layer is planarized to provide a flat reflective surface with very little surface roughness. In one embodiment, this may be accomplished through chemical mechanical polishing (CMP), but other embodiments may use other techniques (e.g., magneto-rheological polishing, ion milling, etc.). In one embodiment, the surface is planarized to a surface roughness of less than 1.0 nm rms, but other embodiments may have a surface roughness outside this range.
At 340 the combined sensor and reflective layer are packaged to provide a suitable structure for mounting and protecting them. At 350 electrical connections are made so that the sensor may be electrically coupled to suitable circuitry for converting the sensor output to usable electrical signals.
Multi-Layer Reflector and Sensor
FIG. 4 shows a cross section of a detector comprising with a multi-layer reflector, according to one embodiment of the invention. In the illustrated detector 400 , substrate 410 provides a base for the remaining materials. Substrate 410 may also comprise other details not shown, such as electrical connections between the remaining layers and other circuitry. In one embodiment the substrate 410 comprises silicon, but other embodiments may use other materials such as ultra low expansion glass, etc. The illustrated embodiment shows a hole through substrate 410 in which sensor 420 is inserted, but other embodiments may use other techniques, for example, fabricating a sensor on and/or in the substrate.
Sensor 420 may comprise material that reacts to electromagnetic radiation in a way that permits the generation of an electrical signal representing the amount of electromagnetic radiation received. In one embodiment sensor 420 comprises a pyroelectric material (e.g., lithium tantalate, lithium niobate, strontium barium niobate, lead zirconate titanate, etc.), but other embodiments may use other types of sensors (e.g., a diode sensor, etc.)
Insulating layer 430 may comprise a material that is essentially electrically non-conductive to provide electrical insulation between the substrate 410 and control layer 440 , and is also optically transmissive (at least at the EUV wavelengths) to convey EUV radiation to sensor 420 from above. In one embodiment, insulating layer 430 comprises silicon dioxide (SiO 2 ), but other embodiments may comprise other materials, such as silicon nitride (Si 3 N 4 ), etc. In one embodiment insulating layer 430 has a thickness of between approximately 50 and approximately 100 nm, but other embodiments may use other thicknesses.
Control layer 440 may be used to controllably reduce the amount of EUV radiation that reaches the sensor 420 , by restricting the area through which the EUV radiation may pass. In one embodiment, control layer 440 is comprised of chromium (Cr) to limit the radiation reaching the detector (at normal incidence, reflection would be minimal). In one embodiment, the control layer 440 has a thickness between approximately 190 and approximately 200 nm. Other embodiments may use other materials and/or other thicknesses.
Control layer 440 may contain a control hole 450 through which a predetermined percent of the electromagnetic radiation received from above may pass through to insulating layer 430 . This technique may be used to keep the expected levels of EUV radiation received by the sensor 420 within the linear region of the sensor and above the noise threshold of the sensor. The insulating layer 430 may absorb some of the EUV radiation that passes through the control hole 450 , which may be accounted for in determining the proper size of the control hole 450 . In one embodiment, a single hole per sensor is used, but other embodiments may use multiple holes per sensor. In various embodiments, the control hole 450 may be cylindrically shaped with a diameter of between approximately 40 nm and approximately 1 mm, but other embodiments may have holes of other shapes and sizes.
In some embodiments, control hole 450 is filled with a filler material to filter out unwanted wavelengths of radiation. In a particular embodiment, the hole is filled with Zirconium (Zr) to filter out infrared, visible and ultra-violet radiation. After filling, the filler material may be planarized to create a smooth surface at the top of the control hole 450 . In one embodiment the control layer 440 and filler material may be planarized in the same operation to present a uniform flat smooth surface for both the control layer material and filler material.
A multi-layer (ML) reflector may be disposed on the control layer. An ML reflector has alternating layers of two different materials with different refractive indices, so that the interface between any two adjacent layers will reflect a portion of incident radiation and allow another portion to pass through the interface. The layers may be spaced so that the reflected radiation from one interface will be substantially in-phase with reflected radiation from the adjacent interface. In the illustrated embodiment alternating layers of a first material 460 and a second material 470 are disposed directly above the control layer 440 to form an ML reflector. In one embodiment, the two materials are comprised of molybdenum (Mo) and silicon (Si), but other embodiments may use other combinations of materials, such as Mo and beryllium (Be).
In FIG. 4 the layers of first material 460 are shown with a different thickness than the layers of second material 470 , but that is only for clarity of illustration. The thickness of each layer may be chosen so that electromagnetic radiation reflected from each layer will be in phase with electromagnetic radiation reflected from higher layers. Thus the thickness of each layer may be determined by the wavelength of electromagnetic radiation being used, the angle of incidence, and the refractive index of the materials being used. In one embodiment the thickness of each layer is between approximately 5 nm and approximately 10 nm, but other embodiments may use other thicknesses.
The number of bilayers (where a bilayer is a layer of the second material directly above and in contact with a layer of the first material) may be selected to achieve the desired percentage of electromagnetic radiation that is to be reflected and/or the percentage that is to reach the control layer. In one embodiment the number of bilayers is between approximately 30 and approximately 60, but other numbers of bilayers may also be used. In a particular embodiment the number of bilayers is approximately 40.
FIG. 5 shows a schematic of the effects of a multi-layer reflector, according to one embodiment of the invention. In the illustrated example, each bilayer (numbered 1 through n, and with a thickness d) has a first material A (with a thickness d A ) and a second material B (with a thickness d B ). The illustrated embodiment has an equal number of layers of material A and material B, but other embodiments may not. The illustrated embodiment shows two different types of layers, but other embodiments may have three or more different types of layers.
FIG. 6 shows an example graph of reflectivity vs. the number of bilayers, according to one embodiment of the invention. The graph is for an embodiment using EUV with a wavelength of approximately 13.5 nm, with bilayers of Mo and Si. As can be seen, beyond a certain number of bilayers (in this example approximately 60), additional bilayers do not contribute significantly to reflectivity, but might reduce the amount of energy reaching the detector.
FIG. 7 shows a flow chart of a method of fabricating a detector, according to one embodiment of the invention. FIGS. 8A through 8I show a cross section of elements of a detector during fabrication, according to one embodiment of the invention. The following description discusses elements of FIG. 7 (labeled 7 xx ) and elements of FIG. 8A through 8I (labeled 8 xx ) together. However, it is understood that the embodiment of FIG. 7 and the embodiment of FIGS. 8A through 8I may also be practiced separately.
The process may begin with a substrate 810 . At 710 a hole is created in the substrate and a sensor 815 is mounted in the hole. The hole may be created by various techniques, such as machining, laser drilling, etc. Various types of sensors may be used, such as diode sensors, pyroelectric sensors, etc. Alternately, a sensor may be fabricated on the substrate as a part of the fabrication process. At 720 an insulating layer 820 is placed on the substrate 810 . The insulating layer 820 may be comprised of various materials (e.g., silicon dioxide, silicon nitride, etc.) In one embodiment, chemical vapor deposition (CVD) is used to create the insulating layer, but other techniques may also be used (e.g., sputtering, thermally growing an insulating layer, etc.).
At 725 a control layer 830 is deposited on the insulating layer 820 . The control layer may be comprised of material that prevents transmission of radiation to the sensor. One embodiment uses chromium for the control layer 830 , but other embodiments may use other materials. Various techniques may be used to deposit the control layer 830 , e.g., physical vapor deposition (PVD), sputtering, etc. At 730 a control hole 835 is created in the control layer. The control hole 835 may be sized to control the percentage of radiation striking the control layer that is passed through to the insulating layer 820 and ultimately to the sensor 815 . In one embodiment the control hole is formed through lithographic patterning, but other embodiments may use other techniques (e.g., laser micromachining, e-beam writer, etc.). Although a single control hole 835 is shown, other embodiments may have multiple control holes above the sensor.
At 735 the control hole 835 is filled with a filler material 840 . One embodiment uses Zirconium as a filler material, but other embodiments may use other materials. In the illustrated embodiment, the filler material 840 is deposited on the control layer 830 through any of various techniques (e.g., sputtering), filling the control hole 835 and coating the surface of the control layer 830 , and the excess filler material 840 is then removed at 740 so that the filler material 840 remains only in the control hole 835 . At 740 the surface is planarized to create a smooth, planar surface upon which the remaining layers may be placed. In one embodiment, CMP is used to both remove the excess filler material 840 and to planarize the surface. Other techniques may also be used, for example magneto-rheological polishing, ion milling, etc.
A multi-layer reflector may then be fabricated by depositing alternating layers of a first reflective material 850 (as indicated at 745 ) and a second reflective material 860 (as indicated at 750 ). At 755 this process is repeated as many times as necessary to get the required number of alternating layers in the multi-layer reflector. The materials may be chosen with different refractive indices at the chosen wavelength, so that the interface between each pair of adjacent layers will reflect a first known portion of incident light and allow a second known portion of the incident light to pass through into the next layer. In one embodiment the two materials 850 , 860 are molybdenum and silicon, but other embodiments may use other pairs of materials (e.g., Mo and Be, etc.). In one embodiment the two materials 850 , 860 are deposited using magnatron sputtering, but other embodiments may use other techniques (e.g., ion beam coater, etc.).
In one embodiment the final layer is planarized at 760 to provide a smooth planar surface for the multi-layer reflector, but other embodiments may skip this operation. At 765 electrical connections 805 are made to the sensor 815 so that the final detector may be placed into service.
FIG. 9 shows portions of an EUV lithography system, according to one embodiment of the invention. System 900 may include a source 910 of EUV radiation, a reflective apparatus 920 coupled to a sensor 925 , a focusing reflector 930 , a mask 940 , and a target device 950 . In the illustrated system, the source 910 provides EUV radiation traveling in a parallel beam and striking reflective apparatus 920 at an angle. The angles shown in FIG. 9 are for clarity of illustration and may not be the angles used in an actual system.
In one embodiment reflective apparatus 920 comprises a layer of material (e.g., ruthenium, gold, etc.) that reflects a major portion of the incident EUV radiation to focusing reflector 930 , while absorbing a smaller portion of the incident EUV radiation and converting the absorbed EUV radiation to thermal energy that may be detected by sensor 925 , thus permitting the strength of the incident EUV radiation to be measured. In a particular embodiment the angle of incidence between the EUV radiation and the layer of material is less than approximately 20 degrees, but other embodiments may have other angles.
In another embodiment reflective apparatus 920 comprises a multi-layer reflector that reflects a major portion of the incident EUV radiation to focusing reflector 930 , while permitting a smaller portion of the incident EUV radiation to pass through to sensor 925 , thus permitting the strength of the incident EUV radiation to be measured. In a particular embodiment the angle of incidence between the EUV radiation and the multi-layer reflector is greater than approximately 45 degrees, but other embodiments may have other angles
Focusing reflector 930 may be used to reflect and focus the EUV radiation received from reflective apparatus 920 in a path that will take the EUV radiation to a target area. The focusing reflector 930 may have a curved and very smooth surface so as to focus the EUV radiation accurately at the surface of target 950 . In one embodiment target 950 is a wafer being fabricated to create integrated circuits. Reflective mask 940 may be used to create the pattern being focused on the target 950 . In one embodiment the reflective mask 940 comprises a pattern of material that is essentially non-reflective to EUV radiation, disposed on the surface of a material that is essentially reflective to EUV radiation. In another embodiment a reflective material may be disposed on a non-reflective surface. In either embodiment the pattern of material on the mask 940 determines the pattern of radiation that reaches the target 950 . In some embodiments the pattern of EUV radiation that reaches the target 950 is a reduced-size version of the pattern on mask 940 .
Although the illustrated embodiment shows the elements of system 900 in a particular order, other embodiments may have the elements arranged in a different order (e.g., focusing reflector 930 might be disposed in the optical path between source 910 and reflector 920 , focusing reflector 930 might be disposed in the optical path between mask 940 and target 950 , etc.)
The foregoing description is intended to be illustrative and not limiting. Variations will occur to those of skill in the art. Those variations are intended to be included in the various embodiments of the invention, which are limited only by the spirit and scope of the appended claims. | A detector for extreme ultraviolet (EUV) energy uses incidence reflectance of the EUV beam off the detector to both capture a small but controllable fraction of the EUV energy and to redirect most of the energy to its target. In one embodiment, a reflective coating of material on a sensor surface is used. In another embodiment, a multi-layer reflector on a sensor is used. A method of making the multi-layer reflector/sensor is also described. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The field of invention relates to fluid pump structure, and more particularly pertains to a new and improved fluid pump apparatus arranged to provide for variable facing displacement of pump gears relative to one another to control volumetric flow through the pump structure.
2. Description of the Prior Art
Fluid pumps of various types have been utilized throughout the prior art such as exemplified in the U.S. Pat. Nos. 4,934,913; 4,830,952; 4,898,525; 5,062,776; and 5,076,770.
The instant invention attempts to direct the use of a pump structure providing for axial displacement of pump gears to vary the facing relationship of the pump gears relative to one another in a cooperating manner and thereby alter and vary volumetric flow through the associated pump and in this respect, the present invention substantially fulfills this need.
SUMMARY OF THE INVENTION
In view of the foregoing disadvantages inherent in the known types of fluid pump apparatus now present in the prior art, the present invention provides a fluid pump apparatus wherein the same is directed to permit axial displacement and associated engagement of confronting fluid pump gears relative to one another. As such, the general purpose of the present invention, which will be described subsequently in greater detail, it to provide a new and improved fluid pump apparatus which has all the advantages of the prior art fluid pump apparatus and none of the disadvantages.
To attain this, the present invention provides a fluid pump arranged to employ cooperating gears that are arranged for axial displacement relative to one another, whereupon a volumetric chamber positioned between a surrounding housing and one of a plurality of inter-nesting first and second cylindrical housings permits displacement of the first and second cylindrical housing towards one another that in turn effects axial displacement of the gears relative to one another to control inter-engagement and associated volumetric displacement relative to the gear structure.
My invention resides not in any one of these features per se, but rather in the particular combination of all of them herein disclosed and claimed and it is distinguished from the prior art in this particular combination of all of its structures for the functions specified.
There has thus been outlined, rather broadly, the more important features of the invention in order that the detailed description thereof that follows may be better understood, and in order that the present contribution to the art may be better appreciated. There are, of course, additional features of the invention that will be described hereinafter and which will form the subject matter of the claims appended hereto. Those skilled in the art will appreciated that the conception, upon which this disclosure is based, may readily be utilized as a basis for the designing of other structures, methods and systems for carrying out the several purposes of the present invention. It is important, therefore, that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention.
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.
It is therefore an object of the present invention to provide a new and improved fluid pump apparatus which has all the advantages of the prior art fluid pump apparatus and none of the disadvantages.
It is another object of the present invention to provide a new and improved fluid pump apparatus which may be easily and efficiently manufactured and marketed.
It is a further object of the present invention to provide a new and improved fluid pump apparatus which is of a durable and reliable construction.
An even further object of the present invention is to provide a new and improved fluid pump apparatus which is susceptible of a low cost of manufacture with regard to both materials and labor, and which accordingly is then susceptible of low prices of sale to the consuming public, thereby making such fluid pump apparatus economically available to the buying public.
Still yet another object of the present invention is to provide a new and improved fluid pump apparatus which provides in the apparatuses and methods of the prior art some of the advantages thereof, while simultaneously overcoming some of the disadvantages normally associated therewith.
These together with other objects of the invention, along with the various features of novelty which characterize the invention, are pointed out with particularity in the claims annexed to and forming a part of this 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 amd descriptive matter in which there is illustrated preferred embodiments of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein:
FIG. 1 is an isometric illustration of the invention.
FIG. 2 is an orthographic view, taken along the lines 2--2 of FIG. 1 in the direction indicated by the arrows.
FIG. 3 is an isometric illustration of the second cylindrical housing mounting the first shield and the second pump gear.
FIG. 4 is an orthographic view, taken along the lines 4--4 of FIG. 3 in the direction indicated by the arrows.
FIG. 5 is an orthographic view, taken along the lines 5--5 of FIG. 2 in the direction indicated by the arrows.
FIG. 6 is an isometric illustration of an individual pump gear of the invention.
FIG. 7 is an isometric illustration of a typical shield structure as employed by the invention.
FIG. 8 is an isometric illustration of a tubular sleeve complementarily receiving the gear in cooperating engagement with the gear ribs therewithin.
DESCRIPTION OF THE PREFERRED EMBODIMENT
With reference now to the drawings, and in particular to FIGS. 1 to 8 thereof, a new and improved fluid pump apparatus embodying the principles and concepts of the present invention and generally designated by the reference numeral 10 will be described.
More specifically, the fluid pump apparatus 10 of the instant invention essentially comprises a primary cylindrical housing symmetrically oriented about an axis 11a, having a cylindrical side wall 11 and a first end wall 12 spaced from and parallel a second end wall 13. A fluid means is provided to include a hydraulic pressure conduit 14 is directed into the first end wall 12, wherein a fluid pressure source 15 such as a pump or a bleed-off from an outlet conduit 18 of the apparatus 10 directed through the side wall 11 is provided in communication with a valve 16 directing fluid into the hydraulic pressure conduit 14. An inlet conduit 17 is directed into the cylindrical side wall 11 diametrically opposed through the cylindrical side wall 11 relative to the outlet conduit 18.
Respective first and second cylindrical housings 19 and 21 are reciprocatably mounted and coaxially aligned along the axis 11a arranged for telescoping reception relative towards one another. The first housing includes a first housing first end wall 20 spaced from and parallel a first housing second end wall 20a, wherein the second housing 21 includes a second housing first end wall 22 spaced from and parallel a second housing second end wall 22a. A second housing slot 23 is directed into the second housing (see FIG. 3), wherein a similar such slot such as a first housing slot 24 is directed into the first housing 19. A first C-shaped shield 29 is fixedly mounted to the second housing at the second housing second end wall 22a and received within a first housing C-shaped cavity 19a directed into the first housing second end wall 20a. Similarly, a second C-shaped shield 30 fixedly mounted to the first housing 19 and more specifically to the first housing second end wall 20a is received within a second housing C-shaped cavity 21a directed into the second housing 21 through the second housing second end wall 22a. The C-shaped configuration is indicated in FIG. 3 relative to the second housing, wherein it is understood that the complementarily configured first housing is provided with a like C-shaped housing cavity to receive the first C-shaped shield 29. The first and second slots 24 and 23 are arranged to receive the respective second and first ribs 32 and 31 of the first and second respective C-shaped shields 29 and 30. Respective first and second housing cylindrical cavities 25 and 26 each parallel and offset relative to the axis 11a are directed into the respective first and second housings 19 and 21 respectively into the respective first and second housing second end walls 20a and 22a respectively. The first and second cylindrical cavities 25 and 26 rotatably receive first and second tubular sleeves 27 and 28 having respective first and second parallel gear ribs 27a and 28a directed within the tubular sleeves to complementarily receive the respective second and first pump gears 35 and 37. The first and second pump gears 35 and 37 include respective second and first pump gear shafts 36 and 38 that rotatably project through the respective second and first housings and through the respective second and first end walls 12 and 13. The second and first pump gear shafts 36 and 38 are arranged for rotary displacement, and wherein at least the first pump gear shaft 38 is mounted in operative communication to a suitable drive means. The second gear pump shaft 36 may be employed in a manner to effect input to a suitable control means such as a speed vs. time controller and the like. Further, as indicated in FIG. 5 for example, respective first and second gaps 33 and 34 are oriented between the respective first and second C-shaped shields 29 and 30 in adjacency to the respective inlet and outlet conduits 17 and 18, wherein the shield structure provides for pressurized displacement of fluid from the inlet conduit 17 directed through the outlet conduit 18 in a pressurized manner. The surface engagement of the respective second and first pump gear shafts 35 and 37 is effected through the fluid and volumetric filling of the fluid control chamber 39 (see FIG. 5) receiving fluid through the hydraulic pressure conduit 14 and oriented between the first end wall 12 of the primary cylindrical housing and the second housing first end wall 22.
Accordingly, axial displacement and engagement of the pump gears 35 and 37 permits volumetric control of fluid directed through the apparatus in a variable manner.
As to the manner of usage and operation of the instant invention, the same should be apparent from the above disclosure, and accordingly no further discussion relative to the manner of usage and operation of the instant invention shall be provided.
With respect to the above description then, it is to be realized that the optimum dimensional relationships for the parts of the invention, to include variations in size, materials, shape, form, function and manner of operation, assembly and use, are deemed readily apparent and obvious to one skilled in the art, and all equivalent relationships to those illustrated in the drawings and described in the specification are intended to be encompassed by the present invention.
Therefore, the foregoing is considered as illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly, all suitable modifications and equivalents may be restored to, falling within the scope of the invention. | A fluid pump is arranged to employ cooperating gears that are arranged for axial displacement relative to one another, whereupon a volumetric chamber positioned between a surrounding housing and one of a plurality of inter-nesting first and second cylindrical housings permits displacement of the first and second cylindrical housings towards one another that in turn effects axial displacement of the gears relative to one another to control inter-engagement and associated volumetric displacement relative to the gear structure. | 5 |
BACKGROUND OF THE INVENTION
The invention relates to a water-steam cooled cyclone separator and, more particularly, to the fabrication of a roof for such a cyclone separator, where the roof is to be fabricated separately from the remainder of the cyclone separator.
Water-steam cooled cyclone separators are known. An example is shown and described in U.S. Pat. No. 4,904,286 of Magol et al., the disclosure of which is incorporated by reference.
For ease of fabrication and shipping, it is desirable to fabricate the roof of the cyclone separator separate from the remainder of the cyclone separator. The roof alone may weigh between four and seven tons and have a diameter of fifteen to twenty feet. Despite its great size and weight, the roof must be fabricated to close tolerances so that the individual tubes of which it is composed can be mated on site to the barrel portion of the cyclone. Adding to the difficulty is that significant internal stresses are present that tend to warp the structure as it is being made. These stresses arise from the welding operations that occur in welding the tubes to the header of the cyclone and in welding fin material and the like to the tubes in order to form gas-tight surfaces. This effect even further adds to the difficulty of fabricating a cyclone roof.
SUMMARY OF THE INVENTION
It is therefore an object of the current invention to allow the economic assembly of parts of a massive roof unit to close tolerances.
It is a further object of the current invention to allow the construction of a welded cyclone roof and to maintain tolerances through the step of addressing the problem of distortion that otherwise would result from welding.
It is a still further object of the current invention to provide for the fabrication and delivery of a welded cyclone roof that can be transported and that will mate to a cyclone barrel after transportation.
It is still a further object of the current invention to provide a welding fixture and method of assembly of a cyclone roof to provide for trouble-free welding and welds of higher quality.
Toward the fulfillment of these and other objects, the current invention provides a method of fabricating a roof for a water-steam cooled cyclonic separator of the type having a water-wall formed of coolant conduits disposed below a header, the method achieving predetermined dimensional tolerance and comprising the steps of: providing a header member configured to form at least a portion of the header tank and having formed therein a plurality of coolant exit openings; providing a plurality of tubing members configured to cooperate with the header member to form a roof member of a water-cooled cyclonic separator; supporting the header member; supporting a plurality of the tubing members in fluid communication with respective ones of the coolant exit openings of the header member so as to create first ends of the coolant conduits; supporting a plurality of the tubing members with ends thereof disposed at the bottom of the roof member so as to form second ends of the coolant conduits; locating the second ends of the coolant conduits in fixed and predetermined locations with respect to the respective coolant exit openings of the header member and with respect to each other, said fixed and pre-determined locations being within pre-determined dimensional tolerance for the completed roof; restraining the second ends in said fixed and pre-determined locations; during said restraining, performing welding operations on the header member and the tubing members to form a roof member; and during said restraining, heating the roof member to a temperature and for a duration that are effective to achieve stress relief of the roof member.
Another aspect of the invention pertains to apparatus for making a roof for a water-steam cooled cyclonic separator of the type having a water-wall formed of coolant conduits disposed below a header tank, the apparatus comprising: a frame of a composition capable of withstanding the temperatures of a stress relief operation, the frame comprising a platform and means for supporting the platform above a floor, the platform being formed of members disposed substantially in a plane and having an extent at least sufficient to accommodate a roof member; header member support means fixed with respect to the frame for supporting a header member; tubing support means for supporting a plurality of tubing members in predetermined relation to the header member; and restraining means for positioning the ends of tubing members to predetermined dimensional tolerances and for effectively maintaining said predetermined dimensional tolerances through welding and stress relief operations.
BRIEF DESCRIPTION OF THE DRAWINGS
The above brief description as well as further objects, features and advantages of the present invention will be more fully appreciated by reference to the following detailed description of presently preferred but nonetheless illustrative embodiments in accord with the present invention when taken in conjunction with the accompanying drawings wherein:
FIG. 1 is a partially broken-away perspective of a cyclone roof of a type that may be manufactured according to the current invention;
FIG. 2 is a top view of a universal welding fixture according to the current invention;
FIG. 3 is an elevation taken along line 3--3 of FIG. 2 with the addition of associated support hardware configured according to the individual cyclone roof being manufactured;
FIG. 4 is an elevation of a header of a cyclone roof illustrating a step in a method according to the current invention;
FIG. 5 is an enlargement of a portion of a fixture according to the current invention, also showing in phantom a portion of a roof member during a stage of fabrication according to the current invention;
FIG. 6 is a plan view of a unit of a lacing plate;
FIG. 7 is a perspective of a cyclone roof in a fixture according to the current invention, illustrating a further stage of fabrication;
FIG. 8 is a perspective of the fixture and cyclone roof in a still further stage of fabrication;
FIG. 9 is an enlargement of a portion of FIG. 8 and
FIG. 10 is a schematic illustration of one half of the assembled cyclone is of and fixture in a heat treating furnace.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 is a partially broken-away perspective of a cyclone roof 10 of a type that may be made using the current invention. It is illustrative only, and many of the broad principles of the current invention may be used in making other forms of water-steam cooled cyclone roofs.
Water-steam cooled cyclones per se are known. Typically they include a cyclone entrance portion and an exit opening for separated gases. Accordingly, the roof 10 includes an entrance portion 12 and an exit opening 14 into which will be disposed a solid exit tube or other apparatus having a diameter substantially equivalent to the diameter of the exit opening 14.
The cyclone roof comprises a water-wall formed of a plurality of coolant conduits, preferably in the form of lengths of continuous tubing members 16 bent to the desired shape of the particular cyclone roof. In the illustrated embodiment, a typical tubing member 16 defines a lower end 18 which also is the lower end of its coolant conduit, a vertical run 20, a lower run 22, a knuckle 24, an upper run 26, and an upper end 28. Those tubing members 16 that define the cyclone entrance portion 12 have somewhat different shapes, as shown in FIGS. 1 and 7.
The upper end 28 of each tubing member 16 is in fluid communication with a header 30.
The roof as shown in FIG. 1 has been shipped to the site of its intended use in the form of four separate roof members 31, as suggested by the welds 33. It is an object of the current invention to provide for the fabrication of roof members 31 so as to provide for the best available fit of the roof members 31 when they arrive on site, both with other roof members 31 and with the underlying cyclone barrel assembly. For example, tolerance of the diameter of a fabricated roof has successfully been held to less than one-eighth inch.
The number of roof members 31 is a matter of choice and typically will depend on such factors as the size of the cyclone and shipping constraints. An alternative typical roof 10 might comprise six roof members 31, each extending through an arc of sixty degrees.
A completed roof member 31 typically will comprise a header member 32, a number of associated tubing members 16 welded to header member 32, a number of tension links 36 (FIG. 9) to be discussed later, fin material welded between the tubing members along the vertical runs 20 and lower runs 22 in order to form a gas-tight seal. Where needed some small bars or the like may be welded between the tubes along the knuckles 24, where the tubes are nearly tangent, and further, a non-gas-tight seal of optional design disposed along the upper runs 26, which is an area of the roof not exposed to combustion gases.
FIG. 2 is a top view of a universal fixture 100 according to the current invention. The fixture 100 comprises first frame 102 and second frame 104 held together along line 3--3 by removable bolts 106 or the like. Each frame 102, 104 comprises a platform made of platform members 108 and frame legs 110 (FIG. 3) for rigidly mounting the platform above a floor 109 or other work surface so that the various assembly operations may be carried out.
Each frame 102, 104 is made of a geometry and composition capable of withstanding the weight of the cyclone roof and the temperatures of a stress relief operation to be described later. In the illustrated embodiment, the platform members 108 are made of metallic I-beams.
In the illustrated embodiment, the fixture 100 is more than twenty-six feet across. It measures about ten feet from the floor to the top of the legs 110.
As seen in FIG. 3, the upper surfaces of the platform members 108 collectively define a platform reference surface 111 that serves as an initial reference point for the location of subsequently added hardware and roof members. The fixture as shown in elevation in FIG. 3 is in an intermediate stage of being modified for the construction of a specific cyclone roof by the addition of saddles 116 and adapter beams 114, in numbers and locations determined in accord with the particular cyclone roof to be constructed.
Referring back to FIG. 2, the future locations of the saddles 116 are indicated by the symbols "S," and the future locations of the adapter beams 114 are indicated by the symbols "B." Because the fixture 110 is a universal fixture, it is adapted to accommodate a variety of locations of the saddles and adapter beams.
In particular, a number of the platform members 108 extend radially from a line 113 (FIGS. 2 and 5) that will form the longitudinal center line of the cyclone roof. In this manner, they provide for location of the saddles 116 and adapter beams 114 at any radial distances. This means that cyclone roofs of any diameter may be manufactured.
Furthermore, a number of mounting plates 112 have been welded to the platform. These plates 112 may extend any desired distance laterally of the members 108. They serve further to increase the number of locations where the saddles 116 and adapter beams 114 may be mounted on the platform. In this way, the mounting plates 112 further increase the universality of the fixture 100.
The saddles 116 are welded to the frames and serve as means for supporting the header members in a pre-determined and fixed relationship with respect to the frame. The current invention is not limited to saddles such as those illustrated. Any apparatus capable of performing the function would be acceptable.
It may be seen from FIG. 3 that the heights of the adapter beams 114 above the platform reference surface 111 is not as great as the heights of the tops of the legs 110. Accordingly, when the fixture 100 is later inverted as shown in FIGS. 8 and 9 for purposes to be described below, the adapter beams 114 will not extend completely to the floor.
FIG. 5 illustrates in phantom a header member 32 and a single tubing member 16 configured to cooperate with other tubing members 16 to form a roof member 31 Also shown in FIG. 5, in solid line, is certain additional hardware that is welded to the universal fixture in locations that are determined by the geometry of the particular roof member being constructed.
In particular, a lacing plate 120 is welded to a lacing plate support 128, one of which, in turn, is welded to each of the adapter beams 114. The lacing plate 120 is a template mounted in a fixed and pre-determined location with respect to the frame. It cooperates with the lower ends 18 of the tubing members in a manner to be described.
In the illustrated embodiment, the template is essentially a metallic arc extending in a circumferential direction around the periphery of what will be the lower portion of the roof. FIG. 6 illustrates a single unit 122 of an embodiment of a lacing plate having holes 124 for individually receiving the lower ends 18 of the tubes 16. As shown in FIG. 7, a series of lacing plate units 122 are welded in place to define the entire lower portion of the cyclone roof.
Also shown in FIG. 5 is a lower run support ring 130 for the lower run 22. Lower run support ring 130 is seen in cross-section and is a metallic ring extending circumferentially of the roof member. The lower run support ring 130 is held in a fixed and pre-determined location by supports 132 welded to the adapter beams 114.
Not only does the lower run support ring 130 serve to provide general support to the tubing member 16, but more specifically it supports the center line of the lower run 22 at a fixed and pre-determined elevation above the reference surface 111. In a similar and analogous fashion, FIG. 5 shows an upper run support ring 134 that performs the same function for the upper run 26.
The support rings 130, 134 need not necessarily be arcuate or continuous. However, the illustrated structure is a convenient one. It might be possible to eliminate one or both of the support rings 130, 134, for example if a cyclone roof 10 having a different geometry were to be fabricated.
It may be seen from FIG. 5 that the supports 128, 132 may be welded to the adapter beams 114 at any elevation. Similarly, the lacing plate 120 and support rings 130, 134 may be disposed at substantially any appropriate radial distance from the roof center line. These capabilities further add to the universality of a fixture according to the current invention.
A method of making a water-steam cooled cyclone roof assembly according to the current invention will now be described.
The initial condition of the fixture 100 is such that the first frame 102 and second frame 104 are held together as shown in FIG. 2 and disposed in an upright configuration as shown in FIG. 3. The saddles 116 and adapter beams 114 are welded to the frames according to the geometry of the particular cyclone roof to be manufactured. In similar fashion the lacing plate 120 and support rings 130, 134 are welded in their appropriate locations according to the geometry of the particular roof to be manufactured, the elevations of the lacing plate 120 and lower run support ring 130 being determined by the locations at which their respective supports 128, 132 are welded to the adapter beams 114. The above-described operations establish known pre-determined dimensional relationships among the platform reference surface 111, saddles 116, lacing plate 120, and upper and lower run supports 130, 134.
As shown in FIG. 4, a complete header 30 is assembled externally of the fixture 100 and temporarily held together along field joints 38. Any appropriate means may be used to hold together the header members 32. In the illustrated embodiment, field joint flanges 42 are welded to the header members 32 and joined by threaded tie rods 40.
Also visible in FIG. 4 are a plurality of coolant exit openings 34 to which the individual tubing members 16 will be welded. It is desirable for the openings 34 to be surrounded by recesses that are larger than the outside diameters of the tubes 16 in order to provide for effective tack welding and final welding, to be described below.
The header 30, temporarily held together by the tie rods 40 or the like, is placed in the saddles 116. The coolant exit openings 34 are carefully aligned with respect to the elements of the lacing plate 120. As best seen in FIG. 5, the header 30 is then secured in place by U-tie rods 136 or the like, which may be threadedly secured to the saddles 116 in a known manner.
Then, the individual tubes are installed by introducing their ends 18 individually to the lacing plate 120 and, as necessary, supporting their upper and lower runs on supports 130, 134. With the upper ends 28 of the tubes mounted to the coolant exit openings 34 of the header members 32, a tack weld is made to join each tube to its header member.
The above-described process defines what will be the lower portion of the cyclone roof and further serves to locate the tubes in fixed and pre-determined locations with respect to the coolant exit openings of the header member. In this manner, the geometry of the roof is established.
The lacing plate cooperates individually with each tube 16 to establish its location. Any apparatus capable of performing that function, and the restraint function to be described later, would be an acceptable substitute for the embodiment shown and described.
From the initial condition described above, the necessary welding operations to create a particular cyclone roof member may be carried out in any desired order and orientation. What follows is a description of the welding operations presently preferred in manufacturing a cyclone roof member of the type shown and described.
With the fixture 100 oriented in the upright configuration shown in FIGS. 3 and 5, and with the header members 32 and tubes 16 in-place and tack-welded to the header members, fin material and bars are installed and tacked, as needed, along the vertical run 20, lower run 22, and knuckle 24. This operation is carried out along surfaces that are facing either upwardly or oriented vertically with respect to FIG. 5. Accordingly, all welding may be accomplished in the "down hand" orientation, which allows for the highest quality welds to be produced and for the welding to proceed most quickly. The fixture affords good access to the various elements of the roofing member.
It is preferred for every other fin space to be welded initially, except for the knuckle. Then, a check for shrinkage may be made and certain welds may be broken and re-tacked as necessary. Adjoining tubes 16 disposed in locations corresponding to the header field joints 38 remain unwelded. The unwelded tubes define the opposite ends of the roof members 31.
Then, the fixture is attached to a crane or the like, for example by making shackle attachments to lifting lugs disposed on the tops of the legs and on the sides of the platform members 108. The fixture is tilted through ninety degrees so that the longitudinal axis 113 of the roof is correspondingly tilted by ninety degrees, and the fixture rests on the floor 109 along lengths of two of its legs as shown in FIG. 7. In this orientation, knuckle welding may occur from inside the cyclone exit opening 14. It is desirable to knuckle weld every other space, to re-set as necessary based on shrinkage, and then to weld the remaining knuckle spaces. Also in this orientation, the upper ends 28 of the tubes are completely welded to the header members 32.
It is desirable to perform these knuckle and header welding steps in the above-mentioned "down hand" orientation. Accordingly, the roof may be rotated about its longitudinal center line by successively resting the fixture 100 on various pairs of its legs. Again, the design of the fixture 100 provides for good access to the header members 32 in order to weld the tubes to them.
Finally, the fixture is moved to its inverted orientation as shown in FIGS. 8 and 9 for the final welding steps With the fixture inverted, the back sides of the fin material and tubes are disposed close to the floor, as shown, and may be welded quite easily in the "down hand" orientation. Also at this time, the above-mentioned tension links 36 may conveniently be welded between the header members 34 and the bends of the tubing where the vertical run 20 meets the lower run 22. At this stage a kinetically-formed plate or the like (not shown) may be welded to the upper runs 26 to form a non-gas-tight cover.
If desired, the above-described welding steps may be carried out in a different sequence However, during all of the welding steps, the fixture and its associated elements, notably including the saddles 116 and lacing plate 120, have kept the elements of the roof members 32 in place and, in particular, have restrained them from undergoing the warpage that otherwise would result from the stresses that arise during the welding operations. More particularly, the roof members are held to the desired final tolerances during the welding operations.
As a result of the above-described restraint, the roof members will be under internal stress following the welding operations. In order to relieve such stress, the fixture 100 is separated into its halves by the removal of bolts 106. Then, the first frame 102 and second frame 104 are sequentially introduced into an appropriate furnace 138 as illustrated schematically in FIG. 10. The roof members are heated to a temperature and for a duration necessary to accomplish the desired stress relief. By separating the fixture 100 into two halves, one is a able to accomplish the stress relief step by using a reasonably-sized existing furnace 138.
During the stress relief operation, the tubes 16 and header members 32 are again supported and restrained in the upright configuration as shown in FIG. 5 so that, upon cooling, the roof member is substantially stress-free and within the desired dimensional tolerance of the final product.
In order to protect the frames 102, 104 against themselves sagging during the stress relief operation, legs 118 (FIG. 3) may be added to support the platform members 108.
After the stress relief operation, the roof members 32 are complete. They may be removed from the first and second frames 102, 104 and mated to appropriate fixtures designed to support them during shipping and to accommodate the shipping mode selected.
A latitude of modification, change and substitution is intended in the foregoing disclosure and in some instances some features of the invention will be employed without a corresponding use of other features. Accordingly, it is appropriate that the appended claims be construed broadly and in a manner consistent with the scope of the invention therein. | Method and apparatus for making a roof of a water-steam cooled cyclonic separator. The fixture locates, supports, and restrains portions of the roof during welding operations. By continuing that restraint through a stress relief step, the method and apparatus address the problem of distortion that otherwise would occur during welding. The method and fixture provide good access to the roof during the welding operations and, in particular, allow for faster welding and welds of higher quality by maximizing the availability of "down hand" welding techniques. The fixture is a universal fixture, designed to accommodate roofs of varying geometries. | 8 |
This is a continuation of application Ser. No. 803,473 filed June 6, 1977.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to circuits for use in recording and playback system and, more particularly, to semiconductor amplifier circuits designed for use in magnetic tape recording and playback systems.
2. Description of the Prior Art
In the past, it was generally necessary among other things to change from the recording to the playback mode and vice versa by interchanging the input and output terminals of the amplifier. Typically, a six pole double throw switch was required to change;
(a) The input to the preamplifier.
(b) Preamplifier equalization.
(c) The input to the volume control for setting the loud speaker level to a predetermined level to the recording head,
(d) The Automatic Audio Level Control (ALC) (on or off),
(e) The output drive (to the loud speaker amplifier) switched to the recorder head,
(f) The bias oscillator (on or off).
This complicated switching mechanism of prior art record/playback systems has created mechanical and electrical problems.
The voltage gain of an amplifier designed for tape recording and playback is generally between 1000 and 100,000 times. Because of this high gain, there is a necessity for isolating the input and output circuitry of a high gain amplifier to avoid feedback or regeneration which has always presented a design difficulty and was a potential source of electrical or mechanical failure in tape recorders.
As the state of the art in tape recorder system design advanced through the usage of transistors and other miniature components, a point was reached where the prior art playback/record switch mechanism became larger than the amplifier electronics and thus represented a substantial part of the complexity and cost of the recorder system.
It was recognized quite early that the stability of record/playback switching could be improved by grounding the movable elements of the transfer switch (see U.S. Pat. Nos. 2,971,063 to Genning, issued Feb. 7, 1961 and 3,360,615 to Knockenhauer et al. issued Dec. 26, 1967). Electronic switching has also been previously suggested as a desirable alternative to mechanical and electro-mechanical switching arrangements for use in playback/record (P/R) systems (see U.S. Pat. No. 2,853,559 to Leonard, issued Sept. 23, 1958.). However, this prior art patent used a balanced bridge and bulky iron cored components which were costly and sensitive to hum pickup.
Thus, a need existed to provide a single semiconductor chip that would have a simple, reliable P/R switching feature plus other important features such as, for example, a wide range automatic controller of the recording level and an improved metering circuit which assists the operator in preventing tape overload. Voltage regulation circuits to isolate the active electronic circuit portions from the effects of supply voltage and temperature changes were also needed.
SUMMARY OF THE INVENTION
Accordingly, it is an object of this invention to provide an improved, virtually silent, electronic switching circuit to permit changeover from the record to the playback mode of a recording system.
It is another object of this invention to provide an integrated circuit which has an improved, automatic audio level control (ALC) function for use in a recording system.
It is a further object of this invention to provide an improved output meter driving circuit.
It is a still further object of this invention to provide improved voltage regulation circuit functions to assist in isolation of the various other circuit functions and to reduce the effects of supply voltage and temperature changes.
DESCRIPTION OF THE PREFERRED EMBODIMENT
One embodiment of this invention is an integrated circuit which comprises three amplifier blocks, a P/R integrated logic block which is controllable externally according to the D.C. level at the logic input pin, a meter drive block, and an automatic level control (ALC) block.
In accordance with the embodiment of this invention, a playback/record system is described which comprises an integrated circuit containing playback amplifier means for playing back previously recorded material. The circuit also contains recording means for recording material. Furthermore, the circuit includes switching means for selecting between a playback and record mode of operation.
Additionally the circuit includes logic means connected to the switching means for selectively operating one of the playback amplifier means and the recording amplifier means. The logic means comprises first transistor device means for operating the playback amplifier means, second transistor device means for operating the recording amplifier means, and third transistor device means for selecting between the first and the second transistor means. This embodiment is incorporated in a monolithic silicon chip and preferably encased in a 20 pin DIP.
The foregoing and other objects, features and advantages of the invention will be apparent from the following more specific description of circuit functions covering preferred embodiments as illustrated in the accompanying drawings.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is a block diagram and partial schematic of a recorder/playback system in accordance with one embodiment of this invention.
FIGS. 2A, 2B, 2C and 2D are four parts of a single detailed electrical schematic of the recorder/playback system of FIG. 1 without the external components thereof.
FIG. 1 shows in block and partial schematic form, an IC playback/record system which can be used in a single channel tape recorder. If AC tape head bias is desired, an external bias oscillator, generally referred to as reference numeral 21, is used. Reference numbers 17 through 24 of FIG. 1 also show other external components required to facilitate operation of the chips which are described below. Reference numeral 10, of FIG. 1, is a Source or Recording Amplifier which is a high gain two stage preamplifier suitable for receiving input signals from a dynamic or ceramic microphone Mic. Input 20 or from some other signal source which the user may wish to record.
Reference numeral 12 of FIG. 1 is a Playback Amplifier which is a medium gain preamplifier that amplifies signals from a Tape Head 22 when the IC system is switched to the playback mode. While not specifically shown in FIG. 1, the Playback Amplifier 12 can also be driven via pad 30 (see FIG. 2A) which can be connected to an external low noise transistor (not shown). Signals from a radio or phonograph pickup can be connected to pad 32 (see FIG. 2B). Both preamplifiers 10 and 12 of FIG. 1 can be used with frequency shaping networks 20A MIC Equalizer and 21A (NAB Equalizer) for equalization and pre-emphasis.
Reference numeral 13 of FIG. 1 is an Output Amplifier which is a medium gain amplifier that accepts input signals from amplifiers 10 and 12, and supplies an amplified output signal through capacitor 19A to volume control for Playback Output 19. Alternatively, an output signal is supplied by the Output Amplifier 13 to the recorder Tape Head 22 via conductor 13A through preemphasis network 21A and the Bias Oscillator 21.
An automatic level controller (ALC) 14 is shown as one block in relation to other circuit functions. The ALC or Auto Level block 14 is connected to the common output of Playback amplifiers 10 and 12 via conductor 14A which serves as an input to the ALC 14. The processed signal of the ALC or Auto Level 14 output which is essentially a rectified and filtered analog of the input source signal envelope is applied via conductor 14B to the input of the source amplifier 10. The dynamic impedance of the ALC 14 output on conductor 14B effectively controls the gain of the Source amplifier 10 by acting as a shunt. Reference numeral 24 shown as the dotted box of FIG. 1 contains a shunt capacitor 24A connected across one input to the Source amplifier 10. The capacitor 24A functions as an optional noise reduction arrangement by increasing the high frequency roll-off when the system gain is at maximum, i.e., when the ALC 14 output impedance is at its maximum. The ALC 14 relaxation time for level control can be adjusted as desired by modifying RC network 17 (ALC Timing Network) which is connected to the Auto Level Control 14.
Reference numeral 15 of FIG. 1 is a Meter Drive or Motional Peak Leveler (MPL) also derives its input signal like ALC 14 via conductor 14A from common output 14C of the preamplifiers 10 and 12. VU (Volume Unit) meter 18 and RC response shaping network 18A are connected to the Meter Drive (MPL) 15.
Reference numeral 16 of FIG. 1 shows the Record/Playback (R/P) switching logic block. R/P switching is accomplished by using the R/P logic 16 to selectively disable either the Source amplifier 10 or the P.B. amplifier 12. R/P changeover or transfer switching is accomplished by operation of an externally mounted single pole, Play/Record switch 23 which is connected to both the Bias Oscillator 21 and to the Rec/Play Logic 16 by conductor 16A. A RC decoupling network 16B is connected to the conductor 16A near the Rec./Play Logic block 16. In the record position of the Play/Record switch 23, the switch 23 grounds the logic input to the Rec./Play Logic 16 and also starts the Bias Oscillator 21. In the Play position of the switch 23, the R/P selector switch 23 grounds one terminal of the Tape Head 22. The other terminal of the Tape Head 22 is connected to one input of the PlayBack Amplifier 12 which is enabled or made operational by lack of a signal carried by conductor 16C from an output of the Rec./Play Logic block 16. Reference numeral 14D is an RC decoupling network connected to both Source and Play Back Amplifiers 10 and 12. The common output of preamplifier 10 and 12 is connected via the conductor 14A to both the ALC 14 and the Meter Drive 15. Reference numeral 13B is a pair of feedback attenuation resistors in the two outputs of the Output Amplifier 13 which are connected to a RC feedback network 13C. Coupling capacitors 16D, 14E and 20B are connected respectively to the P.B. Amp. 12, to the input for both the ALC 14 and Meter Drive 15, and to Source Amp. 10. A filter capacitor 26 (see FIG. 1) is connected to V+ bus 42A (see FIG. 2B) by means of Pad 26P. The V+ bus 42 is also connected, as shown in FIG. 1, to the Source Amplifier 10, P.B. Amplifier 12, Output Amplifier 13, Rec./Play Logic 16, Meter Drive 15, and ALC 14. A ground line 43 (see also FIG. 2) is connected, as shown, to the Source Amplifier 10, P.B. Amplifier 12, Output Amplifier 13, Rec./Play Logic 16, Meter Drive and ALC 14. The ground line 43 is also connected to the substrate of an I.C. chip using the electronics shown in FIG. 2.
FIGS. 2A, 2B, 2C and 2D are four parts of a single detailed electrical schematic diagram of the IC described herein as part of a self contained recording and playback system shown in FIG. 1. The external components of FIG. 1 are not shown in FIG. 2. The IC of FIG. 2A, 2B, 2C, 2D utilizes 80 transistors, 9 diodes, 3 current leakage protectors (transistors without base connectors) and 57 resistors. There are also 8 low value capacitors C1-C6 as part of the IC. Capacitors C 1 and C 2 and C1A and C2A located in box 10 and 12 are 5 pf MOS capacitors used for frequency compensation. 9 transistors are used directly in the signal path for amplification (boxes 10, 12 and 13 as described below), 12 transistors are used directly in the R/P logic transfer function 16, and 13 transistors are used in the ALC 14 and MPL meter drive 15. The remaining 40 transistors are used for voltage regulation current control and other functions related to signal isolation and circuit stability.
A detailed description of the various components and interconnections of the 1C shown schematically in FIG. 2 follows. Boxes 10, 12, 13, 14, 15 and 16 of FIG. 2A, 2B, 2C, and 2D are the equivalent to the Sound Amplifier 10, P.B. Amplifier 12, Output Amplifier 13, ALC 14, Meter Drive 15 and Rec./Play. Logic 16 of FIG. 1. The transistors of FIG. 2A, 2B, 2C and 2D are all identified by the use of the letter Q followed by a number. The resistors of FIG. 2A, 2B, 2C and 2D are all identified by the use of the letter R followed by a number. Referring to boxes 10 and 12 of FIG. 1, transistors Q1 and Q2 are low-noise, high beta multiple emitter transistor devices used in the input stages of the Playback Amplifier 12 and the Source Amplifier 10. The collector of Q1 is connected to V+ bus 42A through load resistor R1 (33 K ohms). Q1's collector is also connected to the base of transistor Q3. The MOS capacitors C 1 and C 1A serve as a compensator. The base of Q1 is connected to a Playback input pad 29. The base of Q1 is forward biased through bias resistor R11 (51 K ohms). R11 is connected to the junction of R15 (36 K ohms); and R17 (10 K ohms). Q1's multiple (six are shown) emitters are connected to a playback feedback pad 31. Q9 comes on when you turn on the circuit. Thus, Q9 quickly charges the input capacitor 20B and 16D, FIG. 1 to bring them up to a level where they are going to be biased under circuit operation.
The collector of Q2 is also connected to V+ bus 42A through load resistor R2 (33 K ohms). V+ bus 42A is also connected to the filter capacitor pad 26P (see FIG. 1) which is provided for connection to the external capacitor 26.
The base of transistor Q2 is connected to the Microphone Input pad 20 (see FIG. 1) which is connected to the Microphone Input 20. The base of Q2 is forward biased by connection to the resistor R12. The emitters of Q2 (six are shown) are connected to the microphone feedback pad 27. The collector of Q2 is also connected to the base of Q4. The capacitors C2, and C2A serve as compensators.
Referring to Box 10, the base of Q3 is connected to the collector of Q1 and the emitter of Q3 is connected to both the base of Q5 and to R5 (4.7 K ohms) which is connected to R7 (42 K ohms) which is in turn connected to the ground line 43. The collector of control transistor Q7 is connected to the junction of R5 and R7. The emitter of control transistor Q7 is connected to the ground line 43. The base of Q7 is connected to one of the four collector leads of Q48 in Box 16. The emitter of Q5 in Box 12 is connected to R9 (200 ohms) which is also grounded to the line 43. The collector of Q3 is connected to a first secondary V+ bus 42B through load resistor R3 (30 K ohms). Q5's collector is connected to the junction between the collector of Q6 and the base of Q19 in Box 10 via conductor 28A.
The primary V+ bus 42C is directly connected to V+ pad 42. The V+ bus 42C and 42D which are connected together are part of the V+ bus 42 of FIG. 1. The primary V+ bus 42C is connected to the emitters of transistors Q18 (Box 10D) and Q21 (Box 13). The bases of Q18 and Q21 are connected together to the base of Q13 and the emitter of Q14. The collector of Q14 is connected to ground and Q14's base is connected to the collector of Q13. The base/collector junction of Q14/Q13 is connected to the collector of Q17. The emitter of Q17 is grounded and its base is connected to the bases of Q16 and Q15. The emitters Q16 and Q15 are also grounded. The base connections to Q15, Q16 and Q17 are connected through R18 (10 K ohms) to the collector of Q15 which is also connected to R17 which is in turn connected to the junction of R11, R12 and R15, a part of the stabilized base voltage supply to Q1 and Q2. Another lead goes from the base connections of Q15, Q16 and Q17 to the base of Q20 in Box 10. The emitter of Q13 is connected to the primary V+ potential bus 42C. R 14 (500 ohms) is connected from the first secondary V+ potential source 42B to the tertiary V+ bus 42A which supplies voltage to the emitters of Q1 and Q2.
The base and collector of transistor Q9 are connected together and then through R13 (5 K ohms) to the first secondary V+ bus 42B. The Q9 base/collector junction is also connected to the emitters of Q10 and Q11. The collectors of Q10 and Q11 are connected to ground line 43 through R19. The collectors of Q10 and Q11 and R19 are connected to the base of Q12. The collector of Q12 is connected to the base of Q10 and Q12's emitter is grounded (line 43). The base of Q11 is connected to the collector of Q16 which is connected through R16 (36 K ohms) to the first secondary V+ bus 42B.
The collector of Q4 in Box 10 is energized by the first secondary V+ bus 42B through load resistor R4. The emitter of Q4 is connected to the base of Q6 and also to ground through R6 (4.7 K ohms) and R8 (42 K ohms). The collector of control transistor Q8 is connected to the junction of R6 and R8. The base of Q8 is connected to the third collector lead of transistor Q54 and the emitter of Q8 (in Box 10) is grounded (line 43.). The collector of transistor Q6 (in Box 10) is connected to the base of Q19 and to the collector of Q18 (both are in Box 10). The emitter of Q6 is connected to ground through R10 (200 ohms). The collector of Q19 is connected to the primary V+ bus 42C. The emitter of Q19 is connected to the collector of Q20 and to preamp. output pad 28.
Differentially connected dual collector transistors Q22 and Q23 form the input section of the Output Amplifier 13 (Box 13). The base of Q22 is connected to amplifier input pad 32. The emitter of Q22 is connected to one collector lead of Q21 through resistor R20 (10 K ohms). The base of Q23 is connected to a feedback pad 35. The emitter of Q23 is also connected to the same collector lead of Q21 through resistor R21 (10 K ohms). One collector lead of Q22 and Q23 is connected to ground. the second collector lead of Q22 is connected to the collector of Q24. The emitters of Q24/Q25 are connected to ground. The base of Q24 is connected to the base and collector of Q25 and to the second collector lead of Q23. The junction between the second collector of Q22 and the collector of Q24 is connected to the base of Q26. Capacitor C3 (5 pf) is connected from the base of Q26 to output pad 33 and capacitor C4 (5 pf) is connected from the base of Q26 to output 34. Capacitor C6 is connected from the base of Q26 to ground line 43.
The collector of Q26 is connected to ground line 43. The emitter of Q26 is connected to the base of Q27 and to the other one of the dual collector leads of Q21. The emitter of Q26 is also connected to the anode of diode D1. The cathode of diode D1 is connected to ground through R23 (24 K ohms). The cathode of D1 is also connected to the second collector lead of the triple collector lead of transistor Q28 and to the second collector lead of the triple collector lead of transistor Q29. The collector of Q27 is connected to the primary V+ bus 42C. The emitter of Q27 is connected to the base of Q32 through R24 (30 K ohms) and to the base of Q33 through R25 (30 K ohms). The collector of Q32 is connected to the first collector lead of multi-collector transistor D28 and to the output pad 34. The emitter of Q32 is connected to ground through R26 (200 ohms). The third collector lead of Q28 is connected to the base of Q30 and to the collector of Q76. The emitter of Q30 is connected to the base of Q28 and the emitter of Q28 is connected to the primary V+ bus 42C. The collector of Q33 is connected to the first collector lead transistor Q29 and to the output pad 33. The emitter of Q33 is connected to ground through resistor R27 (200 ohms). The third collector lead of transistor Q29 is connected to the base of Q31 and to the collector of Q77. The collector of Q31 is connected to ground and the emitter is connected to the base of Q29. The emitter of Q29 is connected to the primary V+ bus 42C.
The collector of control transistor Q34 in Box 13 is connected to the junction of R24 and the base of Q32. The emitter of Q34 is connected to ground and its base is connected to the second collector lead of multi-collector transistor Q48 (Box 16). The collector of control transistor Q35 is connected to the junction of R25 and the base of Q33. The emitter of Q35 is connected to ground and its base is connected to the fourth collector lead of transistor Q54 (Box 16).
The base of transistor Q76 (whose collector is connected to the collector/base leads of Q28/Q30 is connected to the collector of Q78 and one end of R53 (10 K ohms). The emitter of Q78 is connected to ground and the base is connected to the sixth collector lead of transistor Q54. The other end of R53 is connected to the emitter of Q75 and to one end of R54 (10 K ohms). The collector of Q75 is connected to second secondary V+ bus 42D which is energized by the emitter of Q51 whose base is connected to the common bases of Q13, Q18 and Q21. The emitters of Q18 and Q21 are connected to the primary V+ bus 42C.
The emitters of Q76, Q77 are connected to ground through resistor R55 (4.7 K ohms). The base of transistor Q77 (whose collector is connected to the third collector lead of Q29 and the base of Q31) is connected to R54 and the collector of Q79. The emitter of Q79 is connected to ground and its base is connected to the first collector lead of transistor Q48. The base of Q75 is connected to the base and collector of diode connected transistor D8. The emitter of D8 is connected to the anode of diode D7. The cathode of D7 is connected to the second secondary V+ bus 42D. The junction of D8 emitter and D7 anode is connected to the ALC timing pad 38, the base of transistor Q67 and the collector of transistor Q59. The ALC timing pad 38 is also connected to the emitter of Q66 through R47 (1 K ohms) and to the emiter of Q65 through R46 (1 K ohms). The collectors of Q65 and Q66 are connected to the second secondary V+ bus 42D.
The base and collector of the diode connected transistor D8 and the base of Q75 are connected to the first collector lead of dual collector transistor, Q51 and to the anode of diode D3. The cathode of D3 is connected to the junction of R43 (27 K ohms), the cathode of D6, the base of Q65 and the base of Q73.
Diode connected transistors D4 and D5 are connected from the junction of D3, D6, R43, Q65 and Q73 to ground to clamp the voltage at this junction to a predetermined value. The other end of R43 is connected to the second secondary V+ bus 42D. The anode of diode D6 is connected to the first collector lead of Q60 through resistors R45 (6.7 K ohms) and R44 (800 ohms). The first collector lead of Q60 is also connected to the collector of Q59 in Box 16. The base of Q59A is connected to the base of Q59, D9, and the collectors of Q58 and Q55 through R57 (10 K ohms). The emitters of Q59 and Q59A are connected to ground. The emitter of D9 is connected to ground through R37 (1.2 K ohms). The base of Q58 is connected to ground through current leaker LQ3 and is also connected to the collector of Q53 in Box 16. The base of transistor D60 is connected to the emitter of Q61. The collector of Q61 is connected to ground. The second collector lead of Q60 is connected to the base of Q61 and to the collector of Q62. The emitter of Q62 is connected to the base of Q63 and to the ALC audio input pad 36, through R42 (2 K ohms).
The collector of Q63 is connected to the collector of Q64, to the base of Q62, and to the second collector lead of Q51. The base of Q51 is connected to the bases of Q50, Q49, Q37 and Q36. The emitters of Q51, Q50, Q49, Q37 and Q36 are all connected to the second secondary V+ bus 42D. The emitter of Q64 is connected to ground. The collectors of Q67 and Q68 are connected to the first secondary V+ bus 42B through R48 (1 K ohms). The emitter of Q67 is connected to the base of Q68 and to the first collector lead of transistor Q54. The emitter of Q68 is connected through R56 (100 ohms) to the base of Q69. The emitter of Q69 is connected to ground and its collector is connected to ALC output pad 37.
The base of Q70 is connected to the junction of R44, R45. The collector of Q70 is connected to the second secondary V+ bus 42D. The emitter of Q70 is connected to the base of Q71, to the collectors of Q73 and Q74 and to the meter timing connection pad 40, through resistor R49 (200 ohms).
The collectors of Q71 and Q72 are connected to the second secondary V+ bus 42D. The emitter of Q71 is connected to the base of dual emitter transistor Q72. One emitter of Q72 is connected to the VU meter output pad 39 and the other emitter of Q72 is connected to the emitter of Q73 which is connected to ground through R50 (6.2 K ohms) and R51 (9.1 K ohms). The base of Q74 is connected to the junction of R50 and R51. The emitter of Q74 is connected to ground through R52 (2 K ohms).
Resistors R38 (7.5 K ohms), R39 (5 K ohms), R40 (5 K ohms) and R41 (7.5 K ohms in Box 16) form a voltage divider network which is connected from the second secondary V+ bus 42D to ground within the Record/Playback Logic circuit shown in Box 16. The base of Q53 is connected to the junction of R38 and R39. The emitter of Q53 is connected to the first collector lead of dual collector transistor Q49 and the first emitter lead of triple emitter transistor Q52. The collector of Q53 is connected to the base of Q58 and the emitter of current leaker LQ3. The base of transistor Q54 is connected to the junction of R39 and R40. The emitters of transistor Q54 are connected to the second emitter lead of triple emitter transistor Q52 and are also connected to the first collector lead of dual collector transistor Q50.
The base of Q56 is connected to the second collector lead of dual collector transistor Q49, to the collector of Q57 and to the base/collector connection of diode connected transistor D2. The emitters of D2 and Q57 (as well as LQ2) are grounded. As previously stated, the base of Q57 is connected to the fifth collector lead of transistor Q54 and to the collector of current leaker LQ2. The base of transistor Q47 is connected to the second collector lead of transistor Q54 and the collector of current leaker LQ1. The collector of Q47 is connected to the base of Q46 and to the first secondary V+ bus 42B through R35 (5 K ohms). The emitter of Q46 is grounded and its collector is connected to control output pad 44.
The base of triple emitter control transistor Q52 is connected to the R/P Logic input pad 41. The collector of Q52 is grounded and, as previously described, the first emitter lead is connected to the emitter of Q53 and to the first collector lead of Q49. The second emitter lead of Q52 is connected to the emitters of Q54 and to the first collector lead of Q50. The third emitter lead of Q52 is connected to the emitter of Q55 and to the second collector lead of Q50.
The first collector lead of transistor Q54 is connected to the emitter/base junction of Q67/Q68. The second collector lead of Q54 is connected to the base of Q47 and the collector of current leaker LQ1. The third collector lead of Q54 is connected to the base of Q8. The fourth collector lead of Q54 is connected to the base of transistor Q35 in Box 13. The fifth collector lead of Q54 is connected to the base of Q57 and to the collector of current leaker LQ2. The sixth collector lead of Q54 is connected to the base of Q78. The base of Q55 in Box 16 is connected to the junction of R40 and R41. The emitter of Q55 is connected to the second collector lead of dual collector transistor Q50 and to the third emitter lead of triple emitter transistor Q52. The collector of Q55 is connected to the collector of Q58 and to the bases of D9, Q59 and Q59A.
Q48 is a transistor with four collectors. The first collector lead of Q48 is connected to the base of Q79. The second collector lead of Q48 is connected to the base of Q34. The third collector lead of Q48 is connected to the base of Q7. The fourth collector lead of Q48 is connected to its own base. The base of Q48 is also connected to the second secondary V+ bus 42D through R36 and to the collector of Q56.
Resistors R33 (2.54 K ohms) and R34 (2 K ohms) are connected as a voltage divider between the first secondary V+ bus 42B and ground. The junction of R33 and R34 is connected to the bases of transistors Q42 and Q43. The emitter of Q42 is connected to ground through resistors R30 (360 ohms) and R31 (3 K ohms). The emitter of Q43 is connected to the junction of R30 and R31. The collector of Q42 is connected to the collector of Q38 and to the base of Q44. The collector of Q43 is connected to the collector of Q39 and to the base of Q40. Capacitor C5 (10 pf) is connected between the junction of the Q39/Q43 collectors and the base of Q40 is connected to ground. The bases of Q38 and Q39 are connected to the emitter of Q44. The collector of Q44 is grounded. The emitters of Q38 and Q39 are connected to the first secondary V+ bus 42B through R28 (1 K ohms) and R29 (1 K ohms). The collectors of Q40 and Q41 are grounded. The emitter of Q40 is connected to the base of Q41. The emitter of Q41 is connected to the base of Q45, to the collectors of Q36 and Q37, and to one end of R32 (100 K ohms). The other end of P32 is connected to the second secondary V+ bus 42D. The emitter of Q45 is connected to the first secondary V+ bus 42B and the collector of Q45 is connected to the second secondary V+ bus 42D.
The bases of transistors Q36 and Q37 are connected to the bases of Q49, Q50 (in Box 16) and Q51, which as already mentioned, are connected to the bases of Q13, Q18 (in Box 10) and Q21 (in Box 13). The emitters of Q36 and Q37 are connected to the second secondary V+ bus 42D as are the emitters of Q48, Q49, Q50 (in Box 16) Q13 and Q51.
EXPLANATION OF THE VARIOUS FUNCTIONS OF THE IC
Referring to FIG. 1, the system illustrated therein shows one possible interconnection arrangement with a number of external components incorporated as part of the system. From the specification and schematic of FIGS. 2A, 2B, 2C and 2D, it can be observed that with the exception of the interconnection on line 28A (from the common pad 28) of the output of the Source 10 and Playback 12 amplifiers, the various pads on the chip are not interconnected and allow for independent external connection. This permits considerable latitude in the choice of transducers, signal sources and output arrangements to be used with the disclosed Record/Playback system.
The following is a brief explanation of the function of the three amplifiers 10, 12, and 13 and the three auxiliary functions 14, 15, and 16 incorporated in the system of the invention.
SOURCE AMPLIFIER 10
In FIG. 2B, Box 10, shows the components and internal connections of the Source Amplifier 10 indicated as the Source Amp. 10 block of FIG. 1. The signal path is from the Mic. Input Pad 20 via Q2, Q4, Q6, Q19 to the preamp output pad 28. The enable/disable function required for R/P selection is exercised via Q8 acting on signal transistor Q4. Transistor Q8 must be turned off to turn on transistor Q4. The Source amplifier 10 requires a fairly large external filter/decoupling capacitor 26 (see FIG. 1) connected to the filter capacitor pad 26P (of FIG. 2). The microphone feedback network may include external frequency shaping elements should be connected between the microphone feedback pad 27 and pad 28.
Box 12 of FIG. 2A shows the components and internal connections of the Play Back Amplifier 12 which is also shown as block 12 of FIG. 1. The signal path is from the playback input pad 29 via transistors Q1, Q3 and Q5 to (using conductor 28A) Q19 of the Source amplifier (Box) 10 to the preamp output pad 28. This is in accordance with the diagram of FIG. 1 which shows the outputs of amplifiers 10 and 12 connected in parallel by means of conductor 28A. Input pad 32, Box 13 of FIG. 2B, can also be used for connection to a radio/phonograph (not shown) or other higher level signal sources, if desired. The emitters of Q1 are connected to the playback feedback pad 31, which permits connection to a frequency shaping network and feedback connection between the Q1 emitters and pad 28. Enable/disable bias as required for R/P switching is applied to the emitter of Q3 and base of Q5 by transistor Q7 which is turned on by transistor Q48 of the Record/Playback Logic 16.
OUTPUT AMPLIFIER 13
Block 13 of FIG. 2B shows the components and internal connections of the Output Amplifier 13 of FIG. 1. The signal path through the Output Amplifier 13 is from the amplifier input pad 32 to transistor Q22, to Q26, to Q27, and thence to either Q33 and output pad 33 or to Q32 and output pad 34. The either/or status of Q32 and Q33 depends on whether Q34 or Q35, respectively, is biased into conduction by the R/P Logic 16. Transistor Q22 connected to at the amplifier input pad 32 forms a differential amplifier in conjunction with Q23. The base of Q23 is connected to feedback input pad 35 to facilitate introduction of negative feedback (see 13B of FIG. 1) into the Output Amplifier 13C. Transistors Q22, Q24 and Q23, Q25 are connected as PNP/NPN complementary pairs and the signal derived from the collectors of Q22/Q24 is fed to the base of Q26. The emitter of PNP Q26 drives the base of Q27 whose emitter is connected to the bases of Q32 and Q33 through 30 K ohm resistors R24 and R25. The function of the 30 K ohm resistors R24 and R25 is to effectively isolate Q32 from Q33 and to assure that Q34 or Q35 when either is biased into conduction will effectively eliminate the signal at the base of either Q32 or Q33, respectively.
Thus, the Output Amplifier 13 performs a dual function. In the Record mode it provides a low impedance signal source at a level suitable for driving the Tape recording Head (see 22 of FIG. 1) and in its playback mode it supplies enough of a signal level to an external volume control (see 19 of FIG. 1) to permit satisfactory operation of an external power amplifier and loud speaker (not shown). It is also necessary that outputs (pads 33 and 34) of the Output Amplifier 13 be completely decoupled in either operating mode. When Q34 is on, then Q33 is enabled and pad 33 is working. When Q35 is on then Q32 is enabled and pad 34 is working. Q76 or Q77 also turn "off" and "on" to provide a biasing current for Q32 or Q33 respectively.
AUTO LEVEL CONTROL (ALC) 14
Box 14 of FIG. 2D shows the components and internal connections of the Automatic Level Controller (ALC) 14. This corresponds to the Auto Level Control (ALC) block 14 shown in FIG. 1. The ALC 14 derives its input signal from the audio input pad 36 (see FIG. 2). The signal path in the ALC 14 is via R42, to the Darlington pair Q63/Q64, which are collector coupled to the base of Q62, thence to Q61 and Q60. The first collector lead of Q60 drives the base of Q66 whose emitter is connected to the base of Q67 (part of Darlington pair Q67/Q68) through R47.
The emitter of Q66 feeds the Darlington pair Q67/Q68 which drive the base of Q69. Q69 is the shunt transistor (connected to ALC output pad 37) which controls the input impedance of the Source amplifier 10 at the microphone input pad 20 by means of conductor 14B (see FIG. 1). To adjust the time constant of the ALC 14, it is necessary to connect an external RC network (see 17 of FIG. 1) from the ALC timing pad 38 to ground.
METER DRIVE (MPL) 15
Box 15 of FIG. 2D shows the components and internal connections of the portion of the IC circuit designed for driving the recording level meter 18 of FIG. 1. This circuit portion corresponds to the block 1 marked Meter Drive (MPL) reference numeral 15 of FIG. 1. The Meter Drive circuit portion 15 obtains its operating signal from the junction of R44 and R45 (in the Auto Level Box 14) to the base of transistor Q70 in the Meter Drive Box 15.
The emitter of transistor Q70 drives the Darlington pair Q71/Q72. The first emitter lead of Q72 is connected to the IC meter output pad 39. The overall attack and decay speed of the recording meter 18 can be adjusted by connecting the RC network 18A (see FIG. 1) from the meter timing pad 40 to ground. The Meter total response varies as the audio level drives the recording Meter Drive 15 toward full scale. This is defined as the Motional Peak Level (MPL) feature. The MPL feature is created by Q73 and Q74, the collectors of which are connected to the base of Q71. The base of transistor Q73 receives a DC reference signal from the base of Q65 located in the ALC Box 14. The base of Q74 is connected to the mid-point of a voltage divider R50, R51 in the emitter circuit of Q73. The second emitter lead of the dual emitter transistor Q72 is connected to the emitter of Q73.
RECORD/PLAYBACK LOGIC 16
Box 16 of FIG. 2C, shows the components and internal connections of the logic circuit portion for changing from the Record to Playback function and vice versa. Box 16 of FIG. 2C corresponds to the block labeled Record/Playback Logic, reference numeral 16 of FIG. 1. The enabling signal for the Record function is initiated by grounding the Record/Playback logic input pad 41, which grounds the base of the multi-emitter PNP transistor Q52 that drives Q54 and Q55 into cut-off. Transistor Q54 when turned on causes Q8 to conduct which allows the playback amplifier 12 to operate. Another collector of Q54 causes Q35 to conduct and disable output pad 33 of the Output Amplifier 13. Conduction in transistor Q52, initiated by grounding its base, also cuts off transistor Q48 because of the phase reversal by Q56. When Q48 is not conducting, Q7 (in the Play Back Amplifier 12) does not conduct, thus enabling the Playback (P.B.) amplifier 12. Conduction in Q48 which does all the switching for the record operation, also turns on Q34 in the Output Amplifier 13. When Q34 is on, then Q33 is enabled and pad 33 is working. If Q54 is turned off, it keeps Q57 off and current source Q49A is then allowed to supply current to diode and transistor Q56 which drives Q48 into conduction. When the R/P logic input pad 41 is open, the base of Q52 is open, current source transistor Q50 supplies current to Q54 and Q54 functions to divide up the current. In the playback mode of operation Q54 is "on". When Q52 is "on" it acts as a current sink for transistor Q50 and thereby turns off Q54. Non-conduction in Q54 also cuts off Q35 in the Output Amplifier 13, rendering output pad 33 operational. Referring to FIG. 2D, Q78 and Q79 are also control transistors. One of these two control transistors is "on" for the record mode of operation. The other one is "on" for the playback mode of operation.
While the invention has been particularly shown and described with reference to the preferred embodiments above, it will be understood by those skilled in the art that the foregoing and other changes in the form and details may be made therein without departing from the spirit and scope of the invention. | This disclosure describes a recorder/playback system which utilizes a silicon chip having bipolar transistors. One feature is an integral electronic switching arrangement which permits silent and smooth change from the record to the playback mode and vice versa by operation of an external single pole switch. Other features include a circuit for driving a recording level meter, an automatic audio level control circuit (ALC) and integral voltage and current regulators. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The following patents and/or patent applications are hereby incorporated by reference: U.S. patent application Ser. No. TBD titled “Movable Office Support System” filed Jun. 22, 2001 (Attorney Docket No. 76507-386); U.S. patent application Ser. No. 09/183,023 titled “Workstation” filed Oct. 30, 1998.
FIELD OF THE INVENTION
[0002] The present invention relates to a movable display support system. The present invention also relates to a support system for a display device or the like which is movable within a work space to support one or more workers in a wide variety of use conditions.
BACKGROUND
[0003] It is known to provide for a display device such as a display panel, video monitor (e.g. CRT), television screen or other video display to present information (in some form) for entertainment or use by one or more workers in an office or other work environment. Display devices are generally associated with electronic equipment or appliances, such as computing devices or video receivers (e.g. television or the like).
[0004] In a typical application, the display device is positioned on a fixed worksurface (such as a table or desk), and thereby is in a relatively fixed or “static” position relative to workers or other persons who enter a work space (such as an office). Where the display device is a conventional video monitor, it may be difficult (if not also inconvenient) to adapt the position of the display device to the needs of one or more workers who may have the need or desire to view or share information presented. Likewise, it can be difficult to move the display device to a less prominent position within the work space, for example when information is to be viewed in private, or when the display device is not in use. In any event, according to known arrangements, it is typically difficult as well as inconvenient to move a display device from an in-use position where information can be viewed and shared readily to a private or stowed position where information is not displayed or not to be shared by persons in the work space. As a result, in many applications, display devices, once installed in a work space, are not repositioned frequently—even if repositioning would be desirable or advisable under the circumstances.
[0005] The more prevalent use of display panels (e.g. flat panel displays) as display devices for computing devices has to some extent lessened the inconvenience of repositioning, but the basic difficulties remain. Moreover, the need to provide a connection for utilities (e.g. power and/or data) to the display device is also a consideration. In typical applications, such connections are made by cables and require suitable proximity to outlets, and cause additional difficulty to be addressed when the display device is to be repositioned within the work space.
[0006] Fixture arrangements for display devices, such as adjustable arms, bases or stands, are known. However, such arrangements are typically positioned in a fixed location within the work space and thereby allow for a limited range of motion or change in orientation of the display device. Moreover, it is typical for such arrangements to accommodate only a single display device. When two (or more) display devices are used, the difficulties of positioning and repositioning may be multiplied.
[0007] Accordingly, it would be advantageous to provide a support system for a display device that allows for convenient repositioning of the display device within a work space. It would also be advantageous to provide a support system for a display device that provides for a wide range of motion and allows for a variety of orientations of the display device. It would further be advantageous to provide for a support system for a display device that can accommodate one or two or more display devices. It would further be advantageous to provide for a support system that provides for convenient management and interconnection of cables providing utilities to the display device (or display devices). It would further be advantageous to provide for a support system for a display device that can readily be integrated with the articles of furniture within a work space. It would further be advantageous to provide for a support system for a display device that can provide an interface for known fixture arrangements used for display devices.
[0008] It would be desirable to provide a system and method having any one or more of these or other advantageous features.
SUMMARY OF THE INVENTION
[0009] The present invention relates to a movable support system for at least one display device. The system includes a track system and a base movably mounted at a first section to the track system. The system also includes a display support assembly adapted for coupling of the display device and pivotally mounted at a second section of the base. The display device installed on the display support assembly may be selectively positioned for use in a variety of locations relative to the track system.
[0010] The present invention also relates to an apparatus providing a movable support for a display device. The system includes a track system providing at least one track and a support movably coupled at a first section to the track system. The system also includes a display support movably coupled to a second section of the support and configured for coupling of at least two display panels. Each of the display panels may be positioned for use in a variety of locations relative to the track.
[0011] The present invention further relates to a movable support system for at least one display device configured to be coupled to utilities such as power or data through cables. The system includes a track and a support movably mounted at a first section to the track. The system also includes a display support adapted for coupling of a display device and pivotally mounted at a second section of the support. The display device installed on the display support may be selectively positioned for use in a variety of locations relative to the track, wherein the support is configured to provide at least one passage for management of cables configured to be coupled to the display device.
[0012] The present invention also relates to a movable support system for use by at least one person in a work space having an entrance. The system includes a track system and a base movably mounted at a first section to the track system. The system also includes a display support assembly adapted for coupling of at least one display device and pivotally mounted at a second section of the base. A display device installed on the display support assembly may be selectively positioned for use in a variety of locations relative to the track system so that each person within the work space may selectively choose a body orientation or a body position relative to the entrance or otherwise within the workspace while using the display device.
FIGURES
[0013] [0013]FIG. 1 is a perspective view of work space providing a display support system according to an exemplary embodiment.
[0014] [0014]FIG. 2 is a front perspective view of the display support system according to an exemplary embodiment
[0015] [0015]FIGS. 3A and 3B are top perspective views of the support system.
[0016] [0016]FIGS. 4A and 4B are top perspective views of the display support system within in a work station providing an article of furniture according to an exemplary embodiment.
[0017] [0017]FIG. 5 is a top perspective view of the support system.
[0018] [0018]FIG. 6 is a bottom perspective view of the support system display.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
[0019] Referring to FIG. 1, a work space 10 is shown including a workstation 12 configurable for use by one or a plurality of workers or other persons. Workstation 12 includes a movable display support system 14 along with other articles of furniture shown as an associated mobile worksurface or table 16 , a fixed worksurface 18 , storage units shown as shelving units 20 and lateral files 22 . Work space 10 also provides walls shown as partial height partition walls including a base wall 24 and side walls 26 as well as a utility threshold 28 movable on a track 30 (not visible in FIG. 1). According to any preferred embodiment, the utility threshold is of a type disclosed in U.S. patent application Ser. No. 09/183,023, titled “Workstation” and filed on Oct. 30,1998, and in U.S. patent application Ser. No. 09/183,021, titled “Work Environment” and also filed on Oct. 30, 1998 (both incorporated by reference herein), providing functionality and features such as power, voice and data connections, display devices or information display panels, lighting, privacy screens, etc. Also shown in work space 10 are chairs 32 (which can be of any conventional type, preferably mobile chairs). As shown, movable display support system 14 includes two display devices shown as display panels 34 .
[0020] Referring to FIG. 2, movable display support system 14 is shown. Support system 14 includes a base 36 mounted to a track system 38 for translating movement (e.g. linear or curved or other) along a path of travel. Track system 38 is installed upon a mounting structure shown as a panel 40 (shown in FIG. 3). A passage in panel 40 shown as groove 41 can be used for routing various cables to base 36 . Support system 14 also includes a display support assembly 42 movably coupled to the base 36 . Support assembly 42 includes flanges 44 configured for attachment of a fixture or structure shown as an articulable arm 46 used to support an information display device shown as a display panel 34 (or any other structure such as a base or fixture of any conventional type providing one or more points or “joints” for movement of a mounted display device). According to an exemplary embodiment, support assembly 42 is pivotably coupled to base 36 and each articulable arm 46 is movably coupled to flange 44 to allow suitably positioning and/or orientation of display panel 34 in any of a variety of directions (e.g., up, down, laterally, pivotably) at each point or joint allowing articulation (e.g. translation, extension, retraction, rotation, etc.). As shown in FIGS. 3A and 3B, the selective movement of base 36 with respect to the mounting structure shown as panel 40 (e.g. along track system 38 ) and/or of support assembly 42 with respect to base 36 provides for the positioning and orientation of one or more of display panels 34 within a substantial range of motion in work space 10 ; selective movement of display panel 34 with respect to support assembly 42 provides for additional range of motion within work space 10 .
[0021] According to an exemplary embodiment shown in FIGS. 4A and 4B, panel 40 for track system 38 is installed horizontally between two storage units 48 ; a worksurface 50 may be installed within work space 10 over track system 38 . According to any preferred embodiment, the system may be integrated with or within articles of furniture in the work space.
[0022] Referring to FIGS. 5 and 6, movable display support system 14 is shown in a reverse view so that the underside of base 36 is visible. Base 36 includes a set of passages 52 and an aperture 54 for routing of cables 56 (for utilities such as power, communication and/or data, which may be routed to base 36 through passage or groove 41 of panel 40 ) to each of display panels 34 . Base 36 also includes a hub 58 providing paths or slots 60 for maintaining or retaining cables 56 below the coupling of display support assembly 42 . As shown in FIG. 5, track system 38 includes a set of tracks or rails 62 providing for guided and bounded motion of base 36 . As shown in FIG. 6, a set of roller guides 64 on base 36 engage rails 62 of track system 38 . According to a particularly preferred embodiment, hub 58 is rotatable within base 36 and display support assembly 42 is mounted to hub 58 to allow for rotation of display panels 34 . Display support assembly 42 may provide a worksurface 66 as well as a handle 68 (both shown in FIG. 2) to facilitate movement of the display devices.
[0023] According to any preferred embodiment, the system will provide for a wide range of motion for one or more display devices, including one or more of the following arrangements or combinations of arrangements for positioning and repositioning: (a) translating movement of the base along the track system, e.g. from one part of the work space to another for open use or stowing (see FIGS. 3 A and 3 B); (b) rotation of the display support assembly within a range of motion, e.g. to allow open viewing or privacy or stowing of the display device (see FIGS. 2 and 3A and 3 B); (c) articulation of the structure or arm, e.g. further to optimize the viewing angle/position (such as to remove glare or enhance visibility) of the display screen or further to enhance sharing/revealing or privacy/concealment of information. According to any preferred embodiment, the wide range of motion provided by the system will enhance the ability of workers or other persons to work collaboratively or to maintain privacy with information or to open or stow the display device (or display devices) conveniently—relatively quickly and easily—and without requiring significant concern for management of cables.
[0024] According to alternative embodiments, the movable display support system may be configured for one information display device or two or more information display devices; the information display devices may be of any type, including flat display panels or other types of video monitors (e.g. CRT) or any other type of data or information display device or appliance. The information display device may be associated with any type of appliance or device, such as a computing device or a television or network, etc.
[0025] In a conventional arrangement for associating a display device within a work space, where the display device is positioned on a fixed worksurface, constraints are typically imposed upon the orientation of a user or users relative to the entrance of the work space or adjacent aisles or opportunities for potential shared zones for viewing the display device with others. For example, if the display device is positioned on a worksurface to the back (or in one side or back corner) of the work space, the user of the work space may be constrained to work with her or his back to the entrance of the work space and information on the display device may be visible to those who enter the work space or walk along the adjacent aisle; if the display device is positioned on a worksurface near the center or front of the work space, the user of the work space may be constrained to “work around” the display device and may be less able to share information on the display device with those who enter the work space.
[0026] According to any preferred embodiment, the support system will provide enhanced functionality in comparison with such conventional arrangements, and allow the display device (or display devices) to be positioned selectively to enhance privacy or openness, or generally to facilitate the work to be performed in the work space; the support system is intended to allow the repositioning (including physical placement and orientation) of the display device to suit the needs of the worker. That is, according to any preferred embodiment of the support system, the user or users (without having to adapt or adjust their own posture and/or position) will be able to adapt the positioning and orientation of the display device or devices for various use conditions.
[0027] According to other exemplary embodiments, the display devices may be associated with other articles of furniture and/or physical structures (such as panels, partitions, or walls). It is important to note that the term “article of furniture” is intended to be a broad term and not a term of limitation. The term “article of furniture,” as used in this disclosure, may include, without limitation: systems furniture (e.g., partition wall systems, architectural walls, space frames, work stations, etc.), casegoods (e.g., file cabinets, storage bins, containers, closets, etc.), seating products (e.g., chairs, stools, lounges, etc.), work surfaces (e.g., tables, desk systems, credenzas, etc.), lighting systems, and other accessories.
[0028] It is important to note that the term “information” is intended to be a broad term and not a term of limitation. The term “information” may include information of any type or form or combination. It is also important to note that the terms “worksurface” and “work space” are intended to be given broad scope and are not terms of limitation. It is also important to note that the construction and arrangement of the elements of the system as shown in the preferred and other exemplary embodiments is illustrative only.
[0029] Although only a few embodiments of the present inventions have been described in detail in this disclosure, those skilled in the art who review this disclosure will readily appreciate that many modifications are possible (e.g., variations in sizes, dimensions, structures, shapes and proportions of the various elements, values of parameters, mounting arrangements, use of materials, colors, orientations, protocols, etc.) without materially departing from the novel teachings and advantages of the subject matter recited in the claims. Accordingly, all such modifications are intended to be included within the scope of the present invention as defined in the appended claims. The order or sequence of any process or method steps may be varied or re-sequenced according to alternative embodiments. In the claims, any means-plus-function clause is intended to cover the structures described herein as performing the recited function and not only structural equivalents but also equivalent structures. Other substitutions, modifications, changes and omissions may be made in the design, operating conditions and arrangement of the preferred and other exemplary embodiments without departing from the spirit of the present inventions as expressed in the appended claims. | A movable support system for at least one display device is disclosed having a track system and a base movably mounted at a first section to the track system. A display support assembly adapted for coupling of the display device is pivotally mounted at a second section of the base. The display device installed on the display support assembly may be selectively positioned for use in a variety of locations relative to the track system. An apparatus is also disclosed providing a movable support for a display device, including a track system providing at least one track and a support movably coupled at a first section to the track system. The apparatus also includes a display support movably coupled to a second section of the support and configured for coupling at least two display panels. Each of the display panels may be positioned for use in a variety of locations relative to the track. | 0 |
This application claims the benefit of Provisional Patent Application No. 60/540,074 filed Jan. 28, 2004.
BACKGROUND OF THE INVENTION
(1) Field of the Invention
The present invention pertains to a method of assembling articles using laser projection devices and a photoreactive material. More specifically, the present invention pertains to a method of assembling an article using one or more laser projectors and a material that is applied to the component parts of the article being assembled, where the material reacts when it is exposed to the laser light emitted by a projector. The material is applied to the article being assembled and when exposed to the laser light, the appearance of the material changes to mark a location on the material and thereby mark a location on the article where an assembly operation is to take place.
(2) Description of the Related Art
As a result of the competitive business environment, in businesses involving the assembly of large-scale articles such as automobiles, aircraft, large home appliances and others, there is a need to streamline the assembly of the component parts of the articles. A reduction in assembly time results in a reduction in manufacturing costs.
In the assembly of articles requiring a high degree of precision, specialized “hard” tooling is used to locate critical features of the component parts, for example fastener holes and fasteners, and to accurately position component parts relative to each other. As a further example, in assembling sections of a sheet metal body to a frame of an article such as an automobile or aircraft, a tool is manually positioned in engagement with a portion of the frame and a portion of the sheet metal section to properly position the sheet metal section relative to the frame. This enables the sheet metal section to be accurately attached in its desired position relative to the frame. In the assembly of a large article such as an automobile or aircraft, a large number of assembly tools would be designed and manufactured, with each tool being used to accurately position different component parts of the article being assembled. Each of these assembly tools is expensive to design, to manufacture, and to store and maintain. The use of assembly tools also contributes to inefficiencies in assembling of an article because an individual involved in the assembly of the article must retrieve, use and then store the assembly tool each time it is utilized in the assembly of the article.
Laser projection systems were designed to overcome the disadvantages associated with the use of assembly tools in the assembling of large-scale articles requiring precision assembly. Laser projection systems project laser light onto the component parts of the article being assembled. Typically, the software of the laser projection system utilizes a computer aided design (CAD) model of the article being assembled and makes calculations based on the CAD model to direct the laser light beam of the laser projection system in the desired pattern. The projected laser light is used to accurately locate machined portions of the component parts. For example, the laser light projection would be used to accurately locate drilled holes. Laser projection systems are also used to accurately project illuminated lines and curves onto the surfaces of the article being assembled to precisely identify assembly locations of component parts relative to each other during the assembly of the parts. The projection of the lines and curves onto the article being assembled is useful for, among other things, locating where component parts are to be assembled on the article without requiring hard tooling, and for confirming the configurations of the article when compared to the nominal design dimensions of the article.
However, one of the drawbacks in using layer projection systems in the assembly of articles is that the line of projection of the laser light to the assembly area must be maintained. In the assembly of large articles such as automobiles and aircraft, it is often necessary for several individuals to work in the assembly area assembling component parts of the article. As the individuals move about in the assembly area, they often move into the path of the laser light projection, thus obstructing the projection and the display of assembly information on the article provided by the laser light. To overcome this problem, it was necessary to “scribe” or trace the projected information onto the component part. This added significantly to the assembly time, and often lead to errors in the “scribed” information.
SUMMARY OF THE INVENTION
The present invention provides a method of assembling articles, for example automobiles, aircraft, and other types of articles that require precision positioning of at least some of their component parts, using light projection systems. The method of the invention makes use of known light projection systems, such as the model LPT1 manufactured by Laser Projection Technologies of Londonderry, N.H. The operation of the laser projection devices of the system of the invention is controlled by control software of the system, as is known in the art. A principle benefit of the invention is obtained by the use of a photoreactive material in conjunction with the laser projection system. The photoreactive material is applied to the surface of a component part of the article being assembled, and the laser light of the system produces a semi-permanent mark or indication on the surface of the component part through the reaction of the laser light with the photoreactive material. The markings produced by the photoreactive material on the component parts provide assistance to the individuals assembling the component parts in precisely positioning the component parts and/or checking the positioning of the component parts during assembly of the article. With the marks being produced on the component parts by the reaction of the laser light with the photoreactive material, the marks are not obstructed by the individuals assembling the article moving in front of the projected laser light. Because the individuals assembling the article are free to move about the assembly area without concerns for obstructing the projected laser light, the assembly of the article becomes more time efficient and more cost efficient.
The method of assembly of the present invention employs several of the known method steps of assembling an article employing projected laser light. At least one component part of the article to be assembled is positioned in an assembly area, and one or more laser light projectors are positioned in the assembly area. The laser light projector is controlled to emit laser light toward the component part in the assembly area where the laser light will be projected onto a surface of the component part.
A photoreactive material is applied to the surface of the component part in the area illuminated by the laser light. The photoreactive material can be provided in several forms. As one example, the material could be in the form of a self-adhesive tape or film applied to the surface of the component part. The photoreactive material can also be applied to the surface of the component part as a liquid that is sprayed onto the component part, as a dust that is dusted onto the component part, as a paste that is rubbed onto the component part, etc. When the laser light illuminates the photoreactive material applied to the surface of the component part, the pattern of the laser light projection creates a marking on the photoreactive material.
Movement of the laser light can be controlled to create a variety of different types of markings on the photoreactive material applied to the surface of the component part. The laser light can be moved to create cross-hair indications on the treated surface of the component part where holes are to be produced in the part, or where fasteners are to be located on the part. Lines can be formed on the treated surface of the component part by the movement of the laser light to provide a visual indication of the position of where a second component part is to be positioned relative to the one component part when assembling the two parts together. In addition, the movement of the laser light could project graphics onto the photoreactive material applied to the surface of the component part that provide information on a second component part to be assembled to the one component part, for example dimensions and materials of a fastener to be used with the one component part.
After the assembly of the article is completed, the photoreactive material applied to the surfaces of the component parts is removed. The removal of the photoreactive material is dependent on the form of the photoreactive material used. For example, the photoreactive material applied as a liquid spray would preferably be water based, enabling the easy removal of the photoreactive material from the surface of the assembled article by spraying or wiping water over the surface. A photoreactive material applied as a dust to the surface of the article component parts could be removed by a vacuum or by wiping the material from the surface. Photoreactive material applied to the surface of the component part as a paste would preferably be water based, enabling easy removal of the paste from the part's surface by spraying or wiping water over the surface. The material applied as a tape could be pulled from the article after assembly.
The method of the invention provides the benefits of the use of laser projection systems in the assembly of articles, without the associated disadvantage of avoiding interruption of the projected laser light. The method enables the maintaining of the accuracy of the laser projected data, as well as providing a quick and efficient manner of delivering required assembly information directly to the individuals assembling the article.
BRIEF DESCRIPTION OF THE DRAWING FIGURES
Further features of the invention are set forth in the following detailed description of the preferred embodiment of the invention, and in the drawing figures wherein:
FIG. 1 is a schematic representation of an assembly area in which the method of the invention is used;
FIG. 2 shows a portion of a component part of an article with which the method of the invention is used;
FIG. 3 shows component parts of an article with which the method of the invention is used; and,
FIG. 4 shows component parts of an article with which the method of the invention is used.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
As stated earlier, the present invention provides a method of assembling the component parts of an article, for example, assembling the component parts of an automobile or an aircraft to name only two examples, where the assembly of certain component parts requires a great deal of precision in the positioning of the component parts, and where projected light systems are employed to assist in the precision positioning of the component parts. The method of the invention makes use of the known laser light projection systems, for example the Model LPT1 manufactured by Laser Projection Technologies of Londonderry, N.H. Laser projection systems of this type and their method of use are known. The operation of a laser projection system is controlled by the control software of the system. Typically, the software of the laser projection system utilizes a computer aided design (CAD) model of the article being assembled, and makes calculations based on the information provided by the CAD model to direct the laser beam of the laser projection system in a desired pattern into an assembly area where the article is being assembled.
A novel feature of the method of the invention is the use of a photoreactive material in conjunction with the laser projection system. The photoreactive material reacts to the wave length of the laser light projected by the laser light projection system and changes in appearance, for example changing in color, at the portions of the photoreactive material on which the laser light is directed. Only those portions of the photoreactive material on which the laser light is directed change in appearance. The remainder of the photoreactive material remains unchanged. Thus, the change in the appearance of the photoreactive material, and the control of the movement of the laser light directed onto the photoreactive material enables producing markings on the surfaces of the component parts of the article being assembled to which the photoreactive material has been applied. Various types of markings can be produced on the photoreactive material to assist the individuals assembling the component parts of the article in precisely positioning the component parts and/or checking the positioning of the component parts during the assembly of the article. These markings will remain on the photoreactive material as individuals move about the assembly area and move into the line of projection of the laser light obstructing the laser light. Because the individuals assembling the article are free to move about the assembly area without concerns for obstructing the projected laser light and without the necessity of scribing or tracing the laser light projected information onto the component part, the assembly of the article becomes more time efficient and more cost efficient.
It is necessary to use different types of photoreactive materials with different laser projection systems having different wavelengths. In the illustrative embodiment of the invention to be described in which the above-identified laser projection system is employed, the photoreactive material employed is XP-4200, manufactured by the Rohm and Hauss Company of Philadelphia, Pa.
As stated earlier, the method of the present invention employs several of the known method steps of assembling the component parts of an article employing projected laser light. FIG. 1 shows a schematic representation of an assembly area 12 in which the method of the invention is practiced. In the assembly area 12 , one or more laser light projectors 14 are positioned at predetermined positions where the laser light projected from the projectors 14 will be directed toward areas of an article being assembled where the precision positioning of the articles component parts is necessary. In FIG. 1 a pair of laser light projectors 14 is shown. Depending on the article being assembled, one laser light projector may be sufficient, or a larger number of laser light projectors may be needed. As is known in the art, the laser light projected from each of the projectors 14 is controlled by the software of the laser light projection system. The control software (not shown) not only controls the direction of the projected laser light, but also controls the duration of the projected laser light.
At least one component part 16 of the article to be assembled is positioned in the assembly area 12 at a predetermined location relative to the predetermined location of at least one laser light projector 14 . Depending on the size of the article being assembled, it may be desirable to first position the one component part 16 of the article in the assembly area 12 before positioning the laser light projector 14 in the assembly area. In the illustrative example of FIG. 1, the one component part 16 is shown as a tubular or cylindrical frame that could be a frame for a fluid containing tank, a frame for a section of aircraft fuselage or a frame from some other similar article. The one component part 16 shown in FIG. 1 is only an example of a component part of an article with which the method of the invention may be practiced. The component part 16 should not be interpreted as limiting.
The photoreactive material, in the illustrative embodiment XP4200, is applied to the surface of the component part 16 in the areas toward which the laser light of the projectors 14 is directed. There are several ways in which the photoreactive material could be applied to the component part 16 in accordance with the invention. In addition, the photoreactive material could be applied to the component part 16 in many different forms. In one example, the entire component part 16 could be immersed in the photoreactive material in a liquid form. In further examples, the photoreactive material could be sprayed onto the entire component part 16 , or only portions of the component part, as a liquid spray or fine particulate dust. The photoreactive material could also be rubbed onto the surface of the component part 16 as a paste.
In the illustrative embodiment shown in the drawing figures, the photoreactive material is provided in the form of a flexible tape 22 shown in FIG. 2 . The tape 22 is applied to an area of the surface of the component part 16 . The photoreactive material tape 22 is applied in those areas in which precision assembly operations are required on the component part 16 . In some applications it may be required to cover a substantial area or the entire surface of the component part 16 with the photoreactive material tape 22 . In other situations it may only be necessary to cover a certain, limited area of the surface of the component part 16 .
With the photoreactive material tape 22 having been applied to the surface of a component part 16 in the desired area of the surface, the laser light projector 14 is controlled by its control software to direct laser light in a predetermined pattern onto the photoreactive material tape 22 . The laser light from the projector 14 illuminating portions of the photoreactive material tape 22 causes those portions of the tape to change in appearance. In one example, the tape 22 of photoreactive material could be substantially clear before reacting with the laser light. As it reacts with the laser light and subsequent to the reaction with the laser light, those portions of the photoreactive material tape 22 onto which the laser light is directed would change in appearance, for example, changing to a color. The control system of the laser light projector 14 controls the laser light to move in a predetermined pattern that in turn traces or illuminates a predetermined pattern on the photoreactive tape 22 . The movement of the laser light causes the illuminated portions of the photoreactive material tape 22 to change in appearance to depict the pattern of the laser light illuminating the portions of the tape. The control of the laser light can cause the change in appearance of the photoreactive tape to depict a cross hair 24 (shown in FIGS. 2 and 3) that locates a precision point in which an assembly operation, for example, the drilling of a hole should be positioned.
As a further example (shown in FIG. 4 ), the cross hair 24 could provide a precision location for a fastener 26 to be located in the component part 16 . This information could be used to position the fastener 26 on the component part 16 , or check that the fastener 26 has been properly positioned on the component part 16 .
In a still further example, the predetermined pattern of the directed laser light could cause the photoreactive material tape 22 to react and change in appearance to depict a line 28 (shown in FIGS. 2 and 3) relative to the one component part 16 where a second component part, for example a section of sheet metal 32 is to be positioned and attached to the one component part 16 . The projected laser light could cause the photoreactive material tape 22 to react and produce an indication of the both a line where the sheet material 32 is to be positioned, as well as cross hairs 34 indicating the positions of fasteners to hold the sheet material 32 to the one component part 16 .
Still further, the controlled movement of the projected laser light could cause the photoreactive material tape 22 to react to depict graphic information 36 on the one component part 16 , for example dimensions and materials of a fastener to be used with the one component part 16 and/or the torque to be applied to the fastener when attaching it to the component part.
After the assembly of the component parts 16 , 32 of the article has been completed, the photoreactive material 22 applied to the surfaces of the component parts is removed. The removal of the photoreactive material is dependent on the form of the photoreactive material used. In the illustrative example of the photoreactive material tape 22 described herein, after the assembly operations performed on the component part 16 are completed, the tape 22 is easily removed by peeling the tape from the areas of the component part 16 to which it had been applied.
When the photoreactive material is used in the form of a liquid that is sprayed on the surface of the component part 16 , preferably the liquid is water-based, enabling the easy removal of the photoreactive material from the surface of the component part 16 by spraying or wiping water over the surface.
A photoreactive material applied as a dust to the surface of the component part 16 could be removed by a vacuum or by wiping the material from the surface.
A photoreactive material applied to the surface of the component part 16 as a paste would also preferably be water-based, enabling easy removal of the paste from the part's surface by spraying or wiping water over the surface.
The method of the invention provides the benefits of the use of laser projection systems in the assembly of an article's component parts, without the associated disadvantages of avoiding interruption of the projected laser light or the need to “scribe” the data displayed onto the component part of the assembly. The method enables maintaining the accuracy of the laser light projected data, as well as providing a quick and efficient manner of delivering required assembly information directly to the individuals assembling the component parts of an article.
Although the method of the invention has been described above by reference to specific embodiments, it should be understood that modifications and variations can be made to the method of the invention without departing from the intended scope of the following claims. | A method of precision assembly of component parts of an article uses a laser light projection system in combination with a photoreactive material. The photoreactive material is applied to the component parts of the article being assembled, where the photoreactive material is exposed to the laser light emitted by the projector system. When the photoreactive material is exposed to the laser light, the appearance of the material changes to mark a location on the material and thereby on the component part where an assembly operation is to take place. | 1 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a U.S. National Stage Filing under 35 U.S.C. §371 and claims priority from International Application No. PCT/IB2016/051972, filed on Apr. 7, 2016, which application claims priority under 35 U.S.C. §119 from India Application No. 1444/MUM/2015, filed on Apr. 7, 2015. The entire contents of the aforementioned applications are incorporated herein by reference.
TECHNICAL FIELD
[0002] This disclosure relates generally to the field of perceptual cognitive traits, and more particularly to a system and method of estimating and improvising perceptual-cognitive traits of a subject.
BACKGROUND
[0003] Cognitive load, in general, is defined by the amount of short term memory used by an individual for a given task and primarily depends on how an individual perceives, assimilates and responds to an external stimulus. Usually, the actions of an individual are mediated and influenced by external environment and ability of an individual to understand and effectively interact with the environment is dependent on the cognitive traits of an individual. Hence in order to achieve the best results and exhibit best performance, the cognitive load on the individual should be optimum since too much cognitive load might result in stress, anxiety, etc. On the other hand, very less cognitive load is actually a un-utilization of one's cognitive capacity and ability.
[0004] It will however be agreeable that optimum level of cognitive load may vary from one individual to another, and is basically dependent on inherent cognitive skills of an individual. Developing basic cognitive skills of an individual, however remains an ardent task, to which education has a supreme role to play. The process by which a person learns best is also different across different people.
[0005] Bloom's taxonomy of learning domains is known to promote higher forms of thinking in education such as analyzing and evaluating concepts, processes, procedures, and principles. It majorly defines six major categories of cognitive skills that are arranged according to the increasing order of cognitive maturity as knowledge, comprehension, application, analysis, synthesis and evaluation. There are usually two measures of cognitive load:
[0006] a) Subjective Measures of Cognitive Load—This domain has been well read by many to find that various instructional methods can be used to improve the short term memory operations
[0007] b) Objective Measures of Cognitive Load—This includes estimation using different physiological signals and in order to measure the cognitive skills of an individual, particularly in the field of education area is relatively a new area of search. To make it more accessible, the sensing mechanism needs to be low cost and commercially available.
[0008] Recently, there have been various works to analyze the cognitive load of an individual for a given task using commercial EEG devices. As part of the education psychology, the cognitive load is analyzed based on the continuous EEG signals during the learning from hypertext and multimedia contents. EEG signals are being used in diverse application areas like estimation of video quality, ease of reading texts, and scientific problem solving. Apart from EEG, other physiological parameters like eye tracking, skin conductance and heart-rate are also used to investigate the effect of stimulus on the mental stress. There has been an attempt in past to study the students' learning trajectories and teachers' effect on problem solving abilities, however there has been complete reliance on the students' outcomes and never used brain signals. Many have also used Elementary Cognitive Tasks (ECTs) to investigate how the level of complexity (low and high cognitive load) manifests in the EEG and various physiological parameters.
[0009] However, none of the above works objectively analyze the relationships between the various ECTs or focus on investigating the relationship between the ECTs and Bloom's categories.
OBJECTIVES
[0010] In accordance with the present invention, the primary objective is to provide a system and method for analyzing elementary cognitive tasks with Bloom's Taxonomy using low cost commercial EEG device.
[0011] Another objective of the invention is to provide a system and method to objectively analyze the relationship among various ECTs and also between various elementary cognitive tasks (ECTs) and Bloom's categories.
[0012] Another objective of the invention is to provide a system and method to characterize an unknown stimulus and also derive various performance attributes of a subject.
[0013] Yet another objective of the invention is to provide a method and system for estimating or improvising perceptual-cognitive traits of a subject by creating Electroencephalogram (EEG) models for the cognitive skills defined in the Bloom's taxonomy.
[0014] A further object of this disclosure is to evaluate cognitive behavior of an individual using duster analysis of EEG features for different stimuli or tasks.
[0015] Other objects and advantages of the present invention will be more apparent from the following non-restrictive description of illustrative embodiments thereof, when read in conjunction with the accompanying figures, which are not intended to limit the scope of the present disclosure.
SUMMARY
[0016] Before the present methods, systems, and hardware enablement are described, it is to be understood that this invention in not limited to the particular systems, and methodologies described, as there can be multiple possible embodiments of the present invention which are not expressly illustrated in the present disclosure. It is also to be understood that the terminology used in the description is for the purpose of describing the particular versions or embodiments only, and is not intended to limit the scope of the present invention which will be limited only by the appended claims.
[0017] Accordingly, in a preferred embodiment the disclosure provides a method for estimating or improvising perceptual-cognitive traits of a subject. The steps for estimating perceptual-cognitive traits of a subject comprise, firstly retrieving and pre-processing the data and associated metadata indicative of brainwave activity of the subject to obtain effect of a plurality of elementary cognitive tasks, followed by identification of cognitive categories within a cognitive domain of cognitive learning model. Next, plurality of elementary cognitive tasks to be performed by the subject are mapped with the identified cognitive categories and duster analysis on each of the mapped elementary cognitive tasks is performed. Further, separation index values are determined from cluster analysis in relation to the identified cognitive categories and finally metrics are generated from the separation index values to estimate the perceptual-cognitive traits of a subject.
[0018] According to another embodiment of the disclosure, the data is electroencephalogram (EEG) signals captured using low resolution EEG devices.
[0019] In one significant embodiment of the present disclosure, the system for estimating and improvising perceptual-cognitive traits of a subject is disclosed. The system broadly comprises a processor, a data bus coupled to said processor; and a computer-usable medium embodying computer code, said computer-usable medium being coupled to said data bus, said computer program code comprising instructions executable by said processor and configured for:
[0020] retrieving and pre-processing data and associated metadata indicative of brainwave activity of the subject to obtain a plurality of elementary cognitive tasks;
[0021] identifying cognitive categories within a cognitive domain of cognitive learning model;
[0022] mapping plurality of elementary cognitive tasks to be performed by the subject with identified cognitive categories;
[0023] performing duster analysis on each of the mapped elementary cognitive tasks and determining separation index values therefrom the cluster analysis in relation to the identified cognitive categories; and
[0024] generating metrics from the separation index values for estimation or improvisation of perceptual-cognitive traits of the subject.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] The foregoing summary, as well as the following detailed description of preferred embodiments, are better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there is shown in the drawings exemplary constructions of the invention; however, the invention is not limited to the specific methods and system disclosed. In the drawings:
[0026] FIG. 1 of the present disclosure is a schematic functional block diagram of an exemplary architecture for the system, in accordance with one embodiment of present disclosure;
[0027] FIG. 2 is a block diagram illustrating the flow of EEG signal processing, in accordance with one embodiment of present disclosure;
[0028] FIG. 3 is a graph showing comparison of various feature components for F I peak F I mean in accordance with one preferred embodiment of present disclosure; and
[0029] FIG. 4 is a graph showing result of Xie-Beni index variation among subjects for different feature combinations, in accordance with one embodiment of present disclosure.
DETAILED DESCRIPTION
[0030] Some embodiments of this invention, illustrating all its features, will now be discussed in detail.
[0031] The words “comprising,” “having,” “containing,” and “including,” and other forms thereof, are intended to be equivalent in meaning and be open ended in that an item or items following any one of these words is not meant to be an exhaustive listing of such item or items, or meant to be limited to only the listed item or items.
[0032] It must also be noted that as used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural references unless the context clearly dictates otherwise. Although any systems and methods similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, the preferred, systems and methods are now described.
[0033] The disclosed embodiments are merely exemplary of the invention, which may be embodied in various forms.
[0034] The elements illustrated in the Figures interoperate as explained in more detail below. Before setting forth the detailed explanation, however, it is noted that all of the discussion below, regardless of the particular implementation being described, is exemplary in nature, rather than limiting. For example, although selected aspects, features, or components of the implementations are depicted as being stored in memories, all or part of the systems and methods consistent with the attrition warning system and method may be stored on, distributed across, or read from other machine-readable media.
[0035] The techniques described above may be implemented in one or more computer programs executing on (or executable by) a programmable computer including any combination of any number of the following: a processor, a storage medium readable and/or writable by the processor (including, for example, volatile and non-volatile memory and/or storage elements), plurality of input units, and plurality of output devices. Program code may be applied to input entered using any of the plurality of input unit to perform the functions described and to generate an output displayed upon any of the plurality of output device.
[0036] Each computer program within the scope of the claims below may be implemented in any programming language, such as assembly language, machine language, a high-level procedural programming language, or an object-oriented programming language. The programming language may, for example, be a compiled or interpreted programming language. Each such computer program may be implemented in a computer program product tangibly embodied in a machine-readable storage device for execution by a computer processor.
[0037] Method steps of the invention may be performed by one or more computer processors executing a program tangibly embodied on a computer-readable medium to perform functions of the invention by operating on input and generating output. Suitable processors include, by way of example, both general and special purpose microprocessors. Generally, the processor receives (reads) instructions and data from a memory (such as a read-only memory and/or a random access memory) and writes (stores) instructions and data to the memory. Storage devices suitable for tangibly embodying computer program instructions and data include, for example, all forms of non-volatile memory, such as semiconductor memory devices, including EPROM, EEPROM, and flash memory devices; magnetic disks such as internal hard disks and removable disks; magneto-optical disks; and CD-ROMs. Any of the foregoing may be supplemented by, or incorporated in, specially-designed ASICs (application-specific integrated circuits) or FPGAs (Field-Programmable Gate Arrays). A computer can generally also receive (read) programs and data from, and write (store) programs and data to, a non-transitory computer-readable storage medium such as an internal disk (not shown) or a removable disk.
[0038] Any data disclosed herein may be implemented, for example, in one or more data structures tangibly stored on a non-transitory computer-readable medium. Embodiments of the invention may store such data in such data structure(s) and read such data from such data structure(s).
Definitions
[0039] Bloom's Taxonomy: Bloom's Taxonomy is an essential model for promoting higher forms of thinking in an individual by providing appropriate learning conditions. Bloom's taxonomy classifies different learning objectives into three domains, namely, Cognitive, Affective and Psychomotor, and the element of discussion for present disclosure is Cognitive domain that involves knowledge, comprehension, application, analysis and evaluation of a particular topic.
[0040] Cognitive load primarily depends on how an individual perceives, assimilates and responds to an external stimulus. The present disclosure attempts to create Electroencephalogram (EEG) models for the cognitive skills defined in the Bloom's taxonomy using low cost, commercial EEG devices.
[0041] The present disclosure comprises a system which may be used for estimating and improvising perceptual-cognitive traits of a subject. The embodiments of the present disclosure may be applied in educational psychology to provide individual assistance according to one's learning style and traits, although it should be understood that the scope of the present invention is in no way limited to these applications.
[0042] In an embodiment of the present disclosure, as presented in FIG. 1 , the system 100 comprises a processor 104 , a data bus 106 coupled to said processor 104 , and a computer-usable medium like a memory 102 embodying computer code and coupled to a data bus 106 , wherein the computer program code comprises instructions executable by said processor 104 and is configured to relate the brain signals generated by various cognitive tasks to different cognitive categories of Bloom's taxonomy. The actual modulations originating in brain are captured which in turn control the ultimate thinking process for each and every response/action, eventually enabling measurement of improvisation in cognitive skills of an individual.
[0043] While different techniques may be used for reading and analyzing brain function, most widely used ones being—Electroencephalogram (EEG), functional magnetic resonance imaging (fMRI), functional near infra-red spectroscope (fNIRs), positron emission tomography (PET) etc. For the purposes of present disclosure, EEG has been selected as it is a non-invasive and relatively in-expensive method having excellent temporal resolution. More specifically, 14 lead EEG device from Emotiv has been used for capturing and analyzing brain signals.
[0044] A set of Elementary Cognitive Tasks (hereinafter referred to as ECTs) focusing on visual perceptions and cognitive speed is recognized and defined as the stimulus as ECTs are directly linked with general mental ability and intelligence of an individual. As a non-limiting example, the factors that are being considered for visual perception includes speed of closure and flexibility of closure.
[0045] In one exemplary embodiment, the stimulus is presented and EEG data and associated metadata is captured using python based capture tool. For EEG data collection a 14-lead Emotiv headset is used. The subject is presented with a set of questions that he is expected to answer using any of plurality of input devices 108 (referring to FIG. 1 )—a cursor control, such as a mouse, a trackball, or cursor direction keys for communicating information and command selections to processor. After completion of questionnaire and data collection process, the subject is evaluated in terms of response time and accuracy and the result is displayed on the commonly known output device 110 (shown in FIG. 1 ).
[0046] The EEG signals and associated metadata are analyzed as depicted in FIG. 2 . The metadata may include the time stamps for the EEG signals; presentation time of the stimulus, instruction and fixation slides; time stamps and the entries of the user responses. The relation between the accuracy and the response time of the subjects for each stimulus are analyzed.
[0047] The raw EEG signal is preprocessed and segmented based on predefined markers and then analyzed in time-frequency domain for feature extraction and clustering as shown in FIG. 2 . First in the pre-processing step, the signal is normalized to zero mean and fed to a low pass filter of predefined frequency range, e.g. 35 Hz to limit the signal to the frequency band of interest. EEG signal is vulnerable to different artifacts, the dominant of them being the eye blink related artifact.
[0048] One of the described embodiments of the present disclosure, Hilbert-Huang Transform (HHT) based approach is used to remove the artifact. After that the clean data is segmented into baseline and trial epochs. Then these epochs are partitioned in windows of N seconds with 50% overlap.
[0049] In one selected embodiment, N is selected to be 20 seconds for baseline epoch and 5 seconds for trial epochs. This is particularly done to examine multiple trial windows with a single baseline window. Both the trial and baseline windows are decomposed in the time-frequency domain using S-transform of N seconds with 50% overlap. From this decomposition the mean frequencies are computed using the following formula:
[0000]
f
(
ω
)
=
∑
i
=
0
n
-
1
I
ω
(
i
)
f
ω
(
i
)
∑
i
=
0
n
-
1
I
ω
(
i
)
(
1
)
[0000] Where ω is the frequency band under analysis, n is the number of frequency bins in ω, f i is the frequency at bin i and I i is the energy density of ω at frequency bin i
[0050] In a single window, the maximum and average powers of all the mean frequencies are extracted for both trial and baseline. Finally the feature vector is computed with the peak and average energy shifts (ΔE Ii max , ΔE Ii avg ), the corresponding frequency shifts (Δf Ii max , Δf Ii avg ) between the baseline and trial in the frequency band i for channel I. Here both alpha (α) and theta (θ) bands are considered. The feature vectors used are given by (2), where F I peak and F I mean respectively denote the feature vectors comprising features computed from maximum and average powers of all the mean frequencies for channel I.
[0000]
F
peak
I
=
{
Δ
E
max
I
,
a
,
Δ
f
max
I
,
a
,
Δ
E
max
I
,
θ
,
Δ
f
max
I
,
θ
,
L
max
I
}
F
mean
I
=
{
Δ
E
avg
I
,
a
,
Δ
f
avg
I
,
a
,
Δ
E
avg
I
,
θ
,
Δ
f
avg
I
,
θ
,
L
avg
I
}
}
,
1
≤
I
≤
14
(
2
)
[0000] where L 1 max or L 1 avg is defined as the cognitive load, computed taking maximum or average powers respectively and 1≦I≦14 denotes the 14 leads of the Emotiv EEG device. The final feature vectors F peak and F mean are obtained by concatenating the vectors F I peak or F I mean respectively for all I. Feature selection is performed to select a subset of the above EEG features. If f is the number of features per channel of EEG data then the feature vectors from all 14 channels are concatenated to form R 14f dimensional feature vector.
[0051] The ECT or stimulus is categorized according to Bloom's categories; Table 1 below depicts mapping of stimulus or ECTs to identified Bloom's categories, namely Understand, Remember and Analyze. However, it has to be understood that the identification of three given Bloom's categories is only for exemplary purposes. Similar mapping can be done for Bloom's six categories namely remember, understand, apply, analyze, evaluate and create.
[0000]
TABLE 1
Mapping Stimuli to Bloom's Categories
Relationship to
Stimulus
Task Details
Measure
Bloom's category
1. Scattered
Find number of
Perceptual
Understand &
X's (SX)
times ‘X’
Speed
Remember
appears on
screen
2. Finding A
Count words
Perceptual
Analyze &
(FA)
containing ‘a’
Speed
Remember
from a full page
of words
3. Hidden
Find a target
Flexibility of
Analyze
Pattern (HP)
pattern from a
closure
list of five
complex
patterns
4. Visual
Count the
Perceptual
Understand &
Pursuit (VP)
number of
Speed
Remember
occurances of a
target image
from an array of
multiple
complex images
5. Finding
Count the non-
Perceptual
Understand &
Number
matching
Speed
Remember
(FN)
number pairs
from a list of
number pairs
6. Gestalt
Look at an
Speed of
Understand
closure test
incomplete
closure
(GC)
image and
identify the
object
[0052] The EEG signals are first cleaned from various artifacts and then analyzed using standard machine learning techniques. Having also identified the cognitive categories within the Bloom's taxonomy and mapped plurality of ECTs with identified cognitive domains of Bloom's taxonomy, a cluster analysis is performed on the features of EEG signals using K-means algorithm. An unsupervised approach has been adapted to objectively measure the effects of various ECTs on individual subjects.
[0053] An optimum number of clusters for an individual are identified by performing K means based clustering on the EEG features. Referring to afore-given non limiting description of illustrative embodiment wherein 6ECTs have been identified, the K is varied from 2 to 10. The value of K that generates compact clusters and also separates the clusters well, is determined using the minimum Xie-Beni index, in accordance with one exemplary embodiment of present disclosure. Further, relationships between the dusters in terms of distance between the centroids and the insights with the Bloom's categories are determined. It should however be noted that the scope of the invention is in no way limited to this example, and alternative variations of this task or given ECTs are possible and included within the scope of the invention.
[0054] Let, referring to above example, the maximum number of minimum time response is obtained in the task “Finding A” (FA) and maximum number of maximum time response is obtained in “Visual Pursuit” (VP) task. Similarly let maximum accuracy is achieved in FA and minimum accuracy is achieved for “Hidden Pattern” (HP). Thus FA provides maximum accuracy at minimum response time.
[0055] For exemplary purposes, all the tasks are of comparable load with a slight variation in their spread. As all the ECTs impart similar levels of cognitive load upon the subjects, the choice for the stimuli is justified.
[0056] Next, a feature selection is performed on the total feature list given in equation (2) above. Maximal Information Co-efficient (MIC) is used to choose the most appropriate feature subset among F I peak and F I mean . The MIC score of the corresponding peak (F I peak ) and mean (F I mean ) feature ratios in logarithmic unit is shown in FIG. 3 . The positive values indicate that F I peak is a better subset. Here individual features' MIC values are averaged across all 14 channels and then summed over all the participants.
[0057] While performing the duster analysis, firstly the effects of taking peak energy and frequency shifts, average energy and frequency shifts or both in the feature vector are analyzed. This is illustrated in FIG. 4 . It can be observed that taking a five dimensional feature vector F peak gives the best clustering performance (in terms of smaller Xie Beni Indices) compared to F mean or a ten dimensional feature vector F both , where F both ={F peak , F mean )}. Hence all further analyses are carried out using only F peak as feature.
[0058] As can be seen from Table II below, results obtained from clustering analysis in terms of Xie-Beni indices have been summarized.
[0000] TABLE II XIE BENI INDEX FOR DIFFERENT SUBJECTS AND FEATURES Subject Features (K min ) F1 F2 F3 F4 F5 F6 F7 S1 (6) 1.9786 1.0073 2.2869 0.9156 1.0671 0.8103 0.8366 S2 (6) 1.7380 0.7125 0.8235 0.8935 0.7652 0.6745 0.6413 S3 (6) 1.7120 0.6637 1.1722 0.8462 1.2651 0.9040 0.7244 S4 (6) 1.3938 0.3777 1.2208 0.4630 1.2085 0.5866 0.3305 S5 (6) 1.3834 0.7948 0.9361 0.5566 1.6100 0.6423 0.5830 S6 (6) 2.3961 1.0465 0.9508 0.7961 2.4843 0.9268 0.7878 S7 (2) 0.8770 0.1607 1.2089 0.1583 0.9118 0.6000 0.1648 S8 (6) 1.0398 0.4943 1.1652 0.8390 1.0400 0.7440 0.6183 S9 (6) 1.2961 0.9185 1.5184 0.9483 0.8828 0.7383 0.8391 S10 (6) 1.7442 0.6232 1.5616 0.6209 0.8355 0.7891 0.5216
Here F 1 to F 5 , denote the following features:
F 1 =L 1 max , F 2 =ΔE I,α max , F 3 =Δf I,α max , F 4 =ΔE I,θ max , F 5 =Δf I,θ max
F 6 is a combination of the F 1 through F 5 while F 7 is a combination of F 2 and F 4 . It is found that 9 subjects show the best performance i.e. lowest Xie-Beni index for K=6 while only one shows better results with K=2. These are reported as K min in Table II. Also it is found that compared to using the F 6 , only F 2 for subjects S3, S4, S8 and S10; or only F 4 for subjects S5, S6 and S7 gives better results. Thus feature F 7 is selected as it gives a better performance compared to F 6 for eight out of ten subjects.
[0059] Next the distance between cluster centroids for each ECTs is computed. Let, say that for K number of clusters, K C 2 different combinations of distances between clusters are obtained. From the given number of combinations, the duster centers having minimum and maximum distance for each individual are identified. A study on these distance pairs with respect to relation with Bloom's categories is presented in Table III. Here the attempt is to group subjects with similar relative cognitive skills. As for example, it can be seen from the Table III that it can be inferred for S1, S2 and S3 the FN-HP pair is having minimum distance i.e. maximum similarity. Here, S7 is neglected as number of clusters with minimum Xie-Beni index is 2 which is different from all the remaining subjects.
[0000]
TABLE III
Cluster centers with minimum and maximum distances
Pair with min/max
distance between
Subjects
centroids
Remarks
S1
Min: FN-HP
Min: Though they are from separate
Max: SX-VP
categories, the subject treats number as
a pattern.
Max: Though both are in same category,
the alphabets and shapes are treated
differently.
S2
Min: FN-HP
Min: Though they are from separate
Max: FN-GC
categories, the subject treats number as
a pattern.
Max: Same categories but FN needs
remembering also.
S3
Min: FN-HP
Min: Though are from separate
Max: FN-GC
categories, the subject treats number as
a pattern.
Max: Same categories but FN needs
remembering also
S4
Min: FA-SX
Min: Different category but, searching
Max: FN-GC
“A” (in FA) is similar to searching
“X” (in SX).
Max: Same categories but FN needs
remembering also
S5
Min: GC-VP
Min: They are from same category and
Max: FN-VP
are treated similarly as both are related
to patterns.
Max: Same category but the numbers
and patterns are treated differently.
S6
Min: GC-VP
Min: They are from same category and
Max: GC-HP
are treated similarly as both are related
to patterns.
Max: Separate categories.
S8
Min: FN-VP
Min: Same category - numbers and
Max: GC-HP
patterns are treated similarly.
Max: Separate categories.
S9
Min; FN-SX
Min: Same category - numbers and
Max: FN-HP
patterns are treated similarly.
Max: Separate categories.
S10
Min: SX-VP
Min: Same category - the “X” (in SX) is
Max: SX-GC
treated as a pattern as in VP.
Max: Same category but for SX, user
needs to remember as well.
[0060] Following the unsupervised cluster analysis on the EEG features for segregating the cognitive categories, one or more metrics are introduced for EEG based identification of the Traits of Cognitive Perception (TCP) among different individuals. In one aspect of the disclosure, if C i and C j be the centers of the i th and the j th clusters respectively for a particular subject, the separation Index (SI i,j ) between these two clusters is given as (3), where ∥.∥ denotes the Euclidean Distance between them.
[0000] SI i,j =∥C i −C j ∥ (3)
[0000] If, say there are N number of clusters formed, N C 2 pair-wise SI i,j values are obtained. Next, search is made for the pair of dusters that lead to the maximum and minimum separation index values SI min and SI max for each subject. Further, the ratio S r of SI min upon SI max is computed as can be seen in equations. (4), (5) and (6) below.
[0000] SI min =minimum( S i,j ) (4)
[0000] SI max =maximum( S i,j ) (5)
[0000] S r =SI min /SI max (6)
[0061] The above obtained SI min , SI max and S r values are used as metrics to identify the TCP of a particular subject. While, it is obvious that SI min (or SI max ) determines the how similarly (or dissimilarly) a subject treats the pair of tasks, S r determines the spread of cognitive perception. A value of S r close to 1 indicates almost similar interpretation of all tasks by the subject. This pertains to the subject wise study of TCPs. Now, depending on the SI min , SI max and S r values across all subjects, they are grouped into different categories of TCPs. This amounts to the stimulus-wise study of TCPs across all subjects.
[0062] Likewise, a similar approach can be used to analyze a new task (say T new ). In such a scenario a set of subjects are considered who belong to the same group of TCP. Then the EEG signal is captured by presenting the new task. The EEG signals are analyzed to understand the relative structure with respect to the C i . Assuming that there are N ECTs, then 1<=i<=N. The centroid of the EEG features for the T new is C new . Then the weight of each ECT present in the new task is given by equation (7) as follows.
[0000]
W
i
=
1
-
C
i
-
C
new
∑
i
=
1
N
(
C
i
-
C
new
)
(
7
)
[0063] In the interest of clarity, not all of the routine features of the implementations of the perceptual-cognitive-system and method are shown and described. It will, of course, be appreciated that in the development of any such actual implementation of the perceptual-cognitive system and method, numerous implementation-specific decisions may need to be made in order to achieve the system specific goals, and that these specific goals will vary from one implementation to another and from one application area to another.
[0064] It is to be understood that the invention is not limited in its application to the details of construction and parts illustrated in the accompanying drawings and described herein-above. The invention is capable of other embodiments and of being practiced in various ways. It is also to be understood that the phraseology or terminology used herein is for the purpose of description and not limitation. Hence, although the present invention has been described hereinabove by way of illustrative embodiments thereof, it can be modified at will, within the scope of the appended claims, without departing from the spirit, scope and nature of the subject invention. | The present disclosure envisages a computer implemented system and method to derive a relationship between Elementary Cognitive Tasks (ECTs) and the underlying cognitive skills of individuals through Electroencephalogram (EEG) analysis. The aim is to evaluate or improve the perceptual-cognitive traits of a subject that comprises disintegrating a given task into elementary task that are further mapped to identified cognitive categories of Bloom's Taxonomy, upon which a cluster analysis is performed. The separation index between the clusters thereafter establishes that individuals have different thinking process which is characteristics of that subject. | 6 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is based upon and claims benefit of copending U.S. Provisional Patent Application Ser. No. 62/026,249 entitled “WELDED ROOF FOR MODULAR BUILDING UNITS,” filed with the U.S. Patent and Trademark Office on Jul. 18, 2014 by the inventor herein, the specification of which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] This invention relates generally to modular building construction, and more particularly to a welded roof assembly for a modular building unit configured to receive various gutter system configurations.
BACKGROUND OF THE INVENTION
[0003] Roofing members for modular buildings are typically attached by way of screws or other fasteners, and are supplied in sheets arranged in a tile configuration with a portion of one roofing sheet overlapping a portion of an adjacent roofing sheet. In order to channel rainwater and water from snow and ice melt away from the modular building, gutters may be provided along the edges of the modular building unit. However, the type of gutter assembly, and in fact whether a gutter system is required at all, can vary from location to location based upon annual weather patterns, and particularly rain, snow, and ice amounts received in a given area. Different weather patterns may call for different gutter configurations, and at times even no gutter. Moreover, even with water diversion and drainage, conditions may result in water collecting on the roof and leaking into the modular building unit, such as through gaps between adjacent roofing sheets, gaps between the roofing sheets and the frame of the modular building unit, openings around fasteners, and the like. While silicone or other fillers may be provided, they are temporary and subject to failure and leakage over time. While differing gutter configurations may be provided to address different rain, snow, and ice conditions, they will require varied adaptations of the roof structure as well in order to accommodate the varied environmental conditions.
[0004] Thus, there remains a need in the art for a roofing configuration for a modular building unit that is able to accept gutters of varied configurations without requiring adaptation or modification of the building unit structure, and that protects against water leakage through the roof in all such gutter configurations, and in the case of no gutter.
SUMMARY OF THE INVENTION
[0005] Disclosed is a roof assembly for a modular building unit that comprises a roofing sheet that is welded to the frame of the modular building unit so as to form a unitary, continuous sealed weld between the roofing sheet and the structural frame of the modular building unit, and that is pitched to downwardly direct water on the roofing sheet toward one end of the modular building unit. The welded roof assembly prevents water infiltration into the modular building unit, and such watertight structure may then receive any gutter configuration the user wishes to implement without risking water infiltration into the building unit. Further, the welded roof assembly allows the modular building unit to carry a heavy snow load, as the welds attaching the roofing sheet can easily carry heavy loads. The welded roofing sheet avoids the use of screws, and the associated possibility of water leakage around the screws and into the building unit. The welded roof also permits attachment, e.g. via welding, of safety rings or other accessories directly on the roof sheet without need for specialized holes or other configurations or specific location requirements. The welded roof also is able to employ a single slope all of the way through the full span of the roof, thus avoiding the need for a centrally pitched roof assembly, and its unitary construction avoids the tiling effect that results from the use of multiple, overlapping roofing sheets. The welded roof also avoids the need for silicon or other filler agents between the unitary roofing sheet and the frame of the modular building unit. Still further, the recessed roofing panel within the exterior frame formed by the upper rails of the building unit, along with the horizontal top surfaces of such rails, provided for easy vertical stacking of modular building units atop one another.
[0006] In accordance with certain aspects of an embodiment of the invention, a roof assembly is provided for a modular building unit, comprising: a first long rail having a top wall, an exterior wall, and an interior wall; a second long rail parallel to the first long rail and having a top wall, an exterior wall, and an interior wall; a first short rail extending between the first and second long rails and having a top wall, an exterior wall, and an interior wall; a second short rail extending between the first and second long rails and having a top wall and an exterior wall, wherein the first and second long rails and the first and second short rails are joined to form a rectangular exterior roof frame of a modular building unit; and a roofing sheet, wherein the roofing sheet is joined to the first short rail at a first elevation below the top wall of the first short rail, the roofing sheet is joined to each of the first and second long rails at a point below the top wall of each of the first and second long rails and extending in a downward slope from the first elevation, and the roofing sheet is joined to the top surface of the second short rail at a lowest elevation of the roofing sheet; and wherein the roofing sheet is joined to the first short rail, each of the first and second long rails, and the top surface of the second short rail by a continuous weld.
[0007] In accordance with further aspects of an embodiment of the invention, a method of forming a roof assembly for a modular building unit is provided, comprising the steps of: providing a roof frame comprising a first long rail having a top wall, an exterior wall, and an interior wall; a second long rail parallel to the first long rail and having a top wall, an exterior wall, and an interior wall; a first short rail extending between the first and second long rails and having a top wall, an exterior wall, and an interior wall; and a second short rail extending between the first and second long rails and having a top wall and an exterior wall, wherein the first and second long rails and the first and second short rails are joined to form a rectangular exterior roof frame of a modular building unit; joining a roofing sheet to the first short rail at a first elevation below the top wall of the first short rail; joining the roofing sheet to each of the first and second long rails at a point below the top wall of each of the first and second long rails and extending in a downward slope from the first elevation; and joining the roofing sheet to the top surface of the second short rail at a lowest elevation of the roofing sheet; wherein the steps of joining the roofing sheet to the first short rail, each of the first and second long rails, and the top surface of the second short rail is performed by making a continuous weld.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] The numerous advantages of the present invention may be better understood by those skilled in the art by reference to the accompanying drawings in which:
[0009] FIG. 1 is a perspective view of a modular building unit in accordance with certain aspects of an embodiment of the invention.
[0010] FIG. 2 is a perspective view of a skeletal frame of the modular building unit of FIG. 1 .
[0011] FIG. 3 is a cross-sectional view of the skeletal frame of FIG. 2 .
[0012] FIGS. 4 a through 4 d are close-up, cross-sectional views of the lower roof edge of the frame of FIG. 3 with varying gutter configurations.
[0013] FIG. 5 is a top view of a roof portion of the modular building unit of FIG. 1 .
[0014] FIG. 6 is a perspective view of the roof portion of FIG. 5 .
[0015] FIG. 7 is a close-up, detail cross-sectional view of the frame of FIG. 3 .
[0016] FIG. 8 is a cross-sectional view of a first, higher elevation top short rail of the frame of FIG. 7 .
[0017] FIG. 9 is a perspective view showing connection of the first top short rail and one of the top long rails of the frame of FIG. 7 .
[0018] FIG. 10 is a cross-sectional view of a roofing sheet short side mounting bracket of the frame of FIG. 7 .
[0019] FIG. 11 is a perspective view of the roofing sheet short side mounting bracket of FIG. 10 .
[0020] FIG. 12 is a close-up, detail cross-sectional view of the frame of FIG. 3 along an axis parallel to the first top short rail (showing the long rails in cross-section).
[0021] FIG. 13 is a perspective view of a roofing sheet long side bracket 146 for a first long side of the frame of FIG. 7 .
[0022] FIG. 14 is a rear view of the roofing sheet long side bracket of FIG. 15 .
[0023] FIG. 15 is a cross-sectional view of the roofing sheet long side bracket of FIG. 14 along section line A-A.
[0024] FIG. 16 is a cross-sectional view of the roofing sheet long side bracket of FIG. 14 along section line B-B.
[0025] FIG. 17 is a cross-sectional view of a second, lower elevation top short rail of the frame of FIG. 7 .
[0026] FIG. 18 is a perspective view showing connection of the second top short rail and one of the top long rails of the frame of FIG. 17 .
[0027] FIG. 19 shows an external gutter and drain pipe for use with the roof portion of FIG. 6 .
[0028] FIG. 20 is a cross-sectional view of the gutter and drain pipe of FIG. 19 attached to second top short rail of the frame of FIG. 7 .
[0029] FIG. 21 shows an external water deflector for use with the roof portion of FIG. 6 .
[0030] FIG. 22 is a cross-sectional view of the water deflector of FIG. 21 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0031] The following description is of a particular embodiment of the invention, set out to enable one to practice an implementation of the invention, and is not intended to limit the preferred embodiment, but to serve as a particular example thereof. Those skilled in the art should appreciate that they may readily use the conception and specific embodiments disclosed as a basis for modifying or designing other methods and systems for carrying out the same purposes of the present invention. Those skilled in the art should also realize that such equivalent assemblies do not depart from the spirit and scope of the invention in its broadest form.
[0032] FIG. 1 provides a perspective view of a modular building unit 100 in accordance with certain aspects of an embodiment of the invention. Modular building unit 100 includes a skeletal frame formed by corner support posts 112 , bottom rails 114 , top long rails 115 , a first top short rail 116 (shown in FIG. 2 ), and a second top short rail 117 . This skeletal frame provides the key structural integrity for the modular building unit. Positioned between corner support posts 112 , bottom rails 114 , and top rails 115 , 116 and 117 are wall panels 118 that form the wall structures spanning each side of the modular building unit. Other standard building features, such as doors 120 and windows 122 , may be provided and integrated with individual wall panels 118 .
[0033] FIG. 2 is a perspective view of the skeletal frame forming the modular building unit of FIG. 1 . As shown in FIG. 2 , the skeletal frame comprises four corner posts 112 extending upward from bottom rails 114 and supporting the roof portion of the modular building unit 100 . The roof portion includes top long rails 115 extending lengthwise between adjacent corner support posts 112 , a first top short rail 116 extending between adjacent corner supports posts 112 and generally perpendicular to top long rails 115 , and a second top short rail 117 extending between adjacent corner support posts 112 and generally perpendicular to top long rails 115 . A roofing sheet 140 forms the exterior roof of the modular building unit, and sits within the interior of the frame defined by top long rails 115 , first top short rail 116 , and second top short rail 117 . Roofing sheet 140 may have a thickness of preferably 1 to 3 mm, and more preferably 2 mm, and may either comprise a flat sheet or a corrugated sheet comprised of continuous or segmented ribs as shown in FIG. 2 . If corrugated (which may be desirable depending upon typical roof rain and snow loads in the locale where the modular building unit is to be installed), ribs from the corrugated sheet may help with drainage of water. The roofing sheet 140 is welded around its entire perimeter to top long rails 115 , first top short rail 116 , and second top short rail 117 , all as discussed in greater detail below, to ensure complete water tightness, particularly in the case of snow and ice. Roofing sheet 140 is also welded, such as by spot welding, to purlins 124 spanning the width of the roof portion and extending between parallel top long rails 115 , again as discussed in greater detail below.
[0034] Moreover, and as better shown in the cross-sectional view of the skeletal frame of FIG. 3 , roofing sheet 140 slopes downward from first top short rail 116 to second top short rail 117 so as to direct all water to the lowest elevation of the roof portion of the modular building unit. In order to provide such downward slope, purlins 124 are positioned at progressively lower elevations, with each end of each purlin being rigidly affixed (e.g., welded) to an interior face of each top long rail 115 . Such configuration results in roofing sheet 140 realizing a downward slope of preferably between 0.5% and 5% from one end of the module to the other. In certain configurations, roofing sheet 140 may have two, opposite sloping sections (not shown), each having a downward slope of 0.5% to 5% from the middle of the modular building unit to the end of the modular building unit.
[0035] Because the modular building unit is configured with a fully welded roof, the modular building unit may be configured with varied gutter options, including no gutter. Those varying gutter options are shown in the exemplary configurations reflected in FIGS. 4 a through 4 d . FIG. 4 a shows the lowest roof edge of modular building unit 100 , including roofing sheet 140 welded directly to the top face of second top short rail 117 , which in turn is mounted above wall panel 118 . In this configuration, no gutter is provided, in which case water from the room will directly flow off of the roof, while the weld around the perimeter of roofing sheet 140 prevents infiltration of water into the modular building unit. Next, FIG. 4 b shows the same roof edge of modular building unit 100 , with a water deflector 200 attached to the exterior face of second top short rail 117 , which deflector 200 may aid in directing water flowing from the roof away from the side wall panels 118 of modular building unit 100 . Likewise, FIG. 4 c shows the same roof edge of modular building unit 100 , with gutter 190 attached to the exterior face of second top short rail 117 , which gutter 190 may receive water flowing from the roof and direct such water to a downspout (not shown) as discussed further below. Similarly, FIG. 4 d shows the same roof edge of modular building unit 100 , with an alternative gutter 119 a attached to the exterior face of second top short rail 117 , which alternative gutter 119 a is attached in the same manner as gutter 119 but embodies a decorative design to improve the overall aesthetic appearance of the modular building unit 100 . Those of ordinary skill in the art will recognize that gutter assemblies of other varying configurations may likewise be provided without departing from the spirit and scope of the invention.
[0036] FIG. 5 provides a top view, and FIG. 6 provides a perspective view, of the roof portion of modular building unit 100 . Roofing sheets 140 are shown spanning the full length of the roof, and as mentioned above, may optionally include ribs 142 that may aid in directing water toward the lowest elevation point on the roof (i.e., toward second top short rail 117 ). Optionally, roofing sheets 140 may be provided in separate sections, in which each of the sections are preferably welded together to form the same waterproof, welded seam that is provided along the perimeter of roofing sheet 140 . Mounting brackets are provided at the interior faces of each of first top short rail 116 and the two top long rails 115 . More specifically, roofing sheet short side mounting bracket 144 is affixed to and runs parallel to first top short rail 116 , and roofing sheet long side brackets 146 are affixed to and run parallel to each top long rail 115 . Roofing sheet short side mounting bracket 144 provides a horizontal mounting and welding surface for the highest elevation portion of roofing sheet 140 , while roofing sheet long side brackets 146 provide a downwardly angled mounting and welding surface for the long edges of roofing sheet 140 , resulting in the roofing sheet 140 following a downward slope from first top short rail 116 to second top short rail 117 . The lowest elevation point of roofing sheet 140 is welded directly to the top surface of second top short rail 117 , again allowing water on roofing sheet 140 to flow directly onto and over second top short rail 117 .
[0037] Corner boxes 119 may be provided at each corner of the roof portion of modular building unit 100 , which corner boxes 119 principally serve as corner elements for joining each perpendicular pair of rails and one of corner support posts 112 . Corner boxes 119 may also be provided features, such as openings, in the top and side walls of each corner box 119 to receive a crane hook or other device to aid in lifting the entire modular building unit when necessary for transport or installation.
[0038] FIG. 7 provides a close-up, detailed cross-sectional view of the skeletal frame of modular building unit 100 . First top short rail 116 is shown at the left most portion of FIG. 7 , with roofing sheet short side mounting bracket 144 extending from the interior face of first top short rail 116 and supporting roofing sheet 140 . The underside of roofing sheet 140 overlaps a portion of roofing sheet short side mounting bracket 144 and is welded to short side mounting bracket 144 . Likewise, as roofing sheet 140 extends toward second top short rail 117 , it rests on and is preferably welded to purlins 124 . At the opposite end from first top short rail 116 (i.e., the right edge as viewed in FIG. 7 ), roofing sheet 140 overlaps a portion of second top short rail 117 and is welded to the top of second top short rail 117 .
[0039] Other features, including sealed joints attaching the overall roof portion to wall panels 112 , interior ceiling trays, and subfloor construction details, are shown in FIG. 7 but are not critical to the roofing structure of the instant invention, and thus are not described further here.
[0040] FIG. 8 is a cross-sectional view of first top short rail 116 , and FIG. 9 is a perspective view of first top short rail 116 connecting to one of top long rails 115 through a connecting corner box 119 . As shown in FIGS. 8 and 9 , first top short rail 116 has a planar top face 150 , a planar outer face 152 that forms a portion of the exterior side wall of modular building unit 100 , interior bracket flange 154 , and bottom profile 156 to fit with a modular wall panel as shown in FIG. 7 . Interior bracket flange 154 extends downward from the interior edge of planar top face 150 , and provides an attachment surface for roofing sheet short side mounting bracket 144 .
[0041] FIG. 10 provides a cross-sectional view of roofing sheet short side mounting bracket 144 , and FIG. 11 provides a perspective view of such roofing sheet short side mounting bracket 144 . Bracket 144 comprises a back wall 170 configured for attachment, such as by welding, to interior bracket flange 154 of first top short rail 116 . Bracket 144 also has a short side roofing sheet support surface 172 which, when bracket 144 is mounted on first top short rail 116 , extends generally horizontally and parallel to planar top face 150 of first top short rail 116 . Support surface 172 supports the highest elevation end of roofing sheet 140 , with the underside of roofing sheet 140 resting on the top side of support surface 172 and the two being joined by a continuous weld. Bracket 144 may also include a top lip 174 extending generally parallel to short side roofing sheet support surface 172 , which top lip 174 limits the opportunity for wind to blow water onto top short rail 116 , so that water remains contained on roof sheet 140 . Further, corner notches 176 are provided at opposite ends of support surface 172 to allow contact with edges of roofing sheet long side brackets 146 , in order to provide a continuous surface to receive a continuous weld around the entire perimeter of roofing sheet 140 .
[0042] Next, FIG. 12 provides a cross-sectional view of the skeletal frame of modular building unit 100 along an axis parallel to first top short rail 116 (showing the top long rails 115 in cross section). Top long rails 115 are of generally the same cross-sectional configuration as first top short rail 116 (although obviously with a longer overall length dimension). Roofing sheet long side mounting brackets 146 are affixed (e.g., welded) to interior bracket flange 154 of long rails 115 and support roofing sheet 140 along its long edge. The underside of the long edge of roofing sheet 140 overlaps a portion of roofing sheet long side mounting brackets 146 and is welded to long side mounting brackets 146 . Likewise and as mentioned above, roofing sheet 140 is supported by and is preferably welded to purlins 124 for additional support.
[0043] FIG. 13 is a perspective view of a roofing sheet long side bracket 146 for attachment to a first one of top long rails 115 . Those of ordinary skill in the art will appreciate that the opposite top long rail 115 will receive a similarly configured long side bracket 146 that is the mirror image of the bracket shown in FIG. 13 . Likewise, FIG. 14 is a rear view of roofing sheet long side bracket 146 . Further, FIG. 15 provides a cross-sectional view of bracket 146 along section line A-A of FIG. 14 , and FIG. 16 provides a cross-sectional view of bracket 146 along section line B-B of FIG. 14 . As shown in FIGS. 13 through 16 , bracket 146 includes a back wall 180 providing an attachment surface for attaching (e.g., welding) bracket 146 to interior bracket flange 154 of top long rails 115 . Back wall 180 has a generally horizontal top edge and a downwardly sloping bottom edge. Likewise, bracket 146 has a long side roofing sheet support surface 182 which, when each bracket 146 is mounted on its respective top long rail 115 , extends outward from back wall 180 and provides a downwardly sloping support surface for the long edge of roofing sheet 140 , with the underside of such long edge of roofing sheet 140 resting on the top side of support surface 182 and the two being joined by a continuous weld. Such continuous weld seamlessly extends from the weld joining the highest elevation portion of roofing sheet 140 to short side roofing sheet support surface 172 . Bracket 146 may also include a top lip 184 extending generally parallel to top long rails 115 , again serving to keep water from being blown off of roofing sheet 140 .
[0044] FIG. 17 shows a cross-sectional view of second top short rail 117 , and FIG. 18 is a perspective view of second top short rail 117 connecting to one of top long rails 115 through a connecting corner box 119 . As shown in FIGS. 17 and 18 , second top short rail 117 has a planar top face 160 configured to directly receive an overlapping portion of the lowest elevation section of roofing sheet 140 . As noted above, roofing sheet 140 is welded directly to such planar top face 160 of second top short rail 117 , and such weld seamlessly continues from the weld attaching roofing sheet 140 to each of roofing sheet short side mounting bracket 144 and roofing sheet long side brackets 146 . Second top short rail 117 also has a planar outer face 162 which is configured to directly receive various gutter configurations as discussed in greater detail below, or alternatively to form a portion of the exterior side wall of modular building unit 100 (in cases where no gutter system is to be used). Second top short rail 117 further includes planar interior face 164 and a bottom profile 166 to fit with a modular wall panel as shown in FIG. 7 .
[0045] FIG. 19 shows an external gutter 190 for use with the welded roof described above. External gutter 190 may include a plurality of overflow openings 192 provided on the outermost wall of gutter 190 , and a spigot 194 at one end of gutter 190 . Spigot 194 is shaped to fit within a drain pipe 196 , which drain pipe may be joined to modular building unit 100 with, by way of non-limiting example, an angle bracket 198 , such as to one of corner support posts 112 that is adjacent to second top short rail 117 . Likewise, FIG. 20 shows a cross-sectional view along section line C-C of FIG. 19 of the gutter 190 and drain pipe 196 , with external gutter 190 attached to second top short rail 117 with one or more fasteners 199 , such as a screw.
[0046] Similarly, FIG. 21 shows an external water deflector 200 for use with the welded roof described above, and FIG. 22 provides a cross-sectional view of such water deflector 200 . With reference to both FIGS. 21 and 22 , water deflector 200 has a back wall 202 that is configured for facing attachment to planar outer face 162 of second top short rail 117 , a plurality of openings 204 for receiving connectors (e.g., screws) for such attachment, and an upper angle 206 configured to direct water outward and away from the edge of the roof of modular building unit 100 as it flows off of the roof.
[0047] The foregoing configuration results in a modular building unit having a roof structure that may readily receive a variety of gutter configurations, and that is simultaneously effective with no gutter, in an assembly that protects against water infiltration into the modular building unit regardless of the gutter configuration. Thus, a single modular building unit configuration may be provided in geographies having widely varied rain and snow conditions, with gutters being added (or not) depending upon the specific precipitation conditions of that particular environment, saving the user from having to maintain multiple configurations for differing environements.
[0048] Having now fully set forth the preferred embodiments and certain modifications of the concept underlying the present invention, various other embodiments as well as certain variations and modifications of the embodiments herein shown and described will obviously occur to those skilled in the art upon becoming familiar with said underlying concept. It should be understood, therefore, that the invention may be practiced otherwise than as specifically set forth herein. | Disclosed is a roof assembly for a modular building unit that comprises a roofing sheet that is welded to the frame of the modular building unit to form a unitary, continuous sealed weld between the roofing sheet and the generally horizontal structural frame of the modular building unit, and that is pitched to downwardly direct water toward one end of the modular building unit. The welded roof assembly prevents water infiltration into the modular building unit, and such watertight structure may then receive any gutter configuration the user wishes to implement without risking water infiltration into the building unit. The welded roofing sheet avoids the use of screws or other fasteners, and the associated possibility of water leakage around the screws and into the building unit. The welded roof also is able to employ a single slope all of the way through the full span of the roof, thus avoiding the need for a centrally pitched roof assembly, and its unitary construction avoids the tiling effect that results from the use of multiple, overlapping roofing sheets. The welded roof also avoids the need for silicon or other filler agents between the unitary roofing sheet and the frame of the modular building unit. | 4 |
This application is a continuation, of application Ser. No. 747,423 filed on June 21, 1985 now abandoned.
FIELD OF THE INVENTION
The present invention relates to method and apparatus for state analysis and, more particularly, to method and apparatus for state analysis directed to a line analysis or a two-dimensional scanning image based on elemental state data, such as the chemical bonding state, of elements contained in specimens.
An Electron Probe Micro Analyzer (EPMA) or so is operated to apply electron beam or X-rays as exciting source to the specimens, so that the intensity of characteristic X-rays emitted from the specimens is measured to obtain the elemental data.
DESCRIPTION OF THE PRIOR ART
Conventionally, the EPMA for analyzing the surface state of a specimen is so operated that it irradiates electron beam to the surface of the specimen and detects characteristic X-rays from micro area of about 1 μm to obtain elemental analysis data of the specimen.
Basically, the EPMA is designed and constructed so as to analyze elements, but not to directly analyze any compound. Therefore, even if a specimen contains Fe metal, FeO, Fe 3 O 4 , and Fe 2 O 3 , all of them are detected and equally treated in terms of Fe elemental spectra in the EPMA. However, the spectrum of the characteristic X-rays detected by the EPMA can be changed by the state (mainly, chemical bonding state) of the respective elements in the specimen. Therefore, it may be possible to carry out the state analysis by detecting the change of the spectrum of the characteristic X-rays. Unfortunately, the degree of the spectra change of the characteristic X-rays is normally too small to collect data necessary for the state analysis even when the spectrometer is set in a specific wavelength of the characteristic X-ray with scanning the electron beams.
In view of this, the so-called "point analysis" is carried out wherein the spectrometer is operated to respond to a plurality of wavelengths emanating from a point in connection with an element to be analyzed so as to obtain peak profiles and analyze the wavelength spectra.
Normally, a two-dimensional scanning image in only some specific chemical bonding state cannot be obtained except for some peculiar cases such as in sulfides and sulfuric acids, or CuO and Cu 2 O. The reason is that in the peculiar cases, different inherent peak can appear, being separated depending on the chemical bonding state in L-emission band spectra of sulfur, or Oxygen K-emission band spectra of copper oxides. In these cases, when the spectrometer is set in either inherent peak wavelength, the two-dimensional state distribution image can be given. Such a method, however, is not applicable to the normal cases because the peaks inherent to the element state can rarely appear in the ordinal wavelength of the EPMA (about 1 through 100 Å).
It may be possible in principle that a great number of point analyses are carried out in connection with the respective measurement points of the specimen to analyze their spectra, automatically with a computer. However, in the case of line analysis and the two-dimensional scanning image, the measurement points are about several hundreds to several tens of thousands, so that the operation time and the memory capacity become vast.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide improved method and apparatus for performing a state analysis of elements.
It is another object of the present invention to provide improved method and apparatus for carrying out a line analysis or obtaining a two-dimensional scanning image in substantially real time.
It is a further object of the present invention to provide an improved apparatus being capable of carrying out a line analysis or a two-dimensional scanning image with apparatus of a simple construction.
Other objects and further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. It should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
To achieve the above objects, pursuant to embodiment of the present invention, a state analysis method is characterized in that the intensity or energy level (amplitude) of characteristic X-rays emitted from one or more measurement points of a specimen is detected for two different predetermined spectral wavelengths previously selected by a spectrometer depending on a specific state of an element to be analyzed. The intensity or amplitude values in a single spectrum (the number of photons) in respect to different energy positions is obtained. If the intensity ratio i.e. the ratio of the amplitude values of the respective X-ray energies detected at the two selected wavelengths falls within a predetermined range selected according to the specific state of the element in some measurement points, state detection signals detected only at those measurement points are outputted to display a line analysis or a two-dimensional scanning image. According to the state analysis method of the present invention, the spectral intensity ratio detected with the two different wavelengths selected is used to detect the change of the spectrum in order to determine the state.
A state analysis apparatus of the present invention comprises two wavelength dispersive spectrometers and a comparator. The two wavelength dispersive spectrometers are set to different wavelengths of characteristic X-rays to meet with specific state of the element to be analyzed. The comparator is operated to compare the intensity or energy level (amplitude) of the characteristic X-rays detected at the two wavelengths by the spectrometers with each other and determines whether the intensity ratio of the amplitude values falls within a predetermined range. Only when the intensity ratio falls within the range, the comparator outputs state detection signals.
Further, according to the present invention, one wavelength dispersive spectrometer comprises a wavelength dispersion crystal and a position sensitive detector (PSD) for detecting characteristic X-rays dispersed by the wavelength dispersion crystal. The characteristic X-rays are detected at different positions previously defined by the PSD. A comparator is provided for comparing the intensity of the characteristic X-rays detected at the two positions of PSD with each other. Only if the intensity ratio is within a predetermined range selected depending on the specific state of the element, the comparator outputs state detection signals.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention and wherein:
FIGS. 1 through 4 are graphs of spectra of characteristic X-rays used for explaining a method of the present invention;
FIG. 5 is a schematic arrangement of a state analysis apparatus according to a first preferred embodiment of the present invention.
FIGS. 6 through 8 are block diagrams of the state analysis apparatus of FIG. 5 to process state detection signals;
FIG. 9 is a schematic arrangement of a state analysis apparatus according to a second preferred embodiment of the present invention; and
FIG. 10 is a block diagram of the state analysis apparatus of FIG. 9 to process state detection signals.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1 through 4 are graphs of spectra of characteristic X-rays are helpful in explaining a method of the present invention.
FIG. 1 shows spectra of characteristic X-ray of elements Si or SiO 2 , for example, contained in the specimen. The changing from Si to SiO 2 enables the shift of the peak wavelength in the spectrum of the characteristic X-rays. When the element of Si is in a first state i.e. metallic Si, it provides spectrum 1 of FIG. 1 as the inherent characteristic X-rays. In the spectrum 1, the peak wavelength value is λ 1 . A wavelength value far from λ 1 , at about a half of half width (at most at the peak half width) is λ 2 . Since the values of λ 1 and λ 2 are previously known depending on an element to be analyzed, two spectrometers are set to the wavelengths λ 1 and λ 2 , respectively. When the two spectrometers detect the spectrum, the intensity detected is given to be I 1 and I 2 . It is assumed that they satisfy the following relation.
I.sub.1 ≧αβ.sub.1 I.sub.2 (1)
α is an inherent factor so that the sensitivity of a first spectrometer for measuring the intensity I 1 at the wavelength λ 1 becomes equal to that of a second spectrometer for measuring the intensity I 2 at the wavelength λ 2 . The factor α is defined according to the spectrometers. β 1 is a factor representative of the wavelength shift amount in the characteristic X-ray spectra, the factor being defined with corresponding to the specific state of the element to be analyzed.
In a second state of the Si element, it is the compound of, for example, SiO 2 . The spectra of the Si element in this second state is shifted toward the shorter wavelengths due to the effect of oxygen to be spectrum 2 and displaced from spectrum 1. The peak wavelength value of the spectra 2 is thereby shifted toward the shorter wavelengths.
When the two spectrometers set to the wavelengths λ 1 and λ 2 are used to detect the spectral characteristic X-rays in the second state, the intensity I 1 and I 2 satisfy the following relation.
I.sub.1 <αβ.sub.1 I.sub.2 (2)
Therefore, the characteristic X-rays of the element to be analyzed are detected based on the wavelengths λ 1 and λ 2 previously selected in order to compare the detected intensity data with each other. To detect the first state of the element S 1 , state detection signals are outputted in connection with only some measurement points providing the intensity ratio for satisfying the relation (1), so that a line analysis or a two-dimensional scanning image in the first state can be displayed. To detect the second state of the combination of Si with O, namely SiO 2 , state detection signals are outputted from only some measurement points providing the intensity ratio for satisfying the inequality (2), so that the line analysis or the two-dimensional scanning image in the second state also be displayed.
FIG. 2 shows a graph of spectra of the characteristic X-rays where the intensity ratio of the related peaks are changed depending on the specific state such as the chemical bonding, for example, in the case of Lα and Lβ of Fe or α 3 and α 4 of K satellites.
Two spectrometers are set to peak wavelengths λ 3 and λ 4 of the two related peaks 3 and 4. In the first state, the detected intensity data I 1 and I 2 of the characteristic X-rays at the selected wavelengths λ 3 and λ 4 are assumed to satisfy the following relation.
I.sub.1 ≧αβ.sub.2 I.sub.2 (3)
In the second state, the intensity data I 1 and I 2 are assumed to satisfy the following relation.
I.sub.1 <αβ.sub.2 I.sub.2 (4)
β 2 is a factor representative of the intensity ratio of the related peaks. The line analysis or the two-dimensional scanning image specific to the states can be given by determining whether the spectra of the characteristic X-rays at the measurement points belong to either of the relations (3) and (4).
FIG. 3 shows a graph of the spectrum of the characteristic X-rays wherein symmetry in the spectrum is changed depending on the change of the state such as the chemical bonding states. The two spectrometers are set to wavelengths λ 5 and λ 6 , respectively, which are, for example, about a half of the half width, at the longer and shorter wavelength sides. Determined is whether the intensity data of the characteristic X-rays at the selected wavelengths λ 5 and λ 6 satisfy one of the following relations.
I.sub.1 >αβ.sub.3 I.sub.2 (5)
I.sub.1 =αβ.sub.3 I.sub.2 (6)
I.sub.1 <αβ.sub.3 I.sub.2 (7)
β 3 is a factor representative of asymmetry in the spectrum of the characteristic X-rays. By detecting one of the relations, the line analysis or the two-dimensional scanning image specific to the state to which the spectra belong can be obtained.
FIG. 4 shows a graph of spectrum of the characteristic X-rays where the half width in the spectrum of the characteristic X-rays can be altered depending on the changes of the state such as the chemical bonding state. When it is assumed that the spectrum is altered as shown in spectra 5 and 6 depending on the changes of the state, the wavelengths of the two spectrometers should be selected to be λ 1 of the peak wavelength and λ 2 far from λ 1 at about a half of the half width as shown in FIG. 1. The line analysis or the two-dimensional scanning image can be given in the same method as in FIG. 1 because the detected intensity ratio can be changed at the selected wavelength if the peak half width of the spectra is changed.
FIG. 5 is a schematic representation of a state analysis apparatus according to a first preferred embodiment of the present invention.
An electron beam 12 emitted from an electron gun 11 is incident upon a measurement point on a sample 10 to be analyzed with a focusing lens 13 and an objective lens 14. A scanning coil 15 is provided for enabling the scanning on the sample 10. In response to the application of the electron beam 12, a characteristic X-ray 16 and secondary electrons are emitted from the sample 10.
In the first preferred embodiment of the present invention, a first and second wavelength dispersive spectrometers are provided to detect the characteristic X-rays 16. The first wavelength dispersive spectrometer comprises a spectroscopic crystal 17 as a wavelength dispersion means and a detector 18. The second wavelength dispersive spectrometer comprises a spectroscopic crystal 19 as a wavelength dispersion means and a detector 20. The two spectrometers with the same sensitivity can detect the characteristic X-rays having the wavelengths specified in FIGS. 1 through 4; i.e., one of them is set to λ 1 , λ 3 , or λ 5 , while another to λ 2 , λ 4 , or λ 6 , respectively.
The detectors 18 and 20 may be a proportional counter, position sensitive detector, etc. It is preferable that both spectrometers are positioned adjacently to each other to make a measurement condition similar.
The characteristic X-rays 16 emitted from the sample 10 are dispersed to different wavelengths with the spectroscopic crystals 17 and 19 and are detected by the detectors 18 and 20 at the same time or sequentially. It is assumed that the detected spectral intensity of the two detectors 18 and 20 is I 1 and I 2 , respectively. The intensity value I 2 is changed to "αβI 2 " with an α set means 21 and a βi (i=1, 2, or 3) set means 22 as FIG. 6 shows. A comparison means 23 is provided for comparing I 1 with αβiI 2 so as to determine whether any specific state is specified. While a plurality of measurement points are scanned with displaying the state detection in real time on a display, a line analysis or a two-dimensional scanning image can be displayed.
As FIG. 7 shows, the output signals from the detectors 18 and 20 are stored in memories 24 and 25 in the form of the data I 1 and αβiI 2 , respectively, together with the position information of the measurement point. Thereafter, a computer 26 is operated to compare the data with each other. Otherwise, as FIG. 8 shows, the intensity data I 1 and I 2 from the detectors 18 and 20 are directly stored in memories 27 and 28 together with the position information of the measurement point. Thereafter, a computer 29 is operated to add the two coefficients α and βi and compare the resultant data with each other so as to display the result.
FIG. 9 is a schematic illustration of a state analysis apparatus according to a second preferred embodiment of the present invention. The state analysis apparatus of FIG. 9 is different from that of FIG. 5 in that a single wavelength dispersive spectrometer is provided which comprises a position sensitive detector 30 and a spectroscopic crystal 31 and that the intensity data by the position sensitive detector 30 are detected at two positions, respectively, corresponding to one selected wavelength (λ 1 for example) and another selected wavelength (λ 2 for example).
In case where the two independent spectrometers are provided for measuring the intensity data at the two selected wavelengths λ 1 and λ 2 , each of them can be placed in a completely spectroscopic condition. On the other hand, in case where only the single spectrometer with the position sensitive detector is provided for simultaneously measuring the intensity data at the positions corresponding to the wavelengths λ 1 and λ 2 , a spectroscopic condition is approximated. This is, however, no problem in practice to compare the intensity data between the adjacent wavelengths.
In the second preferred embodiment, as FIG. 10 shows, two portions of the single position sensitive detector 30 provide the intensity data I 1 and I 2 in the two different selected wavelengths, simultaneously or sequentially. In FIG. 10, the intensity data I 1 and I 2 are processed in real time. Otherwise they are processed after being stored within the memories 24, 25, 27, and 28 as shown in FIGS. 7 and 8. A line analysis or a two-dimensional scanning image at the specific state can be thereby displayed.
As described above, in accordance with the present invention, in case where the state of an element contained in a specimen is altered depending on the chemical bonding state, the characteristic X-ray spectra are correspondingly altered in a condition in which a point analysis mode can be applied to analyze the spectra. In such a case, the characteristic X-ray spectra can be effectively separated and altered. A line analysis or a two-dimensional scanning image of a composition distribution in the specimen to be analyzed can be displayed, having the same real time as the conventional case. The capability of the EPMA can be highly expanded beyond the conventional capability only for analyzing the element, in that according to the present invention, the EPMA can afford the important information of the state analysis in analyzing a material.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications are intended to be included within the scope of the following claims. | A method for analyzing a state of an element in a specimen comprises the steps of applying an exciting source to the element, detecting the intensity of characteristic X-rays generated from measurement points at two wavelengths previously selected depending on the state of the element to be analyzed, comparing the intensity ratio of the characteristic X-rays at the two wavelengths to detect some measurement points providing the detected intensity ratio falling within a range selected depending on the state of the element, and outputting state detection signals detected only at said some measurement points to obtain a line analysis or a two-dimensional scanning image. | 6 |
FIELD OF THE INVENTION
[0001] This invention relates to a shave gel or composition that can be used with electric shaving devices and manual razors. The dense lubricious lather enables a close shave with a manual razor and when rinsed off; the conditioning properties of the gel allow the hair to elongate resulting in a closer shave with electric shaving devices.
BACKGROUND OF THE INVENTION
[0002] There are a plethora of electric and manual shaving devices on the market. Along with those devices many shaving gels, lotions, creams and lubrications are sold, some in combination with the shaving apparatus to help assist with the shaving process. In all cases, these shaving formulas serve one purpose to one type of shaving device.
[0003] There are many types of people who may use both electric and manual shaving devices. Categorically, those of African descent or those with thick curly hair are more likely to use electric shaving devices, specifically those who suffer from razor bumps or Pseudofolliculitis barbae and would like to receive a closer shave. Those who use manual razors would also benefit from a multipurpose shave gel when they want to switch to an electric solution.
[0004] A multipurpose shaving solution is needed that will cater to the varying skin and hair types. A shaving solution that is lubricious enough for manual razors and a preparatory skin and hair conditioner for those who use electric shaving devices is needed.
DESCRIPTION OF THE RELATED ART
[0005] As can be seen by reference to the following U.S. Pat. Nos. 5,262,154; 5,756,081; 5,956,848; 6,096,386; and 6,149,981; the prior art are constructions of either a shave gel or preparatory treatment.
[0006] While all of the aforementioned prior art constructions are more than adequate for the basic purpose and function for which they have been specifically designed, none of them serve a multifunctional purpose of a shaving gel and preparatory treatment.
SUMMARY OF THE INVENTION
[0007] The present invention is directed to shave gel compositions comprising from about 0.05% to about 3.0% insoluble cationic conditioner, from about 0.05% to about 5% by weight of a silicone hair conditioning agent, from about 5% to about 60% by weight of a detersive surfactant, from about 0.025% to about 1.5% by weight of selected polyalkylene glycols, preferably polyethylene glycols having from about 1,500 to about 25,000 degrees of ethoxylation, from about 0.25% to about 10% lactylate, from about 0.05% to about 3% water soluble quaternary cellulose derivative and water, and optionally one or more additional materials known for use in conditioning compositions, which compositions provide excellent lubricating and conditioning benefits, and further provide a denser, thicker lather.
DETAILED DESCRIPTION OF THE INVENTION
[0008] The shave gel compositions and corresponding methods of the present invention can comprise, consist of, or consist essentially of the essential elements and limitations of the invention described herein, as well any of the additional ingredients, components, or limitations described herein. All documents referred to herein are incorporated by reference herein in their entirety.
[0009] As used herein, “water soluble” refers to any material that is sufficiently soluble in water to form a substantially clear solution to the naked eye at a concentration of 0.1% in water, i.e. distilled or equivalent, at 25.degree. C.
[0010] All percentages, parts and ratios are based upon the total weight of the shave gel compositions of the present invention unless otherwise specified.
Detersive Surfactant
[0011] The shave gel compositions of the present invention comprise one or more detersive surfactants selected from the group consisting of anionic surfactant, nonionic surfactant, amphoteric surfactant, zwitterionic surfactants, and mixtures thereof. The shampoo compositions preferably comprise an anionic surfactant. Surfactant concentrations range from about 5% to about 60%, preferably from about 10% to about 55%,
Anionic Surfactant
[0012] The shave gel compositions preferably comprise an anionic surfactant, and preferably at concentrations of from about 5% to about 60%, more preferably from about 10% to about 55%, even more preferably from about 15% to about 50%, and most preferably from about 20% to about 45%, by weight of the composition.
Amphoteric and Zwitterionic Surfactants
[0013] The detersive surfactant of the shaving gel compositions may comprise an amphoteric and/or zwitterionic surfactant. Concentrations of such surfactants will generally range from about 0.5% to about 20%, preferably from about 1% to about 10%, by weight of the shampoo compositions.
[0014] Amphoteric surfactants for use in the shaving gel compositions include the derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical is straight or branched and one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
Nonionic Surfactant
[0015] The shaving gel compositions of the present invention may comprise a nonionic surfactant as the detersive surfactant component therein. Nonionic surfactants include those compounds produced by condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
[0016] Preferred nonionic surfactants for use in the shampoo compositions include the following:
[0017] (1) polyethylene oxide condensates of alkyl phenols,
[0018] (2) those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine products;
[0019] (3) condensation products of aliphatic alcohols having from about 8 to about 18 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e.g.,
[0020] (6) long chain dialkyl sulfoxides containing one short chain alkyl or hydroxy alkyl radical of from about 1 to about 3 carbon atoms (usually methyl) and one long hydrophobic chain which include alkyl, alkenyl, hydroxy alkyl, or keto alkyl radicals containing from about 8 to about 20 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety;
[0021] (7) alkyl polysaccharide (APS) surfactants (e.g. alkyl polyglycosides), examples of which are described in U.S. Pat. No. 4,565,647, which description is incorporated herein by reference, and which discloses APS surfactants having a hydrophobic group with about 6 to about 30 carbon atoms and polysaccharide (e.g., polyglycoside) as the hydrophilic group; optionally, there can be a polyalkylene-oxide group joining the hydrophobic and hydrophilic moieties; and the allyl group (i.e., the hydrophobic moiety) can be saturated or unsaturated, branched or unbranched, and unsubstituted or substituted (e.g., with hydroxy or cyclic rings); and
[0022] (8) polyethylene glycol (PEG) glyceryl fatty esters, such as those of the formula R(O)OCH.sup.2 CH(OH)CH.sup.2 (OCH.sup.2 CH.sup.2).sub.n OH wherein n is from about 5 to about 200, preferably from about 20 to about 100, and R is an aliphatic hydrocarbyl having from about 8 to about 20 carbon atoms.
Silicone Hair Conditioning Agent
[0023] The shave gel compositions of the present invention comprise a silicone hair conditioning agent at concentrations effective to provide hair conditioning benefits. Such concentrations range from about 0.05% to about 10%, preferably from about 0.5% to about 8%, more preferably from about 1.0% to about 5%, most preferably from about 1.5% to about 3%, by weight of the shampoo compositions.
[0024] The ethoxylated silicone hair conditioning agents for use in the shave gel compositions are variably soluble in the shave gel compositions depending upon the degree of ethoxylation and are preferably nonvolatile. The degree of ethoxylation can be from about 1 to 200. Cationic silicones are also suitable and included in the scope of this patent.
Polyalkylene Glycol
[0025] The shave gel compositions of the present invention comprise selected polyalkylene glycols in amounts effective to enhance lather performance and enhance spreadability of the shampoo compositions on hair. Effective concentrations of the selected polyethylene glycols range from about 0.025% to about 1.5%, preferably from about 0.05% to about 1%, more preferably from about 0.1% to about 0.5%, by weight of the shave gel compositions.
[0026] The polyalkylene glycols suitable for use in the shave gel compositions are characterized by the general formula: ##STR12## wherein R is hydrogen, methyl or mixtures thereof, preferably hydrogen, and n is an integer having an average value of from about 1,500 to about 25,000, preferably from about 2,500 to about 20,000, and more preferably from about 3,500 to about 15,000. When R is hydrogen, these materials are polymers of ethylene oxide, which are also known as polyethylene oxides, polyoxyethylenes, and polyethylene glycols. When R is methyl, these materials are polymers of propylene oxide, which are also known as polypropylene oxides, polyoxypropylenes, and polypropylene glycols. When R is methyl, it is also understood that various positional isomers of the resulting polymers can exist.
[0027] Specific examples of suitable polyethylene glycol polymers include PEG-2M wherein R equals hydrogen and n has an average value of about 2,000; PEG-5M wherein R is hydrogen and n has an average value of about 5; PEG-7M wherein R is hydrogen and n has an average value of about 7; PEG-9M wherein R is hydrogen and n has an average value of about 9,000; and PEG-14M wherein R is hydrogen and n has an average value of about 14,000.
[0028] Suitable polyaikylene polymers include polypropylene glycois and mixed polyethylene/polypropylene glycols.
[0029] It has been found that these polyalkylene glycols, when added to the conditioning shave gel compositions described herein, enhance lather performance in delivering a richer, denser lather feel as well as a lubriciousness that is conducive to a shaving product. Polyethylene glycols, for example, are known for use in improving lather performance in cleansing compositions, Applicants are aware of prior art which teaches the use of these selected polyalkylene glycols in silicone-containing shampoo compositions. However, there is no such data for a shave gel.
[0030] It has also been found that these selected polyalkylene glycols, when added to shave gel composition, enhance spreadability and lubriciousness of the shave gel compositions in hair. Enhanced spreading, slip and enhanced conditioning of the shave gel composition provides consumers with a smoother, closer shave.
Suspending Agent
[0031] The shave gel compositions of the present invention comprise a suspending agent at concentrations effective for suspending the silicone hair conditioning agent in dispersed form in the shampoo compositions. Such concentrations range from about 0.1% to about 10%, preferably from about 0.3% to about 5.0%, by weight of the shave gel compositions.
[0032] Suitable suspending agents include acyl derivatives, long chain amine oxides, and mixtures thereof, concentrations of which range from about 0.1% to about 5.0%, preferably from about 0.5% to about 3.0%, by weight of the shave gel compositions. These preferred suspending agents include ethylene glycol esters of fatty acids preferably having from about 16 to about 22 carbon atoms. More preferred are the ethylene glycol stearates, both mono and distearate, but particularly the distearate containing less than about 7% of the mono stearate. Other suitable suspending agents include alkanol amides of fatty acids, preferably having from about 16 to about 22 carbon atoms, more preferably about 16 to 18 carbon atoms, preferred examples of which include stearic monoethanolamide, stearic diethanolamide, stearic monoisopropanolamide and stearic monoethanolamide stearate. Other long chain acyl derivatives include long chain esters of long chain fatty acids (e.g., stearyl stearate, cetyl palmitate, etc.); glyceryl esters (e.g., glyceryl distearate) and long chain esters of long chain alkanol amides (e.g., stearamide diethanolamide distearate, stearamide monoethanolamide stearate). Long chain acyl derivatives, ethylene glycol esters of long chain carboxylic acids, long chain amine oxides, and alkanol amides of long chain carboxylic acids in addition to the preferred materials listed above may be used as suspending agents. For example, it is contemplated that suspending agents with long chain hydrocarbyls having C.sub.8 −C.sub.22 chains may be used.
[0033] Other suitable suspending agents may be used in the shave gel compositions, including those that can impart a gel-like viscosity to the composition, such as water soluble or colloidally water soluble polymers like cellulose ethers (e.g., methylcellulose, hydroxybutyl methylcellulose, hydroxypropylcellulose, hydroxypropyl methylcellulose, hydroxyethyl ethyl cellulose and hydroxyethylcellulose), guar gum, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl guar gum, starch and starch derivatives, and other thickeners, viscosity modifiers, gelling agents, etc. Mixtures of these materials can also be used.
Water
[0034] The shave gel compositions of the present invention comprise from about 20% to about 94.8%, preferably from about 50% to about 94.8%, more preferably from about 60% to about 85%, by weight of water.
Optional Hair Conditioning Agents
[0035] The shave gel compositions of the present invention may further comprise water soluble cationic polymeric conditioning agents, hydrocarbon conditioning agents, cationic surfactants, and mixtures thereof.
Cationic Polymer
[0036] Optional cationic polymers for use as hair conditioning agents are those having a weight average molecular weight of from about 5,000 to about 10 million, and will generally have cationic, nitrogen-containing moieties such as quaternary ammonium or cationic amino moieties, and mixtures thereof.
[0037] Other cationic polymers that can be used include polysaccharide polymers, such as cationic cellulose derivatives, cationic starch derivative, and cationic guar gum derivatives. Other material include quaternary nitrogen-containing cellulose ethers as described in U.S. Pat. No. 3,962,418, and copolymers of etherified cellulose and starch as described in U.S. Pat. No. 3,958,581, which descriptions are incorporated herein by reference.
Cationic Surfactants
[0038] Optional cationic surfactants for use as hair conditioning agents in the shave gel compositions will typically contain quaternary nitrogen moieties. Examples of suitable cationic surfactants are described in following documents, all of which are incorporated by reference herein in their entirety: M.C. Publishing Co., McCutcheon's, Detergents & Emulsifiers, (North American edition 1979); Schwartz, et al., Surface Active Agents, Their Chemistry and Technology, New York: Interscience Publishers, 1949; U.S. Pat. No. 3,155,591; U.S. Pat. No. 3,929,678; U.S. Pat. No. 3,959,461 and U.S. Pat. No. 4,387,090.
Other Optional Materials
[0039] The shave gel compositions of the present invention may comprise one or more optional ingredients to improve or otherwise modify a variety of product characteristics, including aesthetics, stability and use benefits. Many such optional ingredients are known in the art and may be used in the shave gel compositions herein, provided that such ingredients are compatible with the essential ingredients described herein, or do not otherwise unduly impair cleansing or conditioning performance of the shave gel compositions.
[0040] Optional materials include foam boosters, preservatives, thickeners, cosurfactants, dyes, perfumes, solvents, styling polymers, anti-static agents, anti-dandruff aids, and pediculocides.
Method of Use
[0041] The shave gel compositions of the present invention are to be use with electric shaving devices or manual razors. An effective amount of the composition for shaving with a manual razor is applied to the area to be shaved, which has preferably been wetted, generally with water, and worked into a lather with either hands or a shaving brush. Such effective amounts generally range from about 1 g to about 10 g, preferably from about 1 to about 5 g. The area is then shaved as per users normal routine For use with electric clippers; an effective amount of the composition for shaving with a manual razor is applied to the area to be shaved, which has preferably been wetted, generally with water, rinsed and blotted dry. Such effective amounts generally range from about 1 g to about 10 g, preferably from about 1 g to about 5 g.
[0042] This method for shaving with a manual razor comprises the steps of:
[0043] (a) wetting the area with water,
[0044] (b) applying an effective amount of the shave gel composition to the area
[0045] (c) working the shave gel composition into a generous lather with hands or shaving brush.
[0046] (d) shave with manual razor.
[0047] This method for shaving with electric clippers comprises the steps of:
[0048] (a) wetting the area with water,
[0049] (b) applying an effective amount of the shave gel composition to the area
[0050] (c) working the shave gel composition into a generous lather with hands
[0051] (d) rinse with water; pat dry, and
[0052] (e) shave with electric clippers
EXAMPLES
[0053] The compositions illustrated in Examples I and II illustrate specific embodiments of the shave gel compositions of the present invention, but are not intended to be limiting thereof. Other modifications can be undertaken by the skilled artisan without departing from the spirit and scope of this invention. The compositions illustrated in Examples I and II are prepared in the following manner (all percentages are based on weight unless otherwise specified).
[0000]
PHASE A
WATER (AQUA)
41.20
PHASE A
DISODIUM EDTA
0.20
PHASE A
PEG-14M
1.00
PHASE A
SODIUM CAPROYL LACTYLATE
1.00
PHASE A
PEG-150 DISTEARATE
0.50
PHASE A
BUTYLENE GLYCOL
2.50
PHASE A
PEG-8 DIMETHICONE PEG-8 RICINOLEATE
0.50
POLYQUATERNIUM-57
PHASE B
COCAMIDOPROPYL BETAINE
8.00
PHASE B
SODIUM LAURETH SULFATE
15.00
PHASE B
SODIUM C14–16 OLEFIN SULFONATE
40.00
PHASE B
COCAMIDE MEA
1.50
PHASE C
FRAGRANCE
0.15
PHASE D
METHYLCHLOROISOTHIAZOLINONE
0.05
METHYLISOTHIAZOLINONE
PHASE D
GLYCOL DISTEARATE SODIUM LAURETH
2.50
SULFATE COCAMIDE MEA LAURETH-7
PHASE D
DICETYLDIMONIUM CHLORIDE
0.75
MANUFACTURING INSTRUCTIONS:
PHASE A
COMBINE WATER AND DISODIUM EDTA AND
MIX UNTIL UNIFORM. DISPERSE POLYOX INTO
WATER AND MIX HEAT TO 80 C. AND ADD
REMAINING PHASE A INGREDIENTS
PHASE B
ADD PHASE B INGREDIENTS TO BATCH SLOWLY
COOL BATCH TO 30 C.
PHASE C
ADD PHASE C TO BATCH WITH MIXING
PHASE D
ADD PHASE D INGREDIENTS ONE AT A TIME
WITH MIXING.
[0054] Preferred viscosities range from about 4500 to about 12,000 centistokes at 25.degree. C. (as measured by a Brookfield RV4@20 RPM).
[0055] The compositions illustrated in Examples I-II all of which are embodiments of the present invention, provide excellent lubricity and conditioning of hair, and further enhance conditioning impression by providing excellent spreading through hair and generate thick, dense lather.
[0000]
PHASE A
WATER (AQUA)
41.20
PHASE A
DISODIUM EDTA
0.20
PHASE A
PEG-7M
0.50
PHASE A
SODIUM LAUROYL LACTYLATE
0.50
PHASE A
PEG-150 DISTEARATE
1.50
PHASE A
GLYCERIN
0.25
PHASE A
PEG-8 DIMETHICONE PEG-8 RICINOLEATE
2.00
POLYQUATERNIUM-57
PHASE B
COCAMIDOPROPYL BETAINE
3.00
PHASE B
SODIUM LAURETH SULFATE
10.00
PHASE B
SODIUM C14–16 OLEFIN SULFONATE
20.00
PHASE B
COCAMIDE MEA
2.00
PHASE C
FRAGRANCE
0.30
PHASE D
METHYLCHLOROISOTHIAZOLINONE
0.05
METHYLISOTHIAZOLINONE
PHASE D
GLYCOL DISTEARATE SODIUM LAURETH
1.50
SULFATE COCAMIDE MEA LAURETH-7
PHASE D
DICETYLDIMONIUM CHLORIDE
0.50
[0056] Preferred viscosities range from about 4500 to about 12,000 centistokes at 25.degree. C. (as measured by a Brookfield RV4@20 RPM). | This invention relates to the composition of a multi-purpose shaving composition; designed to work with electric shaving devices and manual razors. | 0 |
BACKGROUND
This invention relates generally to microscopes with imaging capabilities. Such microscopes may be utilized in conjunction with computers to provide enlarged images of small objects.
The X3 digital video microscope by Intel Corporation and Mattel uses a digital imaging device to provide a magnified color image of an object viewable on the display of a computer system. This product may be used by children to view enlarged images of objects and to transmit those images using electronic mail. Once the image is electronically captured, alteration of the image may also be possible using well known software.
Thus, microscopes of this type provide an educational and entertaining toy for children. They allow children to learn more about computers and at the same time to learn more about the objects being imaged.
In view of the entertainment and educational opportunities afforded by microscopes of this type, there is a continuing interest in more advanced devices which provide further educational and entertainment opportunities.
SUMMARY
In accordance with one aspect, a microscope may include an imaging array. A first light source for the microscope is adapted to selectively produce visible light and a second light source is adapted to selectively produce infrared light.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram of one embodiment of the present invention coupled to a computer system;
FIG. 2 is a schematic diagram of the microscope depicted in FIG. 1;
FIG. 3 is a graphical user interface that may be used in some embodiments of the present invention; and
FIG. 4 is a block diagram of the system shown in FIG. 1.
DETAILED DESCRIPTION
Referring to FIG. 1, a computer system 10 may include an microscopic imaging device 12 and a computer 22 including a housing 24 and a display 26. The microscope 12 may be coupled to the computer system 22 by a cable 13 which may provide serial data from the microscope 12 to the computer system 22. In this way, data captured by the microscope 12 may be displayed on the display 26 of the computer 22.
Turning now to FIG. 2, the microscope 12 may include an imaging sensor 28 which may be a complementary metal oxide semiconductor (CMOS) imaging sensor in one embodiment of the present invention. The sensor 28 may also be a charge coupled device (CCD) imaging sensor in another embodiment of the present invention. In some embodiments, the imaging sensor 28 may capture a digital representation of an object 38 which may be positioned in the sample holder 16 of the microscope 12. A lens 30 may develop an image for capture by the imaging sensor 28. The microscope may be maintained in an upright orientation using a base 14.
Some objects such as polymers and biological specimens such as leaves exhibit different optical properties in the infrared portion of the spectrum. Thus, the same object may have a different appearance as captured by the imaging array 28 and as displayed on the display 26 when viewed under infrared versus visible spectrum light.
Typically, an imaging sensor 28 includes a color filter array (CFA) material. The inventor of the present invention has determined that such color filter array materials are readily transparent to both infrared and visible spectrum light. Thus, the imaging sensor 28 works with both light spectra. In particular, the quantum efficiency of silicon sensors is sufficient in both the infrared and visible spectrums. By providing a high efficiency infrared source, given high transmittance by the color filter array of the infrared light, a silicon imaging sensor is adequate for infrared imaging capabilities. Thus, the combined effect of the improved color filter array transmittance and the reduced quantum efficiency is such that infrared imaging by the same sensor used for visible imaging is feasible.
A pair of separate light sources 40, 42 may be coupled to the computer 22 through an interface 44. The light source 42 may be a relatively pure source of infrared light. The light source 40 may be a relatively pure white light source. The computer 22, under user command, may select one of the light sources 40 or 42 to illuminate the object 38 in the sample holder 16.
The white light source 40 may illuminate the object 38 with white light. The white light is reflected off the object in the direction of the arrow A and is captured by the imaging array 28. The array 28 sends a digital representation of the information to the host computer 22.
The user may provide an input signal to the host computer 22 to select a desired light source for illuminating the object. That selection may be passed from the computer 22 to the interface 44 to operate the appropriate light source 40 or 42. Alternatively, the light sources 40 or 42 may be selected by a switch 23 on the exterior of the microscope 12, as shown in FIG. 1.
A white light emitting diode (LED) may be used as the white light source 40. Suitable diodes include indium gallium nitride (InGaN) diodes available, for example, from Nichia America Corporation (Mountville, Pa. 17554) including the Nichia NSPW500BS and NSPW300BS white light LEDs. See wwwla.meshnet.jp/nichia/lamp-e.htm. These devices show negligible emission in the infrared radiation spectrum (approximately 780 nanometers and higher). The chromaticity coordinates specified by the manufacturer for these diodes are X=0.310, Y=0.320 in the CIE (1931) standard calorimetric system (International Congress on Illumination, Proceedings, International Congress on Illumination, Cambridge, Cambridge University Press).
For the infrared source 42, a gallium aluminum arsenide (GaAlAs) infrared light emitting diode may be utilized. These diodes may emit radiation at wavelengths of about 875 nanometers. Alternatively, gallium arsenide (GaAs) diodes may be used that emit radiation at wavelengths of about 940 nanometers. Such diodes are available, for example, from Vishay Intertechnology Inc. (San Diego, Calif.). Examples of suitable diodes include the TSHA440 infrared light emitting GaAlAs diode from Vishay (www.vishay.de) emitting at 875 nanometers.
Imaging optics 30, which may be a spherical lens of the type used for macro photography, may be positioned between the object 38 and the imaging sensor 28. Its position may be manually adjustable using the rotatable knobs 18 to allow for focusing. In some cases, the spherical lens 30 may be replaced with a flat lens, such as Fresnel lens, adapted for close up viewing.
Since no infrared blocking filter is needed, optical efficiency and cost may be improved in some embodiments. Also, the reliability of LEDs is relatively high compared to filament lamps.
One hardware implementation of the present invention, shown in FIG. 4, includes a processor-based system 10 having a processor 48 coupled to a bridge 50. The bridge 50 is coupled between system memory 56 and graphics accelerator 52. The display 26 may be coupled to the graphics accelerator 52.
The bridge 50 also couples a bus 58 in turn coupled to the microscope 12 through the cable 13 to the imaging sensor 28 and its interface 60. The interface 60 may itself include a processor for conducting analyses on digital representations of the image detected by the microscope 12. Alternatively, as shown in FIG. 4, the interface 60 may simply interface the imaging array 28 with the processor 48.
In one embodiment, a second bridge 62 couples a hard disk drive 64 or other non-volatile storage. The drive 64 may store image processing software 66 for modifying and enhancing the captured images, for example using the graphical user interface shown in FIG. 3.
The bridge 62 is also coupled to another bus 68 which couples conventional devices such as a keyboard 72 and a mouse 74 through a serial input/output (SIO) device 70. A binary input/output system (BIOS) 76 may also be coupled to the bus 68. The lamp interface 44 and lamp switch 23 may also be coupled through the SIO device 70.
Referring to FIG. 3, a graphical user interface, developed by the processor 48 under control of the software 66, may be displayed on the display 26 to assist the user of the host computer system 22 in utilizing the microscope 12. For example, a pair of icons 78 and 80 may be displayed which the user may use to select either infrared or visible spectrum illumination. When the user operates the mouse cursor over the desired icon 78 or 80, the host computer 22 may select the appropriate illumination source 40 or 42.
Similarly, the user can make other image modifications including brightness adjustments as indicated at 82, contrast as indicated at 84, hue as indicated at 86 and saturation as indicated at 88. Each of these input icons, as well as others, may operate on a simple sliding scale where moving the icon to the right using a mouse cursor increases the characteristic and moving to the left decreases the characteristic. After the user has made the desired adjustments, the user can return to displaying the captured image of the object 38 by selecting an icon 78 or 80.
While the present invention has been described with respect to a limited number of embodiments, those skilled in the art will appreciate numerous modifications and variations therefrom. It is intended that the appended claims cover all such modifications and variations as fall within the true spirit and scope of this present invention. | A microscope enables selective illumination using infrared or visible spectrum light. The image captured by a sensor array within the microscope may be displayed on a computer display. Some objects appear differently when exposed to infrared as opposed to visible radiation. | 6 |
TECHNICAL FIELD
The present inventions relate to a clutch assembly for an automobile transmission, more specifically, to a piston-pressure plate connection in the clutch assembly.
BACKGROUND
Conventional automobile transmissions include various clutch assemblies that enable the transmission to power the wheels at different speeds. Clutch assemblies are typically hydraulically actuated using some sort of apply piston. In past arrangements pistons have included pins that connect the piston with a backing plate of the clutch assembly. These pins interface with the backing plate carrying the force or load of engagement when applied. Concentrated over a relatively small surface area, these forces can cause unwanted wear on the piston and pins.
Additionally in certain sections of the transmission—typically near the output shaft of the transmission—the apply pistons can neighbor other transmission components such as speed sensors and park pawls. Accordingly, it can be desirable to restrict the rotational range of movement of the piston in order to ensure that the piston does not disrupt other transmission components when applying the clutch. Very high forces can develop when the piston is directly tied to the transmission case. These forces can cause unwanted wear and brinelling on the piston and neighboring transmission components.
Therefore, it is desirable to have a clutch assembly for a transmission that includes interconnecting members that produce less wear on the piston and other transmission components. It is also desirable to provide a method of manufacturing the clutch assembly that is cost efficient.
SUMMARY
The present inventions may address one or more of the above-mentioned issues. Other features and/or advantages may become apparent from the description which follows.
Certain embodiments of the present inventions provide a piston-actuated clutch assembly for a transmission, including: a clutch pack having a plurality of friction plates; a pressure plate at one end of the clutch pack; a piston adjacent the pressure plate; and interconnecting members integrated into the pressure plate, configured to selectively interlock the piston and the pressure plate during transmission operation. The piston is configured to actuate the clutch pack.
Other exemplary embodiments of the present inventions include a vehicle transmission, having: a housing; a hydraulically actuable clutch pack having a plurality of friction plates configured to selectively engage a planetary gear set; a pressure plate at one end of the clutch pack; a piston adjacent the pressure plate; and interconnecting members integrated into the pressure plate, configured to selectively interlock the piston and the pressure plate during transmission operation.
Another exemplary embodiment of the present inventions includes a method of manufacturing a clutch assembly for a transmission with reduced wear. The method includes: forming a piston; forming at least one receiving member in the piston; forming a pressure plate configured to selectively engage the piston; and forming an interconnecting member attached to the pressure plate and matable with the receiving member.
One advantage of some of the techniques discussed in the present disclosure is that they reduce wear in the transmission. There is less force in the apply piston and less wear on the piston and neighboring transmission components.
Another advantage of the present teachings is that they provide an inexpensive method of manufacturing a transmission with clutch assembly having reduced wear and greater durability.
In the following description, certain aspects and embodiments will become evident. It should be understood that the inventions, in their broadest sense, could be practiced without having one or more features of these aspects and embodiments. It should be understood that these aspects and embodiments are merely exemplary and explanatory and are not restrictive of the inventions.
The inventions will be explained in greater detail below by way of example with reference to the figures, in which the same references numbers are used in the figures for identical or essentially identical elements. The above features and advantages and other features and advantages of the present inventions are readily apparent from the following detailed description of the best modes for carrying out the inventions when taken in connection with the accompanying drawings. In the figures:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a partial cross-sectional view of a vehicle transmission with a clutch assembly according to an exemplary embodiment of the present inventions.
FIG. 2 is a perspective view of the clutch assembly of FIG. 1 .
FIG. 3 is a perspective view of the pressure plate and interconnecting members of FIG. 2 .
FIG. 4 is a perspective view of the piston of FIG. 2 .
FIG. 5 illustrates a method of manufacturing a transmission according to another exemplary embodiment of the present inventions.
Although the following detailed description makes reference to illustrative embodiments, many alternatives, modifications, and variations thereof will be apparent to those skilled in the art. Accordingly, it is intended that the claimed subject matter be viewed broadly.
DETAILED DESCRIPTION
Referring to the drawings, FIGS. 1-5 , wherein like characters represent the same or corresponding parts throughout the several views there is shown various transmission clutch assemblies. The clutch assemblies include a pressure plate that is engaged by a hydraulic apply piston. There are any number of interconnecting members formed in the pressure plate between the plate and piston to selectively interlock the piston and pressure plate. The placement and configuration of the interconnecting members yields greater durability and less wear on the piston and other transmission components.
Referring now to FIG. 1 , there is shown therein a partial cross-sectional view of an automobile transmission 10 . This cross-section shows the rear section of the transmission 10 or the section closest an output shaft 20 of the transmission. The shown transmission 10 is a six speed transmission. An exemplary piston-actuated clutch assembly 30 shown in FIG. 1 is configured to selectively engage a planetary gear set 40 . The shown gear set 40 and clutch pack 50 enables the transmission 10 to operate in neutral, a first speed and reverse. In this manner the clutch assembly 30 is sometimes referred to as a low-reverse clutch assembly.
Clutch assembly 30 , as shown in FIG. 1 , includes a hydraulically actuable clutch pack 50 having five clutch or friction plates 60 that selectively engage the ring or carrier gear 70 of the planetary gear set. A pressure plate 80 is located at one end of the clutch pack 50 . The pressure plate 80 has a series of splines 90 on an outer surface; pressure plate 80 is splined to and engages a transmission housing 100 . The splines 90 engage the transmission housing 100 and substantially prevent the pressure plate 80 from rotating. Pressure plate 80 is configured to move axially, transferring pressure to the friction plates 60 and enabling friction plates to engage the gear set 40 . Pressure plate 80 is actuated by an apply piston 110 . Pressure plate 80 includes several interconnecting members 120 attached to the pressure plate. Interconnecting members 120 are configured to engage the apply piston 110 and interlock the piston and pressure plate 80 when so engaged. Each interconnecting member 120 includes a chamfered edge. In the shown embodiment, interconnecting members 120 are rectangular and are integrally formed with the pressure plate 80 .
Piston 110 is configured to apply pressure to the pressure plate 80 and actuate clutch pack 50 . Piston 110 includes receiving members 130 that are matable with interconnecting members 120 . In the illustrated embodiment of FIG. 1 , receiving members 130 are slots or perforations at one end of the piston 110 . Piston 110 also includes an alignment member 140 on an outer surface. Alignment member 140 assists in positioning piston 110 , with respect to the transmission housing 100 during assembly. Alignment member 140 further partially prevents piston 110 from tilting with respect to the transmission housing 100 . Alignment member 140 includes a chamfered edge. In the shown embodiment, alignment member 140 is integrally formed with the piston 110 .
With reference to FIG. 1 , piston 110 is journaled onto a hub 170 of the transmission 10 . The output shaft 20 includes a ring gear 150 that is at least partially journaled onto an intermediate shaft 160 of the transmission. The transmission housing 100 includes hub 170 that is journaled onto the output shaft 20 . Bearings 180 , 190 are fitted between the transmission hub 170 and the output shaft 20 . A cylinder 200 is in the transmission housing 100 between piston 110 and ring gear 150 . Piston 110 is nested inside cylinder 200 . Cylinder 200 includes a number of seals 210 to control fluid distribution between the piston 110 and cylinder. When the piston 110 is actuated fluid fills between cylinder 200 and piston to axially move piston toward pressure plate 80 .
A set of annularly arranged coil springs 220 are fixed to the cylinder 200 and positioned against the piston 110 . Springs 220 bias piston 110 toward cylinder 200 . At rest, piston 110 is forced towards cylinder 200 . When actuated the pressure applied by fluid travelling between the piston 110 and cylinder 200 must be greater than the force applied by the coil springs 220 and seal drag to actuate the clutch pack 50 .
The bottom half of the transmission 10 , illustrated in FIG. 1 , shows the clutch assembly 30 in the off or inactive position. Piston 110 is not engaged with pressure plate 80 as shown at 230 . A park lock mechanism 240 for the transmission 10 is located at the bottom of the transmission. The park lock mechanism 240 includes a park pawl 250 and a park gear 260 . Due to the rearward position of clutch assembly 30 , piston 110 is configured to accommodate transmission components located near the output shaft 20 . The park lock mechanism 240 includes the park pawl 250 that engages the park gear 260 that is nested inside of piston 110 . Park gear 260 is fixed to ring gear 150 of the output shaft 20 . When the park pawl 250 engages gear 260 the output shaft 20 is substantially prevented from rotating. Piston 110 includes an orifice 270 through which park pawl 250 can fit. The orifice 270 is sufficiently large so that minor rotations of piston 110 do not cause the piston to touch or disrupt the park pawl 250 .
In FIG. 1 , there is also shown a speed sensing apparatus 280 for the transmission. Speed sensing apparatus 280 includes an arm 290 that has a sensor (not shown) mounted at and end of the arm. The sensor monitors the rotational speed of the output shaft 20 at ring gear 150 . Piston 110 includes an orifice 300 through which the arm 290 of the speed sensing apparatus can fit. In the illustrated embodiment, piston 110 is therefore substantially prevented from rotating to accommodate the speed sensing apparatus 280 and the park lock mechanism 240 .
Referring now to FIGS. 2-4 a piston-actuated clutch assembly 400 is shown removed from a vehicle transmission housing. Specifically with reference to FIG. 2 there is shown therein a perspective view of a clutch assembly 400 . The clutch assembly 400 is rotated 90 degrees clockwise from the operating position. Clutch assembly 400 includes a hydraulically actuable clutch pack 410 , pressure plate 420 and piston 430 . Clutch pack 410 includes several friction plates 440 . Juxtaposed between each friction plate 440 are pressure plates 450 . Pressure plates 450 have splines 460 on the outer surfaces of each plate. At the end of the clutch pack 410 is the pressure plate 420 . Pressure plate 420 is thicker than plates 450 . Pressure plate 420 also has a series of splines 460 on the outer surface. Pressure plate 420 is configured to engage piston 430 .
As shown in FIG. 3 , formed in the pressure plate 420 are three interconnecting members 470 . Interconnecting members 470 interlock piston 430 and pressure plate 420 . Members 470 prevent piston 430 from substantially rotating with respect to the transmission housing. Members 470 also properly align piston 430 with pressure plate 420 during engagement. In the shown embodiment, interconnecting members 470 are rectangular lugs. Interconnecting members 470 are chamfered on all five surfaces of the lug. The face of the lug 470 is chamfered with respect to the side surfaces; each side surface is respectively chamfered as well. The radius of chamfer can be, e.g., 30 degrees. Lugs 470 extend axially along one end of the pressure plate 420 . Interconnecting members 470 are formed integrally with the pressure plate 420 . In this embodiment, interconnecting members 470 are formed of powdered metal processes with the pressure plate. In other embodiments interconnecting members 470 are welded onto the face of pressure plate. Interconnecting members 470 are configured of a sufficient cross-sectional area to sustain forces from the piston 430 . Since these interconnecting members 470 are formed on the pressure plate 420 and interconnect the piston to the housing 100 through the pressure plate, as opposed to directly connecting the piston 430 to the housing 100 , the members undergo much less force during torque reversals.
Referring now to FIG. 4 , there is shown therein a perspective view of the piston 430 . Piston 430 includes three receiving members 480 that are matable with the interconnecting members 470 of the pressure plate 420 (as shown in FIG. 3 ). Receiving members 480 are axial slots located at the end of the piston. Slots 480 are designed to fit interconnecting members 470 therein. Slots 480 are longer than the interconnecting members 470 so that piston 430 does not necessarily engage interconnecting members 470 at surface 490 of piston. This allows a path for lube oil to exit the piston when the piston is applied. Slots 480 are also of a rectangular configuration. In one embodiment, slots 480 include chamfered or beveled edges to facilitate the interaction between interconnecting members and piston.
Also shown in FIG. 4 are several orifices 500 (or holes) in the body of the piston. These holes 500 can be used to accommodate non-rotating transmission components such as the park pawl 250 and speed sensor apparatus 280 , as shown in FIG. 1 . Piston 430 further includes protrusions 510 on the outer surface. Protrusions 510 act as alignment members or features for the piston. Alignment member 510 assists in positioning the piston 430 in the transmission housing during assembly. Alignment member 510 can also prevent the piston from tilting with respect to the housing. Piston 430 includes an orifice 520 at the other end to enable the output shaft to fit therethrough.
Referring now to FIG. 5 , there is shown therein a method of manufacturing a transmission with reduced wear 600 . The steps of the method include forming a piston 610 . Piston can be formed using any number of forming techniques such as, e.g., die casting, machining, and extrusion. The next step is forming at least one receiving member in the piston 620 . Receiving slot can be rectangular or any other shape. Forming a pressure plate configured to selectively engage the piston is also included in the method 630 . Pressure plate can be formed using any number of forming techniques such as, e.g., die casting, machining, and extrusion. Also the method includes forming an interconnecting member attached to the pressure plate and matable with the receiving member 640 . Interconnecting member can be rectangular or of any other shape that is compatible or matable with the receiving member. Interconnecting member can be formed using any number of forming techniques such as, e.g., die casting, machining, and extrusion. In one embodiment, the method includes forming a chamfer on an edge of the interconnecting member. Chamfer can be, for example, machined into the interconnecting member post casting or chamfer can be included in the mold cavity for the pressure plate.
In the shown embodiments the transmission housing, pressure plate, interconnecting members and piston are composed of an aluminum alloy. These components are formed via powder-metal processes, die casted and these components can also be machined, if needed. Any one of these components can be composed of other materials including, e.g., steel or titanium alloys.
Though the illustrated embodiments relate to clutch assemblies that selectively engage a pressure plate and piston, it should be appreciated that the disclosed interconnecting members and receiving members can be used for selective engagement of any number of transmission components. Moreover, interconnecting members and receiving members can be of any number of shapes including, circular and triangular configurations.
For the purposes of this specification and appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the written description or claims are approximations that can vary depending upon the desired properties sought to be obtained by the present inventions. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
It is noted that, as used in this specification and the appended claims, the singular forms “a,” “an,” and “the,” include plural referents unless expressly and unequivocally limited to one referent. Thus, for example, reference to “an interconnecting member” includes two or more different interconnecting members. As used herein, the term “include” and its grammatical variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that can be substituted or added to the listed items.
It will be apparent to those skilled in the art that various modifications and variations can be made to the methodologies of the present disclosure without departing from the scope of its teachings. Other embodiments of the inventions will be apparent to those skilled in the art from consideration of the specification and practice of the teachings disclosed herein. It is intended that the specification and examples be considered as exemplary only.
While the best modes for carrying out the inventions have been described in detail, those familiar with the art to which these inventions relate will recognize various alternative designs and embodiments for practicing the inventions within the scope of the appended claims. | The present disclosure relates to a piston-actuated clutch assembly for a transmission. Interconnecting members are integrated into a pressure plate of the clutch assembly. The interlocking members are configured to selectively interlock the piston and the pressure plate. The location of the interlocking members reduces wear on the piston and other transmission components. | 5 |
TECHNICAL FIELD OF THE INVENTION
The present invention relates generally to the field of managing and removing the waste heat produced by electronic devices and subassemblies.
BACKGROUND OF THE INVENTION
Electronic devices such as, for example, printed circuit boards (PCBs) generate heat due to the flow of electricity and the resistance thereto by components within the electronic device. The heat generated by the electronic device can diminish the performance and reliability of the electronic device. A conventional method of cooling higher heat level electronic devices is to couple the electronic device to a heat exchanger or cold wall which may be of the type shown in FIG. 1 . Heat exchanger 80 includes a flow path 81 through which may flow a heat transfer fluid to absorb heat produced by an electronic device (not shown) which is coupled to heat exchanger 80 . Heat exchanger 80 has an inlet 82 through which a heat transfer fluid is introduced into flow path 81 and an outlet 83 through which the heat transfer fluid exits flow path 81 . As shown in the enlarged cross-sectional partial view 85 , provided in FIG. 1 , the flow path may comprise a plurality of channels 86 through which the heat transfer fluid flows.
For significantly higher heat loads a different type of heat transfer fluid or coolant may be required that absorbs heat by changing from a liquid to a vapor. These heat exchangers are sometimes referred to as two-phase cold walls. Referring to FIG. 1 , with a two-phase cold wall the heat transfer fluid enters the heat exchanger 80 through inlet 82 as a liquid. After absorbing heat the heat transfer fluid becomes a vapor and exits the through outlet 83 . Two phase heat exchangers are considerably more difficult to design for full performance due to the coexistence of liquid and vapor within the same flow passages. Also uneven distribution of the incoming liquid can result due to changing orientation or acceleration loading of the heat exchanger.
SUMMARY OF THE INVENTION
According to the present invention, disadvantages and problems associated with previous thermal management systems and techniques have been addressed.
According to an embodiment of the present invention, a thermal management system, is provided that includes a first heat source and a first thermal management apparatus coupled to the first heat source. The first thermal management apparatus includes a fluid transfer chamber. A heat transfer fluid is disposed within the fluid transfer chamber and a porous fluid transfer element is also disposed within the fluid transfer chamber. The porous fluid transfer element transfers a portion of the heat transfer fluid from a first position to a second position. The second position has a lower liquid density than the first position.
According to another embodiment of the present invention, a method of managing thermal dynamics of a heat source is provided and includes the step of providing a heat transfer fluid in a porous fluid transfer element adjacent the heat source. Then, the heat transfer fluid is wicked from a relatively liquid-rich area within the porous fluid transfer element toward a relatively liquid-poor area within the porous fluid transfer element.
According to another embodiment of the present invention, a thermal management system includes a heat source and a thermal management apparatus disposed adjacent the heat source. A heat transfer fluid is disposed within the thermal management apparatus. A porous fluid transfer element is disposed within the thermal management apparatus. The porous fluid transfer element transfers a portion of the heat transfer fluid from a first position to a second position.
According to another embodiment of the present invention, a thermal management apparatus includes a body having an interior, and a porous fluid transfer element disposed within the interior and adapted to transfer a portion of a heat transfer fluid within the interior from a liquid-rich area toward a liquid-poor area.
According to various aspects of some, none or all of the embodiments, the porous fluid transfer element may either passively or actively transfer heat transfer fluid. Also, heat transfer fluid which has transferred heat with the heat source may be periodically replaced, exhausted, or neither replaced nor exhausted, depending upon the application. Thus, the invention may encompass a one-use, or multi-use, apparatus or system.
Particular embodiments of the present invention may provide one, some, all, or none of certain technical advantages. For example, according to at least one embodiment, the wicking action of the porous fluid transfer element transfers heat transfer fluid from liquid-rich areas toward liquid-poor areas. This transfer may occur against the forces of gravity or other forces caused by movement of an apparatus or system incorporating the invention.
Other technical advantages, aspects and embodiments may be readily apparent to those skilled in the art from the following figures, descriptions, and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
A better understanding of the present invention will be realized from the detailed description which follows, taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a conventional heat exchanger in accordance with the prior art.
FIG. 2 is a cross-sectional view of a heat transfer apparatus having a porous fluid transfer element in accordance with an embodiment of the present invention;
FIG. 3 is a cross-sectional view of a heat transfer apparatus having a porous fluid transfer element in accordance with an embodiment of the present invention;
FIG. 4 is a cross-sectional view of a heat transfer apparatus having a porous fluid transfer element in accordance with an embodiment of the present invention;
FIG. 5 is a cross-sectional view of a heat transfer apparatus having a porous fluid transfer clement in accordance with an embodiment of the present invention; and
FIG. 6 is a cross-sectional view of a heat transfer system in accordance with an embodiment of the present invention.
DETAILED DESCRIPTION
A heat transfer apparatus used to remove heat from electronic devices, such as the cold wall shown in FIG. 1 , has limitations on the amount of heat that can be removed where a heat transfer fluid enters and leaves the cold wall as a liquid. To be able to remove more heat a heat transfer fluid capable of boiling must be used. These types of cold walls and heat exchangers are referred to as two-phase cold walls and two-phase heat exchangers where the heat transfer fluid enters in the liquid phase and leaves in the vapor phase. Conventional two-phase cold walls are built somewhat similar to liquid-only phase cold walls. This approach has several drawbacks. One such drawback is the propensity of the liquid component of the heat transfer fluid to sink to the bottom of fluid flow passages within the heat exchanger. As a result, heated areas are not presented with liquid to absorb heat by changing from liquid to vapor. This condition is particularly troublesome near the outlet of the conventional two-phase heat exchanger because the heat transfer fluid has an even greater concentration of vapor in this area.
A result of these deficiencies is the creation of hot spots across the configuration of the electronic device. Another deficiency in conventional heat exchangers is that they are sensitive to gravity and acceleration induced forces which tend to cause the liquid component of the heat transfer fluid to be forced into certain areas of the heat exchanger, depending upon the orientation of the heat exchanger. For example, if the heat exchanger shown in FIG. 1 was positioned vertically such that the outlet was positioned above the inlet, gravity would tend to force the liquid component of the heat transfer fluid toward the bottom of the heat exchanger passages (i.e., toward the inlet), thereby exacerbating the problem of high vapor concentrations in hot spots near the outlet. External forces may be magnified in certain applications such as, for example, use of the heat exchanger in a high-performance military aircraft.
Among other things, various embodiments of the present invention are directed to systems that use a heat transfer fluid, which changes to vapor as heat is absorbed. Various embodiments also relate to other thermal management systems involving the exchange and transport of heat that use a heat transfer fluid, which changes from a liquid to a vapor as heat is absorbed and the heat is carried off by the vapor stream.
According to an embodiment of the present invention, a heat transfer apparatus, such as a cold wall, is provided that removes heat from a heat source such as an electronic circuit board. The apparatus includes a fluid transfer chamber. A heat transfer fluid is disposed within the fluid transfer chamber and a porous fluid transfer element is also disposed within the fluid transfer chamber. The porous fluid transfer element uses capillary action to enhance the distribution of coolant within the fluid transfer chamber. Using the capillary action of the porous fluid transfer element, the heat transfer fluid is wicked from relatively liquid-rich areas within the porous fluid transfer element toward relatively liquid-poor areas within the porous fluid transfer element.
With two-phase cold walls, as the heat transfer fluid nears the cold wall exit, it will have a significant portion of its flow in the vapor state and a lesser amount entrained as a liquid within the vapor stream. The vapor velocity will essentially propel the liquid portion past the heat transfer surfaces thus impeding the absorption of heat by the coolant. The porous fluid transfer element will capture the liquid portion and passively pump it to areas that are fluid-poor, using the capillary action supplied by the porous fluid transfer element. The capillary action of the porous fluid transfer element also assists in feeding the heat transfer fluid when a cold wall is subject to accelerations and adverse orientations.
Thus, capillary action may be used to enhance coolant flow during adverse orientations. This feature is useful for two-phase heat exchangers such as those in high-performance military aircraft, for example. The porous fluid transfer element will enhance two-phase heat exchanger performance by reducing the amount of area temporarily void of heat transfer fluid during a high-speed maneuver.
Among other things, an embodiment of the present invention is configured to reduce uneven heat exchange and the creation of hot spots, as well as the negative effects of gravity and other forces that affect the heat transfer performance of a two-phase heat exchanger. According to an embodiment of the present invention, a porous material may be incorporated into the heat exchanger to provide capillary action which draws the liquid component of a heat transfer fluid into liquid-poor areas of the heat exchanger against the forces of the vapor component and against the forces of gravity (and other forces caused by orientation and application of the heat exchanger). Suitable heat transfer fluids are fluorinerts, methanol, water, water and methanol mixtures, water and ethylene glycol mixtures, and ammonia.
FIG. 2 , according to an embodiment of the present invention, shows the flow path 21 of a heat transfer apparatus 20 . Heat transfer apparatus 20 may be, for example, a two-phase cold wall. Apparatus 20 is lined with a porous material 23 where heat is inputted into surfaces 24 . The heat transfer fluid flows through channels 22 and converts to vapor as heat is absorbed. As the heat transfer fluid mass flow picks up more heat as it moves towards the cold wall exit (not expressly shown), a greater proportion of its mass flow is in the vapor state and less in the liquid state. As a result, the velocity of the vapor component essentially propels the liquid component past the heat transfer surfaces, thus impeding the absorption of heat by the heat transfer fluid. Porous fluid transfer element 23 captures the liquid portion and passively pumps it to areas that are fluid-poor using the capillary action supplied by the porous fluid transfer element 23 . Porous heat transfer element 23 transports the liquid to the internal side 25 of heated surfaces 24 . Porous fluid transfer element 23 also functions as a fin stock that increases the area from which heat is absorbed. Enclosure 26 can comprise any suitable material such as, for example, aluminum. Other types of materials that may be used include copper, aluminum silicon carbide, and composite materials.
The porous material of element 23 may include any suitable material capable of providing capillary action for the heat transfer fluid selected for use within the thermal management apparatus. Preferably, the porous material is a microporous material made of microporous aluminum, bronze, copper, and composite felts.
FIG. 3 depicts a cross-section of the flow path of a heat transfer apparatus 30 , which may be a two-phase cold wall generally similar to that shown in FIG. 2 . In this embodiment, the apparatus is assembled from interlocking portions joined along a surface 38 . Among other things, this approach offers an alternative that aids in assembly with an alternative method of construction of the porous fluid transfer element 37 .
FIG. 4 depicts a cross-section of the flow path of a heat transfer apparatus 40 , which may be a two-phase cold wall generally similar to that shown in FIGS. 2 and 3 . In this embodiment, the porous fluid transfer element 41 has an increased number of channels 49 through which the heat transfer fluid flows. This embodiment offers an alternative that will allow for less restriction of the heat transfer fluid mass flow while providing more area though which the liquid component of the heat transfer fluid can transported by the capillary action of the porous heat transfer element 41 .
FIG. 5 depicts a cross-section of the flow path of a heat transfer apparatus 50 , which may be a two-phase cold wall generally similar to that shown in FIGS. 2 , 3 , and 4 . In this embodiment, the porous fluid transfer element 51 has additional channels 53 removed from the main channels 52 . Channels 53 provide additional paths through which vapor can exit the porous fluid transfer element 51 . This enhances the capillary action of porous fluid transfer element 51 by minimizing the coexistence of liquid and vapor in porous fluid transfer element 51 .
Thus, main channels 52 comprise a first group of fluid transfer channels and additional channels 53 comprise a second group of fluid transfer channels. According to certain applications, the first group of fluid transfer channels (channels 52 ) provides passage for the transport of both liquid and vapor components of a heat transfer fluid, while the second group of fluid transfer channels (channels 53 ) provides passage for the transport of substantially only the vapor component of the heat transfer fluid.
FIG. 6 depicts a thermal management system 60 which comprises certain basic elements previously depicted and described. Thus, thermal management system 60 includes a thermal management apparatus 61 , having a fluid transfer chamber 62 , and a fluid transfer element 64 disposed within fluid transfer chamber 62 , and a heat transfer fluid disposed within fluid transfer chamber 62 . A heat transfer fluid preferably fills the voids within the porous material that comprises fluid transfer element 64 . Additionally, thermal management system 60 comprises a first heat source 68 and a second heat source 69 . The heat sources 68 and 69 may include any heat-producing element such as an electronic device. As previously discussed, the creation of hot spots by the heat sources may result in a liquid-poor area (such as area B). However, the capillary action of the porous material of fluid transfer element 64 tends to force the liquid component of the heat transfer fluid from liquid-rich areas A into the liquid-poor area B.
According to another embodiment, a system may include multiple thermal management sub-systems, which may be arranged, for example, in a stack. Each thermal management sub-system may include a thermal management apparatus and at least one heat source. The thermal management apparatus heat source may be any of the configurations discussed herein in connection with other various figures. Additionally, the fluid transfer chambers may be linked to one another through one or more linking channels.
The configurations of the heat transfer devices described and depicted herein are provided by way of example only, and may be modified within the scope of the present invention. For instance, the channels and porous fluid transfer element can be provided in any of a variety of configurations.
Channels have been shown in certain figures as having a rectangular cross-section. However, the cross-sectional shape of the channels, for this or any other configuration herein, may be varied depending upon the desired application. Also, in certain figures, channels have been depicted as having a longitudinal axis that is parallel with the plane defined by the thermal management apparatus. However, the longitudinal axis of a channel may extend in a direction different from other channels and non-parallel to the plane of the respective thermal management apparatus. Additionally, the axis of any given channel may change direction along a flow path of the respective channel.
The thermal management apparatus of any of the configurations discussed herein may be self-contained in that the apparatus is pre-loaded with the heat transfer fluid. A vent (not shown) may be provided to allow a portion of the heat transfer fluid to exit the thermal management apparatus. A self-contained configuration, or a configuration with a vent, may be used, for example, in single-use applications. In a single-use application, the heat transfer capacity of the apparatus is preferably used a single time, either partially or completely, after which the spent apparatus is disposable.
Also, a thermal management apparatus may be provided with an inlet and an outlet, such that heat transfer fluid may be continuously pumped into the fluid transfer chamber, and heat transfer fluid that has already exchanged heat with a heat source may exit fluid transfer chamber. According to this configuration, the apparatus is preferably reusable for multiple instances of a single application, or for multiple applications.
Although specific examples of the invention and its advantages have been described above in detail, a person of ordinary skill in the art could make various alterations, additions, and omissions without departing from the spirit and scope of the present invention as defined by the appended claims. | A thermal management system is provided. The system has a thermal management apparatus which may be disposed adjacent to and connected with a heat source. The thermal management apparatus may include a body having a porous fluid transfer element disposed therein. The body may also have a heat transfer fluid disposed therein. The heat source may create relatively liquid-rich and liquid-poor regions within the thermal management apparatus. The wicking action of the porous fluid transfer element may be used to force heat transfer fluid from liquid-rich regions toward liquid-poor regions. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This is a divisional of application Ser. No. 12/139,100, filed on Jun. 13, 2008, which is a divisional of application Ser. No. 11/702,810, filed on Feb. 6, 2007, now U.S. Pat. No. 7,472,589 B1, issued Jan. 6, 2009, which is a continuation-in-part of application Ser. No. 11/438,764, filed on May 23, 2006, which is a continuation-in-part of application Ser. No. 11/268,311, filed on Nov. 7, 2005, now U.S. Pat. No. 7,197,923 B1, issued Apr. 3, 2007.
TECHNICAL FIELD OF THE INVENTION
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
Without limiting the scope of the present invention, its background is described with reference to testing hydrocarbon formations, as an example.
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.
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.
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
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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
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:
FIG. 1 is a schematic illustration of a fluid sampler system embodying principles of the present invention;
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;
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;
FIG. 4 is a cross-sectional view of the pressure source section of FIG. 3C taken along line 4 - 4 ;
FIG. 5 is a cross-sectional view of the actuator section of FIG. 3A taken along line 5 - 5 ;
FIG. 6 is a schematic view of an alternate actuating method for a sampler embodying principles of the present invention;
FIG. 7 is a schematic illustration of an alternate embodiment of a fluid sampler embodying principles of the present invention;
FIG. 8 is a cross-sectional view of the fluid sampler of FIG. 7 taken along line 8 - 8 ; and
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
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.
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 .
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.
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.
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 .
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.
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 .
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 .
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 .
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 .
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 .
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 .
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. 3C ) 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 .
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.
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.
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.
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 .
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.
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 .
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.
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 .
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 .
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 .
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.
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 .
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.
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.
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.
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.
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.
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 .
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.
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 .
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.
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 .
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 .
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 .
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.
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 .
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 .
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.
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 .
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 .
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 .
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 .
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.
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 .
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.
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. | 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 ). | 4 |
This application is a divisional of Serial No. 09/166,722 filed Oct. 5, 1998, now U.S. Pat. No. 5,962,693 and claims the benefit of Provisional Application No. 60/061,707 filed Oct. 6, 1997.
FIELD OF THE INVENTION
The present invention relates generally to processes for the conversion of cyano groups into amidines for the purpose of producing compounds which are useful as antagonists of the platelet glycoprotein IIb/IIIa fibrinogen receptor complex. These compounds may be used for the inhibition of platelet aggregation, as thrombolytics, and/or for the treatment of thromboembolic disorders.
BACKGROUND
There are several methods to convert cyano groups into amidine groups (S. Patai, Z. Rappoport, The Chemistry of Amidines and Imidates, 1991, John Wiley & Sons Ltd.). One of the most widely used methods for the preparation of amidines is the Pinner synthesis (R. Roger, D. G. Neilson, Chem. Rev . 1961, 61, 179-211), which proceeds in two steps through an imidate intermediate.
Abood et al, in U.S. Pat. No. 5,484,946, discusses formation of the amidine moiety from a nitrile group through an amidoxime intermediate. Jendrall et al, in Tetrahedron 1995, 51, 12047-12068, used a similar process to convert a cyano group into the amidinium functionality. Eloy and Leners, in Chem. Rev ., 1962, 62, 155-183, review the preparation of amidoximes from nitrites. Chio and Shine, in J. Heterocyclic Chem ., 1989, 26, 125-128, reported that these amidoximes can be transformed into 1,2,4-oxadiazole derivatives. Judkins et al, in Synthetic Commun . 1996, 26, 4351, describe formation of amidine moiety from nitrile through an amidoxime intermediate under acetylation or acylation conditions.
This literature however, does not disclose any regioselectivity between an amidoxime and an isoxazoline. In fact, Mueller et al, Angew. Chem ., 1994, 106, 1305-1308, report that hydrogenation with 10% Pd/C will reduce a isoxazoline ring system. There is also no precedent for the transformation of a cyano group into an amidine functionality through a 1,2,4-oxadiazole moiety, and therefore the conversion of a 1,2,4-oxadiazole into amidine directly through catalytic hydrogenation is not taught.
Compounds of generic form (I) are antagonists of the platelet glycoprotein IIb/IIIa fibrinogen receptor complex which are currently being evaluated for the inhibition of platelet aggregation, as thrombolytics, and for the treatment of thromboembolic disorders. Consequently, large quantities of these compounds are needed to support drug development studies.
The preparation of compounds of generic form (I) have been disclosed in U.S. Pat. No. 5,446,056, PCT international publication WO 95/14683, PCT international publication Wo 96/38426, pending and commonly owned U.S. application Ser. No. 08/700,906, and in J. Med. Chem ., Xue et al, 1997, 40, 2064-2084. The preparation of (X) has been disclosed by Zhang et al in Tetrahedron Lett . 1996, 37, 4455-4458 and J. Org. Chem . 1997, 62, 2466-2470, which describe amidine formation from a nitrile using the Pinner reaction. Although this process has been able to produce compounds of formula (X) on a multikilogram scale, employing the Pinner reaction on a commercial scale poses several disadvantages. The Pinner approach involves the use of an excess of hydrogen chloride gas which is environmentally unfriendly, and removal of the inorganic salts generated during the Pinner process requires extensive purification protocols. It was therefore necessary to develop an efficient, safer process to produce compounds of formula (I) on large scale.
SUMMARY OF THE INVENTION
The present invention relates generally to processes for the conversion of cyano groups into amidines for the purpose of producing compounds, and intermediates therefore, which are useful as antagonists of the platelet glycoprotein IIb/IIIa fibrinogen receptor complex. These compounds may be used for the inhibition of platelet aggregation, as thrombolytics, and/or for the treatment of thromboembolic disorders.
There is provided by this invention a process for the preparation of compounds of formula (I), (III), (IV), (V) and (VI):
wherein:
R 1 is selected from H or NHR 1a ;
R 1a is selected from the group consisting of:
—C(═O)—O—R 1b ,
—C(═O)—R 1b ,
—C(═O)N(R 1b ) 2 ,
—C(═O)NHSO 2 R 1b ,
—C(═O)NHC(═O)R 1b ,
—C(═O)NHC(═O)OR 1b ,
—C(═O)NHSO 2 NHR 1b ,
—C(═S)—NH—R 1b ,
—NH—C(═O)—O—R 1b ,
—NH—C(═O)R 1b ,
—NH—C(═)—NH—R 1b ,
—SO 2 —O—R 1b ,
—S 2 —R 1b ,
—SO 2 —N(R 1b ) 2 ,
—SO 2 —NHC(═O)OR 1b ,
—P(═S)(OR 1b ) 2 ,
—P(═O)(OR 1b ) 2 ,
—P(═S)(R 1b ) 2 ,
—P(═O)(R 1b )2, and
R 1b is selected from the group consisting of:
C 1 -C 8 alkyl substituted with 0-2 R 1c ,
C 2 -C 8 alkenyl substituted with 0-2 R 1c ,
C 2 -C 8 alkynyl substituted with 0-2 R 1c ,
C 3 -C 8 cycloalkyl substituted with 0-2 R 1c ,
aryl substituted with 0-4 R 1c ,
aryl(C 1 -C 6 alkyl)-substituted with 0-4 R 1c ,
a 5-10 membered heterocyclic ring system having 1-3 heteroatoms selected independently from O, S, and N, said heterocyclic ring being substituted with 0-4 R 1c , and
C 1 -C 6 alkyl substituted with a 5-10 membered heterocyclic ring system having 1-3 heteroatoms selected independently from O, S, and N, said heterocyclic ring being substituted with 0-4R 1c ;
R 1c is H, halogen, CF 3 , CN, NO 2 , C 1 -C 8 alkyl, C 2 -C 6 alkenyl, C 3 -C 11 cycloalkyl, C 4 -C 11 cycloalkylalkyl, aryl, aryl(C 1 -C 6 alkyl)-, C 1 -C 6 alkoxy, and C 2 -C 5 alkoxycarbonyl;
R 2 is selected from H or C 1 -C 10 alkyl;
R 3 and R 4 are independently selected from the group consisting of H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 7 cycloalkyl, and aryl substituted with 0-2 R 3a ;
R 3a is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halo, CF 3 , NO 2 , and NR 3b R 3c ;
R 3b and R 3c are each independently selected from the group consisting of H, C 1 —C 10 alkyl, C 2 -C 10 alkoxycarbonyl, C 2 -C 10 alkylcarbonyl, C 1 —C 10 alkylsulfonyl, heteroaryl(C 1 -C 4 alkyl)sulfonyl, aryl(C 1 -C 10 alkyl)sulfonyl, arylsulfonyl, aryl, heteroarylcarbonyl, heteroarylsulfonyl, and heteroarylalkylcarbonyl, wherein said aryl and heteroaryl are optionally substituted with 0-3 R 3d ;
R 3d is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halo, CF 3 , and NO 2 ;
R 5 is selected from the group consisting of:
hydroxy, C 1 -C 10 alkyloxy, C 3 -C 11 cycloalkyloxy,
C 6 -C 10 aryloxy, C 7 -C 11 arylalkyloxy,
C 3 -C 10 alkylcarbonyloxyalkyloxy,
C 3 -C 10 alkoxycarbonyloxyalkyloxy,
C 3 -C 10 alkoxycarbonylalkyloxy,
C 5 -C 10 cycloalkylcarbonyloxyalkyloxy,
C 5 -C 10 cycloalkoxycarbonyloxyalkyloxy,
C 5 -C 10 cycloalkoxycarbonylalkyloxy,
C 8 -C 11 aryloxycarbonylalkyloxy,
C 8 -C 12 aryloxycarbonyloxyalkyloxy,
C 8 -C 12 arylcarbonyloxyalkyloxy,
C 5 -C 10 alkoxyalkylcarbonyloxyalkyloxy,
5-(C 5 -C 10 alkyl)-1,3-dioxa-cyclopenten-2-one-yl)-methyloxy,
(5-aryl-1,3-dioxa-cyclopenten-2-one-yl)-methyloxy, and
(R 5a )HN-(C 1 -C 10 alkoxy)-;
5a is selected from the group consisting of H, C 1 -C 4 alkyl, aryl(C 1 -C 10 alkoxy)carbonyl, C 2 -C 10 alkoxycarbonyl, and C 3 -C 6 alkenyl;
R 6 is selected from the group consisting of H, CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CF 2 CF 2 CF 2 CF 3 , C 1 -C 8 alkyl, C 1 -C 8 perfluoroalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 11 cycloalkyl, C 4 -C 11 cycloalkylalkyl, aryl (C 1 -C 6 alkyl)-, C 1 -C 6 alkoxy, C 7 -C 10 arylalkyloxy, aryloxy and aryl substituted with 0-5 R 6c ;
R 6c is selected from the group consisting of H, halo, CF 3 , CN, NO 2 , NR 6d R 6e , C 1 -C 8 alkyl, C 2 -C 6 alkenyl, C 3 -C 11 cycloalkyl, C 4 -C 11 cycloalkylalkyl, aryl, aryl(C 1 -C 6 alkyl)-, C 1 -C 6 alkoxy, and C 2 -C 5 alkoxycarbonyl;
R 6d and R 6e are independently selected from the group consisting of H, C 1 -C 10 alkyl, C 2 -C 10 alkoxycarbonyl, C 2 -C 10 alkylcarbonyl, C 1 -C 10 alkylsulfonyl, aryl, aryl(C 1 -C 10 alkyl)sulfonyl, arylsulfonyl, heteroaryl(C 1 -C 4 alkyl)sulfonyl, heteroarylcarbonyl, heteroarylsulfonyl, or heteroarylalkylcarbonyl, wherein said aryl and heteroaryl are optionally substituted with 0-3 substituents selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halo, CF 3 , and NO 2 ;
n is 0-4; and
a is a single or double bond, with the proviso that if a is a double bond, it is not simultaneously substituted with R 3 and R 4 ;
said process comprising one or more of:
(1): contacting a compound of formula (II) with a salt of hydroxyl amine in the presence of a suitable base to form a compound of formula (III);
(2): contacting a compound of formula (III) with an acylating agent of formula R 6 CO—O—COR 6 or R 6 COX, wherein X is fluorine, bromine, chlorine or imidazole, in a suitable solvent to form a compound of formula (IV) or a salt thereof; and
(3): contacting a compound of formula (IV) with hydrogen under a suitable pressure in the presence of a hydrogenation catalyst to form a compound of formula (I) or a pharmaceutically acceptable salt form thereof.
DETAILED DESCRIPTION OF THE INVENTION
In a first embodiment, the present invention provides a process for the preparation of compounds of formula (I):
or a pharmaceutically acceptable salt form thereof; wherein:
R 1 is selected from H or NHR 1a ;
R 1a is selected from the group consisting of:
—C(═O)—O—R 1b ,
—C(═O)—R 1b ,
—C(═O)N(R 1b ) 2 ,
—C(═O) NHSO 2 R 1b ,
—C(═O)NHC(═O)R 1b ,
—C(═O)NHC(═O)OR 1b ,
—C(═O)NHSO 2 NHR 1b ,
—C(═S)—NH—R 1b ,
—NH—C(═O)—O—R 1b ,
—NH—C(═O)R 1b ,
—NH—C(═)—NH—R 1b ,
—SO 2—O—R 1b ,
—SO 2 —R 1b ,
—SO 2 —N(R 1b )2,
—SO 2 —NHC(═O)OR 1b ,
—P(═S)(OR 1b ) 2 ,
—P(═O)(OR 1b ) 2 ,
—P(═S)(R 1b ) 2 ,
—P(═O)(R 1b ) 2 , and
R 1b is selected from the group consisting of:
C 1 -C 8 alkyl substituted with 0-2 R 1c ,
C 2 -C 8 alkenyl substituted with 0-2 R 1c ,
C 2 -C 8 alkynyl substituted with 0-2 R 1c ,
C 3 -C 8 cycloalkyl substituted with 0-2 R 1c ,
aryl substituted with 0-4 R 1c ,
aryl(C 1 -C 6 alkyl)-substituted with 0-4 R 1c ,
a 5-10 membered heterocyclic ring system having 1-3 heteroatoms selected independently from O, S, and N, said heterocyclic ring being substituted with 0-4 R 1c , and
C 1 -C 6 alkyl substituted with a 5-10 membered heterocyclic ring system having 1-3 heteroatoms selected independently from O, S, and N, said heterocyclic ring being substituted with 0-4R 1c ;
R 1c is H, halogen, CF 3 , CN, NO 2 , C 1 -C 8 alkyl, C 2 -C 6 alkenyl, C 3 -C 11 cycloalkyl, C 4 -C 11 cycloalkylalkyl, aryl, aryl(C 1 -C 6 alkyl)-, C 1 -C 6 alkoxy, and C 2 -C 5 alkoxycarbonyl;
R 2 is selected from H or C 1 -C 10 alkyl;
R 3 and R 4 are independently selected from the group consisting of H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 7 cycloalkyl, and aryl substituted with 0-2 R 3a ;
R 3a is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halo, CF 3 , NO 2 , and NR 3b R 3c ;
R 3b and R 3c are each independently selected from the group consisting of H, C 1 -C 10 alkyl, C 2 -C 10 alkoxycarbonyl, C 2 -C 10 alkylcarbonyl, C 1 -C 10 alkylsulfonyl, heteroaryl(C 1 -C 4 alkyl)sulfonyl, aryl(C 1 -C 10 alkyl)sulfonyl, arylsulfonyl, aryl, heteroarylcarbonyl, heteroarylsulfonyl, and heteroarylalkylcarbonyl, wherein said aryl and heteroaryl are optionally substituted with 0-3 R 3d ;
R 3d is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halo, CF 3 , and NO 2 ;
R 5 is selected from the group consisting of:
hydroxy, C 1 -C 10 alkyloxy, C 3 -C 11 cycloalkyloxy,
C 6 -C 10 aryloxy, C 7 -C 11 arylalkyloxy,
C 3 -C 10 alkylcarbonyloxyalkyloxy,
C 3 -C 10 alkoxycarbonyloxyalkyloxy,
C 3 -C 10 alkoxycarbonylalkyloxy,
C 5 -C 10 cycloalkylcarbonyloxyalkyloxy,
C 5 -C 10 cycloalkoxycarbonyloxyalkyloxy,
C 5 -C 10 cycloalkoxycarbonylalkyloxy,
C 8 -C 11 aryloxycarbonylalkyloxy,
C 8 -C 12 aryloxycarbonyloxyalkyloxy,
C 8 -C 12 arylcarbonyloxyalkyloxy,
C 5 -C 10 alkoxyalkylcarbonyloxyalkyloxy,
5-(C 5 -C 10 alkyl)-1,3-dioxa-cyclopenten-2-one-yl)-methyloxy,
(5-aryl-1,3-dioxa-cyclopenten-2-one-yl)-methyloxy, and
(R 5a )HN-(C 1 -C 10 alkoxy)-;
R 5a is selected from the group consisting of H, C 1 -C 4 alkyl, aryl(C 1 -C 10 alkoxy)carbonyl, C 2 -C 10 alkoxycarbonyl, and C 3 -C 6 alkenyl;
n is 0-4;
a is a single or double bond, with the proviso that if a is a double bond, it is not simultaneously substituted with R 3 and R 4 ;
said process comprising:
contacting a compound of formula (IV):
wherein:
R 6 is selected from the group consisting of H, CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CF 2 CF 2 CF 2 CF 3 , C 1 -C 8 alkyl, C 1 -C 8 perfluoroalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 11 cycloalkyl, C 4 -C 11 cycloalkylalkyl, aryl(C 1 -C 6 alkyl)-, C 1 -C 6 alkoxy, C 7 -C 10 arylalkyloxy, C 1 -C 6 alkyloxy, aryloxy and aryl substituted with 0-5 R 6c ;
R 6c is selected from the group consisting of H, halo, CF 3 , CN, NO 2 , NR 6d R 6e , C 1 -C 8 alkyl, C 2 -C 6 alkenyl, C 3 -C 11 cycloalkyl, C 4 -C 11 cycloalkylalkyl, aryl, aryl(C 1 -C 6 alkyl)-, C 1 -C 6 alkoxy, and C 2 -C 5 alkoxycarbonyl;
R 6d and R 6e are independently selected from the group consisting of H, C 1 -C 10 alkyl, C 2 -C 10 alkoxycarbonyl, C 2 -C 10 alkylcarbonyl, C 1 -C 10 alkylsulfonyl, aryl, aryl(C 1 -C 10 alkyl)sulfonyl, arylsulfonyl, heteroaryl(C 1 -C 4 alkyl)sulfonyl, heteroarylcarbonyl, heteroarylsulfonyl, or heteroarylalkylcarbonyl, wherein said aryl and heteroaryl are optionally substituted with 0-3 substituents selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halo, CF 3 , and NO 2 ;
with hydrogen under a suitable pressure in the presence of a hydrogenation catalyst to form a compound of formula (I) or a pharmaceutically acceptable salt form thereof.
In a preferred embodiment, the present invention provides a process for the preparation of a compound of formula (I), wherein:
said suitable pressure is up to 100 psi, and
said hydrogenation catalyst is selected from the group consisting of palladium on carbon, palladium hydroxide on carbon, palladium on calcium carbonate and platinum on carbon.
In a more preferred embodiment, the present invention provides a process for the preparation of a compound of formula (I), wherein:
R 1 is selected from H or NHR 1a ;
R 1a is —C(═O)—O—R 1b or —SO 2 —R 1b ;
R 1b is selected from the group consisting of:
C 1 -C 8 alkyl substituted with 0-1 R 1c ,
C 2 -C 8 alkenyl substituted with 0-1 R 1c ,
C 2 -C 8 alkynyl substituted with 0-1 R 1c ,
C 3 -C 8 cycloalkyl substituted with 0-1 R 1c ,
aryl substituted with 0-3 R 1c ,
aryl(C 1 -C 6 alkyl)-substituted with 0-3 R 1c ,
a 5-10 membered heterocyclic ring system having 1-3 heteroatoms selected independently from O, S, and N, said heterocyclic ring being substituted with 0-4 R 1c , and
C 1 -C 6 alkyl substituted with a 5-10 membered heterocyclic ring system having 1-3 heteroatoms selected independently from O,S, and N, said heterocyclic ring being substituted with 0-4 R 1c ;
R 1c is selected from the group consisting of H, halogen, CF 3 , CN, NO 2 , C 1 -C 8 alkyl, C 2 -C 6 alkenyl, C 3 -C 11 cycloalkyl, C 4 -C 11 cycloalkylalkyl, aryl, aryl(C 1 -C 6 alkyl)-, C 1 -C 6 alkoxy and C 2 -C 5 alkoxycarbonyl;
R 2 is H or C 1 -C 10 alkyl;
R 3 and R 4 are H or C 1 -C 6 alkyl;
R 5 is selected from the group consisting of hydroxy, C 1 -C 10 alkyloxy, C 3 -C 11 cycloalkyloxy, C 6 -C 10 aryloxy and C 7 -C 11 arylalkyloxy;
R 6 is selected from the group consisting of H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 7 cycloalkyl, C 1 -C 8 perfluoroalkyl, C 7 -C 10 arylalkyloxy, C 1 -C 6 alkyloxy, aryloxy, aryl substituted with 0-2 R 6c ;
R 6c is H, halogen, CF 3 , CN, NO 2 , NR 6d R 6e , C 1 -C 8 alkyl, C 2 -C 6 alkenyl, C 3 -C 11 cycloalkyl, C 4 -C 11 cycloalkylalkyl, aryl, aryl(C 1 -C 6 alkyl)-, C 1 -C 6 alkoxy, and C 2 -C 5 alkoxycarbonyl; and
R 6d and R 6e are independently selected from H or C 1 -C 10 alkyl;
n is 1;
a is a single or double bond, with the proviso that if a is a double bond, it is not simultaneously substituted with R 3 and R 4 .
In an even more preferred embodiment, the present invention provides a process for the preparation of a compound of formula (I-a):
or a pharmaceutically acceptable salt form thereof, wherein:
R 1a is —C(═O)OCH 2 (CH 2 ) 2 CH 3 or 3,5-dimethyloxazol-4-yl-sulfonyl;
comprising contacting a compound of formula (IV-a):
wherein R 6 is H, methyl, ethyl, propyl, butyl, pentyl, hexyl C 7 -C 8 arylalkyloxy, C 1 - 5 alkyloxy, aryloxy or aryl;
with hydrogen under a suitable pressure from about 20 to about 50 psi in the presence of palladium on carbon, in the range of about 1% to about 10% by weight of compound (IV), to form a compound of formula (I) or a pharmaceutically acceptable salt form thereof.
In a second embodiment, the present invention provides a process for the preparation of compounds of formula (IV) or a salt thereof comprising:
contacting a compound of formula (III):
with an acylating agent of formula R 6 CO—O—COR 6 or R 6 COX, wherein X is fluorine, bromine, chlorine or imidazole, in a suitable solvent to form a compound of formula (IV) or a salt thereof.
In a preferred second embodiment, the present invention provides a process for the preparation of a compound of formula (IV), wherein:
X is chlorine;
R 1 is NHR 1a ;
R 1a is —C(═O)OCH 2 (CH 2 ) 2 CH 3 or 3,5-dimethyloxazol-4-yl-sulfonyl;
R 2 is H;
R 3 and R 4 are H;
R 5 is methyl;
R 6 is CH 3 ;
n is 1;
a is a single bond; and
said suitable solvent is acetic acid.
In a third embodiment, the present invention provides a process for the preparation of compounds of formula (III), comprising:
contacting a compound of formula (II):
with a salt of hydroxyl amine in the presence of a suitable base to form a compound of formula (III).
In a preferred third embodiment, the present invention provides a process for the preparation of a compound of formula (III), wherein said salts of hydroxyl amine are hydroxylamine hydrochloride and hydroxlyamine sulfate.
In a more preferred third embodiment, the present invention provides a process for the preparation of a compound of formula (III), wherein:
X is chlorine;
R 1 is NHR 1a ;
R 1a is —C(═O)—O—CH 2 (CH 2 ) 2 CH 3 or 3,5-dimethyloxazol-4yl-sulfonyl;
R 2 is H;
R 3 and R 4 are H;
R 5 is methyl;
R 6 is selected from the group consisting of: H, C 1 -C 6 alkyl, C 7 -C 8 arylalkyloxy, C 1 -C 5 alkyloxy,
aryloxy and aryl;
n is 1;
a is a single bond;
said suitable salt of hydroxylamine is hydroxlyamine hydrochloride; and
the suitable base is selected from the group consisting of: triethylamine, diisopropylethylamine and 4-methyl morpholine.
In a fourth embodiment, the present invention provides a process for the preparation of compounds of formula (I):
or a pharmaceutically acceptable salt form thereof, said process comprising:
(a) heating a compound of the formula (IV):
wherein:
R 1 is selected from H or NHR 1a ;
R 1a is selected from the group consisting of:
—C(═O)—O—R 1b ,
—C(═O)—R 1b ,
—C(═O)N(R 1b ) 2 ,
—C(═O)NHSO 2 R 1b ,
—C(═O)NHC(═O)R 1b ,
—C(═O)NHC(═O)OR 1b ,
—C(═O)NHSO 2 NHR 1b ,
—C(═S)—NH—R 1b ,
—NH—C(═O)—O—R 1b ,
—NH—C(═O)R 1b ,
—NH—C(═)—NH—R 1b ,
—SO 2 —O—R 1b ,
—SO 2 —R 1b ,
—SO 2 —N(R 1b ) 2 ,
—SO2—NHC(═O)OR 1b ,
—P(═S)(OR 1b ) 2 ,
—P(═O)(OR 1b ) 2 ,
—P(═S)(R 1b ) 2 ,
—P(═O)(R 1b ) 2 , and
R 1b is selected from the group consisting of:
C 1 -C 8 alkyl substituted with 0-2 R 1c ,
C 2 -C 8 alkenyl substituted with 0-2 R 1c ,
C 2 -C 8 alkynyl substituted with 0-2 R 1c ,
C 3 -C 8 cycloalkyl substituted with 0-2 R 1c ,
aryl substituted with 0-4 R 1c ,
aryl (C 1 -C 6 alkyl)-substituted with 0-4 R 1c ,
a 5-10 membered heterocyclic ring system having 1-3 heteroatoms selected independently from O, S, and N, said heterocyclic ring being substituted with 0-4 R 1c , and
C 1 -C 6 alkyl substituted with a 5-10 membered heterocyclic ring system having 1-3 heteroatoms selected independently from O, S, and N, said heterocyclic ring being substituted with 0-4R 1c ;
R 1c is H, halogen, CF 3 , CN, NO 2 , C 1 -C 8 alkyl, C 2 -C 6 alkenyl, C 3 -C 11 cycloalkyl, C 4 -C 11 cycloalkylalkyl, aryl, aryl(C 1 -C 6 alkyl)-, C 1 -C 6 alkoxy, and C 2 -C 5 alkoxycarbonyl;
R 2 is selected from H or C 1 -C 10 alkyl;
R 3 and R 4 are independently selected from the group consisting of H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 7 cycloalkyl, and aryl substituted with 0-2 R 3a ;
R 3a is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halo, CF 3 , NO 2 , and NR 3b R 3c ;
R 3b and R 3c are each independently selected from the group consisting of H, C 1 -C 10 alkyl, C 2 -C 10 alkoxycarbonyl, C 2 -C 10 alkylcarbonyl, C 1 -C 10 alkylsulfonyl, heteroaryl(C 1 -C 4 alkyl)sulfonyl, aryl(C 1 -C 10 alkyl)sulfonyl, arylsulfonyl, aryl, heteroarylcarbonyl, heteroarylsulfonyl, and heteroarylalkylcarbonyl, wherein said aryl and heteroaryl are optionally substituted with 0-3 R 3d ;
R 3d is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halo, CF 3 , and NO 2 ;
R 5 is selected from the group consisting of:
hydroxy, C 1 -C 10 alkyloxy, C 3 -C 11 cycloalkyloxy,
C 6 -C 10 aryloxy, C 7 -C 11 arylalkyloxy,
C 3 -C 10 alkylcarbonyloxyalkyloxy,
C 3 -C 10 alkoxycarbonyloxyalkyloxy,
C 3 -C 10 alkoxycarbonylalkyloxy,
C 5 -C 10 cycloalkylcarbonyloxyalkyloxy,
C 5 -C 10 cycloalkoxycarbonyloxyalkyloxy,
C 5 -C 10 cycloalkoxycarbonylalkyloxy,
C 8 -C 11 aryloxycarbonylalkyloxy,
C 8 -C 12 aryloxycarbonyloxyalkyloxy,
C 8 -C 12 arylcarbonyloxyalkyloxy,
C 5 -C 10 alkoxyalkylcarbonyloxyalkyloxy,
5-(C 5 -C 10 alkyl)-1,3-dioxa-cyclopenten-2-one-yl)-methyloxy,
(5-aryl-1,3-dioxa-cyclopenten-2-one-yl)-methyloxy, and
(R 5a )HN-(C 1 -C 10 alkoxy)-;
R 5a is selected from the group consisting of H, C 1 -C 4 alkyl, aryl(C 1 -C 10 alkoxy)carbonyl, C 2 -C 10 alkoxycarbonyl, and C 3 -C 6 alkenyl;
R 6 is selected from the group consisting of H, CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CF 2 CF 2 CF 2 CF 3 , C 1 -C 8 alkyl, C 1 -C 8 perfluoroalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 11 cycloalkyl, C 4 -C 11 cycloalkylalkyl, aryl(C 1 -C 6 alkyl)-, C 1 -C 6 alkoxy, C 7 -C 10 arylalkyloxy, aryloxy and aryl substituted with 0-5 R 6c ;
R 6c is selected from the group consisting of H, halo, CF 3 , CN, NO 2 , NR 6d R 6e , C 1 -C 8 alkyl, C 2 -C 6 alkenyl, C 3 -C 11 cycloalkyl, C 4 -C 11 cycloalkylalkyl, aryl, aryl(C 1 -C 6 alkyl)-, C 1 -C 6 alkoxy, and C 2 -C 5 alkoxycarbonyl;
R 6d and R 6e are independently selected from the group consisting of H, C 1 -C 10 alkyl, C 2 -C 10 alkoxycarbonyl, C 2 -C 10 alkylcarbonyl, C 1 -C 10 alkylsulfonyl, aryl, aryl(C 1 -C 10 alkyl)sulfonyl, arylsulfonyl, heteroaryl(C 1 -C 4 alkyl)sulfonyl, heteroarylcarbonyl, heteroarylsulfonyl, or heteroarylalkylcarbonyl, wherein said aryl and heteroaryl are optionally substituted with 0-3 substituents selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halo, CF 3 , and NO 2 ;
n is 0-4;
a is a single or double bond, with the proviso that if a is a double bond, it is not simultaneously substituted with R 3 and R 4 ;
for a time sufficient, and to a temperature sufficient to form a compound of formula (V):
and (b) contacting said compound of formula (V) with hydrogen under a suitable pressure in the presence of a hydrogenation catalyst to form a compound of formula (I) or a salt thereof.
In a preferred fourth embodiment, the present invention provides a process for the preparation of a compound of formula (I), wherein:
said suitable pressure is up to 100 psi;
said hydrogenation catalyst is selected from the group consisting of palladium on carbon, palladium hydroxide on carbon, palladium on calcium carbonate and platinum on carbon;
said sufficient temperature is from about 30° C. to about 120° C.;
said sufficient time is from about 10 minutes to about 24 hours;
wherein an amount of catalyst loaded on carbon is from about 1% to about 10% by weight; and
wherein an amount of a hydrogenation catalyst is from about 1% to about 30% by weight of compound (IV).
In a more preferred fourth embodiment, the present invention provides a process for the preparation of a compound of formula (I), wherein:
R 1 is NHR 1a ;
R 1a is —C(═O)—O—CH 2 (CH 2 ) 2 CH 3 or 3,5-dimethyloxazol-4yl-sulfonyl;
R 2 is H;
R 3 and R 4 are H;
R 5 is methyl;
R 6 is selected from the group consisting of: H, methyl, ethyl, propyl, butyl, pentyl, hexyl, C 7 -C 8 arylalkyloxy, aryloxy, C 1 -C 5 alkoxy and aryl;
n is 1, and
a is a single bond;
said suitable pressure is from about 20 to about 50 psi;
said sufficient temperature is from about 50° C. to about 120° C.;
said sufficient time is from about 10 minutes to about 3 hours;
said hydrogenation catalyst is palladium on carbon;
wherein an amount of catalyst loaded on carbon is from about 3% to about 5% by weight; and
wherein an amount of palladium on carbon is from about 3% to about 7% by weight of compound (IV).
In a fifth embodiment, the present invention provides a process for the preparation of compounds of the formula (I):
or a pharmaceutically acceptable salt form thereof; wherein:
R 1 is selected from H or NHR 1a ;
R 1a is selected from the group consisting of:
—C(═O)—O—R 1b ,
—C(═O)—R 1b ,
—C(═O)N(R 1b ) 2 ,
—C(═O)NHSO 2 R 1b ,
—C(═O)NHC(═O)R 1b ,
—C(═O)NHC(═O)OR 1b ,
—C(═O)NHSO 2 NHR 1b ,
—C(═S)—NH—R 1b ,
—NH—C(═O)—O—R 1b ,
—NH—C(═O)R 1b ,
—NH—C(═)—NH—R 1b ,
—SO 2 —O—R 1b ,
—SO 2 —R 1b ,
—SO 2 —N(R 1b ) 2 ,
—SO 2 —NHC(═O)OR 1b ,
—P(═S)(OR 1b ) 2 ,
—P(═O)(OR 1b ) 2 ,
—P(═S)(R 1b ) 2 ,
—P(═O)(R 1b ) 2 , and
R 1b is selected from the group consisting of:
C 1 -C 8 alkyl substituted with 0-2 R 1c ,
C 2 -C 8 alkenyl substituted with 0-2 R 1c ,
C 2 -C 8 alkynyl substituted with 0-2 R 1c ,
C 3 -C 8 cycloalkyl substituted with 0-2 R 1c ,
aryl substituted with 0-4 R 1c ,
aryl(C 1 -C 6 alkyl)-substituted with 0-4 R 1c ,
a 5-10 membered heterocyclic ring system having 1-3 heteroatoms selected independently from O, S, and N, said heterocyclic ring being substituted with 0-4 R 1c , and
C 1 -C 6 alkyl substituted with a 5-10 membered heterocyclic ring system having 1-3 heteroatoms selected independently from O, S, and N, said heterocyclic ring being substituted with 0-4R 1c ;
R 1c is H, halogen, CF 3 , CN, NO 2 , C 1 -C 8 alkyl, C 2 -C 6 alkenyl, C 3 -C 11 cycloalkyl, C 4 -C 11 cycloalkylalkyl, aryl, aryl(C 1 -C 6 alkyl)-, C 1 -C 6 alkoxy, and C 2 -C 5 alkoxycarbonyl;
R 2 is selected from H or C 1 -C 10 alkyl;
R 3 and R 4 are independently selected from the group consisting of H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 7 cycloalkyl, and aryl substituted with 0-2 R 3a ;
R 3a is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halo, CF 3 , NO 2 , and NR 3b R 3c ;
R 3b and R 3c are each independently selected from the group consisting of H, C 1 -C 10 alkyl, C 2 -C 10 alkoxycarbonyl, C 2 -C 10 alkylcarbonyl, C 1 -C 10 alkylsulfonyl, heteroaryl(C 1 -C 4 alkyl)sulfonyl, aryl(C 1 -C 10 alkyl)sulfonyl, arylsulfonyl, aryl, heteroarylcarbonyl, heteroarylsulfonyl, and heteroarylalkylcarbonyl, wherein said aryl and heteroaryl are optionally substituted with 0-3 R 3d ;
R 3d is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halo, CF 3 , and NO 2 ;
R 5 is selected from the group consisting of:
hydroxy, C 1 -C 10 alkyloxy, C 3 -C 11 cycloalkyloxy,
C 6 -C 10 aryloxy, C 7 -C 11 arylalkyloxy,
C 3 -C 10 alkylcarbonyloxyalkyloxy,
C 3 -C 10 alkoxycarbonyloxyalkyloxy,
C 3 -C 10 alkoxycarbonylalkyloxy,
C 5 -C 10 cycloalkylcarbonyloxyalkyloxy,
C 5 -C 10 cycloalkoxycarbonyloxyalkyloxy,
C 5 -C 10 cycloalkoxycarbonylalkyloxy,
C 8 -C 11 aryloxycarbonylalkyloxy,
C 8 -C 12 aryloxycarbonyloxyalkyloxy,
C 8 -C 12 arylcarbonyloxyalkyloxy,
C 5 -C 10 alkoxyalkylcarbonyloxyalkyloxy,
5-(C 5 -C 10 alkyl)-1,3-dioxa-cyclopenten-2-one-yl)-methyloxy,
(5-aryl-1,3-dioxa-cyclopenten-2-one-yl)-methyloxy, and
(R 5a )HN-(C 1 -C 10 alkoxy)-;
R 5a is selected from the group consisting of H, C 1 -C 4 alkyl, aryl(C 1 -C 10 alkoxy)carbonyl, C 2 -C 10 alkoxycarbonyl, and C 3 -C 6 alkenyl;
n is 0-4;
a is a single or double bond, with the proviso that if a is a double bond, it is not simultaneously substituted with R 3 and R 4 ;
said process comprising:
contacting a compound of formula (VI):
wherein:
Z is selected from R 6 SO 2 — or (R 7 ) 3 Si—;
R 6 is selected from the group consisting of H, CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CF 2 CF 2 CF 2 CF 3 C 1 -C 8 alkyl, C 1 -C 8 perfluoroalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 11 cycloalkyl, C 4 -C 11 cycloalkylalkyl, aryl(C 1 -C 6 alkyl)-, C 1 -C 6 alkoxy, C 7 -C 10 arylalkyloxy, aryloxy and aryl substituted with 0-5 R 6c ;
R 6c is selected from the group consisting of H, halo, CF 3 , CN, NO 2 , NR 6d R 6e , C 1 -C 8 alkyl, C 2 -C 6 alkenyl, C 3 -C 11 cycloalkyl, C 4 -C 11 cycloalkylalkyl, aryl, aryl(C 1 -C 6 alkyl)-, C 1 -C 6 alkoxy, and C 2 -C 5 alkoxycarbonyl;
R 6d and R 6e are independently selected from the group consisting of H, C 1 -C 10 alkyl, C 2 -C 10 alkoxycarbonyl, C 2 -C 10 alkylcarbonyl, C 1 -C 10 alkylsulfonyl, aryl, aryl(C 1 -C 10 alkyl)sulfonyl, arylsulfonyl, heteroaryl(C 1 -C 4 alkyl)sulfonyl, heteroarylcarbonyl, heteroarylsulfonyl, or heteroarylalkylcarbonyl, wherein said aryl and heteroaryl are optionally substituted with 0-3 substituents selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halo, CF 3 , and NO 2 ;
R 7 is selected independently from C 1 -C 10 alkyl or aryl substituted 0-3 R 7a ; and
R 7a is C 1 -C 10 alkyl;
with hydrogen under a suitable pressure in the presence of a hydrogenation catalyst to form a compound of formula (I) or a pharmaceutically acceptable salt form thereof.
In a sixth embodiment, the present invention provides a process for the preparation of compounds of formula (VI):
comprising: contacting a compound of formula (III):
with an agent of formula Z-X, wherein:
X is fluorine, bromine or chlorine;
Z is R 6 SO 2 — or (R 7 ) 3 Si—;
R 7 is selected independently from C 1 -C 10 alkyl or aryl substituted 0-3 R 7a ; and
R 7a is C 1 -C 10 alkyl;
in the presence of a suitable acid scavenger in a suitable solvent to form a compound of formula (IV) or a salt thereof.
In a seventh embodiment, the present invention provides a compound of formula (III-i):
and salt forms thereof.
In a eighth embodiment, the present invention provides a compound of formula (IV-i):
and salt forms thereof.
In a ninth embodiment, the present invention provides a compound of formula (V-i):
and salt forms thereof.
DEFINITIONS
The reactions of the synthetic methods claimed herein are carried out in suitable solvents which may be readily selected by one of skill in the art of organic synthesis, said suitable solvents generally being any solvent which is substantially nonreactive with the starting materials (reactants), the intermediates, or products at the temperatures at which the reactions are carried out, i.e., temperatures which may range from the solvent's freezing temperature to the solvent's boiling temperature. A given reaction may be carried out in one solvent or a mixture of more than one solvent. Depending on the particular reaction step, suitable solvents for a particular reaction step may be selected.
Suitable halogenated solvents include: carbon tetrachloride, bromodichloromethane, dibromochloromethane, bromoform, chloroform, bromochloromethane, dibromomethane, butyl chloride, dichloromethane, tetrachloroethylene, trichloroethylene, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1-dichloroethane, 2-chloropropane, hexafluorobenzene, 1,2,4-trichlorobenzene, o-dichlorobenzene, chlorobenzene, fluorobenzene, fluorotrichloromethane, chlorotrifluoromethane, bromotrifluoromethane, carbon tetrafluoride, dichlorofluoromethane, chlorodifluoromethane, trifluoromethane, 1,2-dichlorotetrafluorethane and hexafluoroethane.
Suitable ether solvents include: dimethoxymethane, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, furan, diethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, anisole, or t-butyl methyl ether.
Suitable protic solvents may include, by way of example and without limitation, water, methanol, ethanol, 2-nitroethanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, ethylene glycol, 1-propanol, 2-propanol, 2-methoxyethanol, 1-butanol, 2-butanol, i-butyl alcohol, t-butyl alcohol, 2-ethoxyethanol, diethylene glycol, 1-, 2-, or 3- pentanol, neo-pentyl alcohol, t-pentyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, cyclohexanol, benzyl alcohol, phenol, or glycerol.
Suitable aprotic solvents may include, by way of example and without limitation, tetrahydrofuran (THF), dimethylformamide (DMF), dimethylacetamide (DMAC), 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU), 1,3-dimethyl-2-imidazolidinone (DMI), N-methylpyrrolidinone (NMP), formamide, N-methylacetamide, N-methylformamide, acetonitrile, dimethyl sulfoxide, propionitrile, ethyl formate, methyl acetate, hexachloroacetone, acetone, ethyl methyl ketone, ethyl acetate, sulfolane, N,N-dimethylpropionamide, tetramethylurea, nitromethane, nitrobenzene, or hexamethylphosphoramide.
Suitable hydrocarbon solvents include: benzene, cyclohexane, pentane, hexane, toluene, cycloheptane, methylcyclohexane, heptane, ethylbenzene, m-, o-, or p-xylene, octane, indane, nonane, or naphthalene.
Suitable carboxylic acid solvents include acetic acid, trifluoroacetic acid, ethanoic acid, propionic acid, propiolic acid, butyric acid, 2-butynoic acid, vinyl acetic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid and decanoic acid.
Suitable pressures range from atmospheric to any pressure obtainable in a laboratory or industrial plant.
Suitable hydrogenation catalysts are those which facilitate the delivery of hydrogen to the N—O bond of an N-acylated hydroxylamine. Such hydrogenation catalysts by way of example and without limitation are palladium on carbon, palladium hydroxide on carbon, palladium on calcium carbonate poisoned with lead and platinum on carbon.
As used herein, suitable acid scavengers include those compounds capable of accepting a proton from a hydroxyamidine during either an acylation, sulfonation or silation reaction without reacting with the agent reacting with the oxygen of the hydroxyamidine. Examples include, but are not limited to tertiary bases such as N,N-diisopropylethylamine, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-lutidine, triethylamine, 2-, 3-, or 4-picoline, pyrrole, pyrrolidine, N-methyl morpholine, pyridine and pyrimidine.
As used herein, suitable bases include those soluble in the reaction solvent and capable of free-basing hydroxylamine. Examples include, but are not limited to: lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, imidazole, ethylene diamine, N,N-diisopropylethylamine, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-lutidine, triethylamine, 2-, 3-, or 4-picoline, pyrrole, pyrrolidine, N-methyl morpholine, pyridine, pyrimidine or piperidine.
As used herein, acylating agent refers to an acid halide or anhydride, which, when reacted with a hydroxyamidine results in O-acylation of the hydroxyl amidine. Such acylating agents by way of example and without limitation are of the general structure R 6c COX or R 6 CO—O—COR 6 , as defined above in the specification. By way of further example, and without limitation, where X is fluorine, chlorine, bromine or imidazole, R 6 is H, CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CF 2 CF 2 CF 2 CF 3 , methyl, ethyl, propyl, butyl, ethenyl, allyl, ethynyl, cyclopropyl, phenyl, benzyl, C 7 -C 10 arylalkyloxy, C 1 -C 10 alkyloxy or aryloxy.
As used herein, agent refers to a compound of the formula Z-X, which, when reacted with a hydroxyamidine results in placement of the Z group on the oxygen of the hydroxyamidine. By way of further example, and without limitation, where X is fluorine, chlorine, bromine or imidazole, Z is either R 6 SO 2 — or (R 7 ) 3 Si—, R 6 is H, CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CF 2 CF 2 CF 2 CF 3 , methyl, ethyl, propyl, butyl, ethenyl, allyl, ethynyl, cyclopropyl, phenyl, benzyl, C 7 -C 10 arylalkyloxy, or aryloxy, and R 7 is independently selected from C 1 -C 10 alkyl or aryl substituted with 0-3 R 7a , and R 7a is C 1 -C 10 alkyl.
The compounds described herein may have asymmetric centers. Unless otherwise indicated, all chiral, diastereomeric and racemic forms are included in the present invention. Many geometric isomers of olefins, C═N double bonds, and the like can also be present in the compounds described herein, and all such stable isomers are contemplated in the present invention. It will be appreciated that compounds of the present invention that contain asymmetrically substituted carbon atoms may be isolated in optically active or racemic forms. Methods on how to prepare optically active forms from optically active starting materials are known in the art, such as by resolution of racemic forms or by synthesis. All chiral, diastereomeric, racemic forms and all geometric isomeric forms of a structure are intended.
When any variable (for example but not limited to R 1b , R 1c , R 3a , R 3b , R 3c , R 6c , etc.) occurs more than one time in any constituent or in any formula, its definition on each occurrence is independent of its definition at every other occurrence. Thus, for example, if a group is shown to be substituted with 0-2 R 3a , then said group may optionally be substituted with up to two R 3a and R 3a at each occurrence is selected independently from the defined list of possible R 3a .
Combinations of substituents and/or variables are permissible only if such combinations result in stable compounds. By stable compound or stable structure it is meant herein a compound that is sufficiently robust to survive isolation to a useful degree of purity from a reaction mixture, and formulation into an efficacious therapeutic agent.
The term “substituted”, as used herein, means that any one or more hydrogen on the designated atom is replaced with a selection from the indicated group, provided that the designated atom's normal valency is not exceeded, and that the substitution results in a stable compound.
As used herein, “alkyl” is intended to include both branched and straight-chain saturated aliphatic hydrocarbon groups having the specified number of carbon atoms; for example, C 1 -C 4 alkyl includes methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, and t-butyl; for example C 1 -C 10 alkyl includes C 1 -C 4 alkyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomer thereof.
As used herein, any carbon range such as “Cx-Cy” is intended to mean a minimum of “x” carbons and a maximum of “y” carbons representing the total number of carbons in the substituent to which it refers. For example, “C 3 -C 10 alkylcarbonyloxyalkyloxy” could contain one carbon for “alkyl”, one carbon for “carbonyloxy” and one carbon for “alkyloxy” giving a total of three carbons, or a larger number of carbons for each alkyl group not to exceed a total of ten carbons.
“Alkenyl” is intended to include hydrocarbon chains of either a straight or branched configuration and one or more unsaturated carbon-carbon bonds which may occur in any stable point along the chain, such as ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl and the like. “Alkynyl” is intended to include hydrocarbon chains of either a straight or branched configuration and one or more triple carbon-carbon bonds which may occur in any stable point along the chain, such as ethynyl, propynyl, butynyl and the like. “Aryl” is intended to mean phenyl or naphthyl. The term “arylalkyl” represents an aryl group attached through an alkyl bridge; for example aryl(C 1 -C 2 )alkyl is intended to mean benzyl, phenylethyl and the like.
As used herin, “cycloalkyl” is intended to include saturated ring groups, including mono-, bi-, or poly-cyclic ring systems, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and adamantyl.
As used herein, “alkyloxy” or “alkoxy” represents an alkyl group of indicated number of carbon atoms attached through an oxygen bridge, for example methoxy, ethoxy, propoxy, i-propoxy, butoxy, i-butoxy, s-butoxy and t-butoxy. The term “aryloxy” is intended to mean phenyl or naphthyl attached through an oxygen bridge;
As used herein, “carbonyl” means a carbon double bonded to oxygen and additionally substituted with two groups through single bonds; “carbonyloxy” means a carbon double bonded to oxygen and additionally bonded through a single bonds to two groups, one of which is an oxygen. As used herein, “sulfonyl” is intended to mean a sulfur bonded through double bonds to two oxygens and bonded to two additional groups through single bonds. As used herein, “hydroxy” means a group consisting of an oxygen and a hydrogen bonded to another group through the oxygen.
“Halo” or “halogen” as used herein refers to fluoro, chloro, bromo and iodo.
As used herein, the term “heterocycle” or “heterocyclic” is intended to mean a stable 5- to 10-membered monocyclic or bicyclic or 5- to 10-membered bicyclic heterocyclic ring which may be saturated, partially unsaturated, or aromatic, and which consists of carbon atoms and from 1 to 3 heteroatoms independently selected from the group consisting of N, O and S and wherein the nitrogen and sulfur heteroatoms may optionally be oxidized, and the nitrogen may optionally be quaternized, 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 to its pendant group at any heteroatom or carbon atom which results in a stable structure. The heterocyclic rings described herein may be substituted on carbon or on a nitrogen atom if the resulting compound is stable. Examples of such heterocycles include, but are not limited to, pyridyl (pyridinyl), pyrimidinyl, furanyl (furyl), thiazolyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, tetrazolyl, benzofuranyl, benzothiophenyl, indolyl, indolenyl, isoxazolinyl, quinolinyl, isoquinolinyl, benzimidazolyl, piperidinyl, 4-piperidonyl, pyrrolidinyl, 2-pyrrolidonyl, pyrrolinyl, tetrahydrofuranyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl or octahydroisoquinolinyl, azocinyl, triazinyl, 6H-1,2,5-thiadiazinyl, 2H, 6H-1,5,2-dithiazinyl, thianthrenyl, pyranyl, isobenzofuranyl, chromenyl, xanthenyl, phenoxathiinyl, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, isothiazolyl, isoxazolyl, oxazolyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, 3H-indolyl, 1H-indazolyl, purinyl, 4H-quinolizinyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, 4aH-carbazole, carbazole, β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, phenarsazinyl, phenothiazinyl, furazanyl, phenoxazinyl, isochromanyl, chromanyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperazinyl, indolinyl, isoindolinyl, quinuclidinyl, morpholinyl or oxazolidinyl. Also included are fused ring and spiro compounds containing, for example, the above heterocycles.
As used herein, the term “heteroaryl” refers to aromatic heterocyclic groups. Such heteroaryl groups are preferably 5-6 membered monocylic groups or 8-10 membered fused bicyclic groups. Examples of such heteroaryl groups include, but are not limited to pyridyl (pyridinyl), pyrimidinyl, furanyl (furyl), thiazolyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, indolyl, isoxazolyl, oxazolyl, pyrazinyl, pyridazinyl, benzofuranyl, benzothienyl, benzimidazolyl, quinolinyl, or isoquinolinyl.
As used herein, “pharmaceutically acceptable salts” refer to derivatives of the disclosed compounds wherein the intermediates or final compound are modified by making acid or base salts of the intermediates or final compounds. Examples of pharmaceutically acceptable salts include, but are not limited to, mineral or organic acid salts of basic residues such as amines; alkali or organic salts of acidic residues such as carboxylic acids; and the like.
The pharmaceutically acceptable salts of the intermediates or final compounds include the conventional non-toxic salts or the quaternary ammonium salts from non-toxic inorganic or organic acids. For example, such conventional non-toxic salts include those derived from inorganic acids such as hydrochloric, hydrobromic, sulfuric, sulfamic, phosphoric, nitric and the like; and the salts prepared from organic acids such as acetic, propionic, succinic, glycolic, stearic, lactic, malic, tartaric, citric, ascorbic, pamoic, maleic, hydroxymaleic, phenylacetic, glutamic, benzoic, salicylic, sulfanilic, 2-acetoxybenzoic, fumaric, toluenesulfonic, methanesulfonic, ethane disulfonic, oxalic, isethionic, and the like.
The pharmaceutically acceptable salts are generally prepared by reacting the free base or acid with stoichiometric amounts or with an excess of the desired salt-forming inorganic or organic acid or base in a suitable solvent or various combinations of solvents.
The pharmaceutically acceptable salts of the acids of the intermediates or final compounds are prepared by combination with an appropriate amount of a base, such as an alkali or alkaline earth metal hydroxide e.g. sodium, potassium, lithium, calcium, or magnesium, or an organic base such as an amine, e.g., dibenzylethylenediamine, trimethylamine, piperidine, pyrrolidine, benzylamine and the like, or a quaternary ammonium hydroxide such as tetramethylammoinum hydroxide and the like.
As discussed above, pharmaceutically acceptable salts of the compounds of the invention can be prepared by reacting the free acid or base forms of these compounds with a stoichiometric amount of the appropriate base or acid, respectively, in water or in an organic solvent, or in a mixture of the two; generally, nonaqueous media like ether, ethyl acetate, ethanol, isopropanol, or acetonitrile are preferred. Lists of suitable salts are found in Remington's Pharmaceutical Sciences , 17th ed., Mack Publishing Company, Easton, Pa., 1985, p. 1418, the disclosure of which is hereby incorporated by reference. The present invention is contemplated to be practiced on at least a multigram scale, kilogram scale, multikilogram scale, or industrial scale. Multigram scale, as used herein, is preferably the scale wherein at least one starting material is present in 10 grams or more, more preferably at least 50 grams or more, even more preferably at least 100 grams or more. Multikilogram scale, as used herein, is intended to mean the scale wherein more than one kilogram of at least one starting material is used. Industrial scale as used herein is intended to mean a scale which is other than a laboratory scale and which is sufficient to supply product sufficient for either clinical tests or distribution to consumers.
The methods of the present invention, by way of example and without limitation, may be further understood by reference to Scheme 1. Scheme 1 details the general synthetic method for synthesis of compounds of formula (I). Compound (II) can be prepared by methods described in J. Org. Chem . 1997, 62, 2466-2470, and Tetrahedron Lett . 1996, 37, 4455-4458. It is understood to one skilled in the art that the anhydride or acid chlorides used in the acylation step can be prepared by conversion of carboxylic acid derivatives as described in Advanced Organic Chemistry , March, 4th edition, John Wiley and Sons, Inc., 1992, p. 401-402 and p. 437-438.
In reaction 1, a compound of formula (II) is dissolved in about 10 liters of suitable solvent per kilogram of compound (II). A suitable salt of hydroxyl amine is added. While a wide range of solvents such as halogenated, protic, aprotic, hydrocarbon, or ethers can be used, protic solvents such as methanol, ethanol and isopropanol are preferred, of which methanol is most preferred. Suitable salts of hydroxyl amine include phosphate, sulfate, nitrate and hydrochloride salts; a most preferred salt is hydroxyl amine hydrochloride. The hydroxyl amine salt is free-based with about 1.0 to about 2.0 equivalents of an appropriate base. Preferrable bases are tertiary amines; most preferred is triethyl amine. The reaction mixture can then be heated for a time sufficent to form a compound of form (III). By way of general guidance, compound (II) may be contacted with free-based hydroxyl amine at about 40° C. to about 65° C. for about 1 to about 5 hours to produce compound (III). Preferred temperatures are from about 55° C. to about 65° C. Preferred reaction times are from about 2 to about 4 hours. The product precipitates as a white solid during the course of the reaction. The solids can then be filtered and the cake washed with a solvent, the choice of which is readily understood by one skilled in the art. The product is dried to afford pure compound (III).
In reaction 2, a vessel is charged with compound (III). The solids are dissolved in a suitable solvent followed by the slow charging of the vessel with a second solution made by dissolving a suitable acylating agent in the solvent being used for the reaction. Preferably, the addition of the acylating agent solution should be done over a period of about 15 minutes to about one hour. While a wide range of reaction solvents such as halogenated, aprotic, hydrocarbon, ether, or organic acids are possible, preferred solvents are acetic acid, trifluoroacetic acid, pyridine, chloroform, dichloromethane, dichlorobenzene, acetonitrile, and tetrahydrofuran. Most preferred are carboxylic acids which are structural derivatives of the acylating agent being used. By way of general example, acetic acid would preferably be used as the solvent when acetic anhydride is the acylating agent, whereas triflouroacetic acid would be preferably used when trifluoroacetic anhydride is the acylating agent. Certain solvents such as aprotic, ether, halogenated and hydrocarbon solvents may require the addition of an acid scavenger. Preferred acid scavengers include tertiary bases such as triethyl amine, diisopropyl ethylamine, N-methyl morpholine and pyridine. Most preferred is triethyl amine. Solvents capable of reacting with the acylating agent, such as alcohols, water and the like are not preferred as is readily understood by one skilled in the art. Preferred acylating agents are anhydrides. Most preferred is acetic anhydride. Further, the acylating agent (and preferable solvent) can be strategically chosen to form the desired salt of the reaction product. By way of general example, acetic anhydride would be selected as the acylating agent if the acetate salt of the product is desired. The choice of acylating agent and solvent in this regard is readily understood by one skilled in the art.
After the addition of the acylating agent, the reaction progression can be monitored by HPLC analysis performed on an aliquot of the reaction solution. The acylation reaction is considered finished when compound (III) is completely consumed. Typical reaction times are in the range of about 5 minutes to about 24 hours. Preferred reaction times are about 5 minutes to about 3 hours. The product can be isolated by the removal of the solvent via distillation and precipitation of the product through the addition of a suitable aprotic solvent. Preferred aprotic solvents are ethers. The choice of precipition solvent and the methods of isolation are readily understood by one skilled in the art. Preferably, the product is carried forward without isolation.
Reaction 3, comprises the hydrogenation of the O-substituted hydroxyamidine. This reaction can be carried out without isolation of compound (IV), by the addition of a slurry of a suitable hydrogention catalyst in the solvent used in the preceding reaction. If compound (IV) is isolated, the hydrogenation can be carried out in protic, aprotic, hydrocarbon, ether, or organic acid solvents. The preferred solvents are methanol, ethanol, 2-propanol, dimethylformamide, ethyl acetate, anisole, acetic acid and trifluoroacetic acid. Most preferred is a mixture of methanol and acetic acid. While numerous hydrogenation catalysts are possible, palladium on carbon is most preferred. The amount of catalyst loaded on the carbon ranges from about 0.5% to about 30%. The preferred amount of catalyst on carbon is about 1% to about 10%. Most preferred is about 3% to 5%. The total weight of the catalyst and carbon per gram of starting material is preferably about 1% to about 10%. Most preferred is about 3% to 7%. The total weight of catalyst and carbon is based on the weight of the O-alkylated hydroxyamidine. The reaction solution is then subjected to a hydrogen atmosphere under a suitable pressure. Preferred pressures range from about 1 psi to 100 psi. Most preferred is 20 psi to 50 psi. The reaction time of the hydrogenation is dependent on cumulative factors, including the amount of catalyst present, the reaction temperature and the hydrogen pressure. By way of general example, an acetylation reaction containing 10.0 kilograms of compound (III) required the use of 0.5 kilograms of 3% palladium on carbon, under 5 psi of hydrogen at room temperature to reach completion in about 5 hours. Varying any one of these conditions will effect reaction time which is readily understood by one skilled in the art.
Reaction completion can be monitored by HPLC analysis performed on aliquots of the reaction mixture. The reaction is considered complete when compound (IV) has been completely consumed. After the reaction is judged complete, the catalyst is filtered off and washed with reaction solvent. The filtrate is concentrated, and the product precipitated by the addition of a suitable aprotic solvent. The most preferred solvent for precipitation is acetone. The choice of precipition solvent and the methods of isolation are readily understood by one skilled in the art. The product is then filtered and dried to give pure compound (I).
In reaction 4, the resultant reaction solution of Step 2 is heated to form compound (V). The heating range is from about 30° C. to the reflux temperature of the solvent. Preferred temperatures are from about 30° C. to about 120° C. Preferred solvents for the cyclization are acetic acid, trifluoroacetic acid, pyridine, chloroform, dichloromethane, dichlorobenzene, acetonitrile, and tetrahydrofuran. The most preferred solvent for the cyclization is acetic acid. The preferred time of reflux is solvent dependent due to the limitations of boiling points. By way of general example, the use of acetic acid as the solvent required a heating time of about 3 hours. The product can be isolated by the removal of the solvent via distillation followed by the drying of the solids. Preferably, compound (V) is carried forward without isolation.
In reaction 4, compound (V) is hydrogenated under the identical conditions of Reaction 3 to give compound (I). The present invention may be further exemplified without limitation by reference to Scheme 2.
The following examples are meant to be illustrative of the present invention. These examples are presented to exemplify the invention and are not to be construed as limiting the inventors scope.
EXAMPLE 1
(R)-Methyl-3-[[[3[4[amino(hydroxyimino)methyl] phenyl]-4,5-dihydro-5-isoxazolyl]acetyl]amino]-N (butoxy-carbonyl)-L-alanine: Compound (III-i)
A 100 gal stainless steel reactor was charged with methanol (87 Kg), compound (II-i) (11 Kg), hydroxylamine hydrochloride (3.6 Kg), and triethylamine (5.2 Kg). The reaction mixture was heated at 60° C. for 3 h and a large amount of solid precipitated during the reaction. After cooling to 0-5° C., the solid was filtered through a Nutsche filter and the cake was washed with a mixture of methanol and water (made from 20 Kg of methanol and 25 Kg of water). After dried the cake, the product (11.8 Kg) was obtained.
EXAMPLE 2
(R)-Methyl-3-[[[3-[4-(aminoiminomethyl)phenyl]-4,5-dihydro-5-isoxazolyl]acetyl]amino]-N(butoxy carbonyl)-L-alanine monoacetate: Compound (I-i)
A 50 gal stainless steel reactor was charged with acetic acid(63 Kg) and (R)-Methyl-3[[[3[4[amino(hydroxyimino) methyl]phenyl]-4, 5-dihydro-5-isoxazolyl]acetyl]amino]-N (butoxy-carbonyl)-L-alanine (Batch 1:10.0 Kg; Batch 2: 10.0 Kg.) A solution of acetic anhydride (Batch 1:2205 g; Batch 2:1983 g) in acetic acid (21 Kg) was charged into the reactor slowly over 30 min from a pressure cylinder using nitrogen pressure at rt (22° C.). Additional 5.3 Kg of acetic acid was then used to rinse the cylinder. After stirring at 22° C. for 30 min or until a clear solution was attained, a small sample was taken for HPLC analysis. After the reaction was complete as determined by HPLC. A slurry of Pd/C(Batch 1:3%Pd/C, 0.5 Kg; Batch 2: 5%Pd/C, 0.4 Kg) in acetic acid (5 L) was added and the resulting mixture was hydrogenated under 5 psi hydrogen pressure for 4-5 h. After the reaction was complete as determined by HPLC, the catalyst was filtered off and washed with acetic acid (21 Kg) to give a solution of the product. Anisole (80 Kg) was then added to the filtrate and the resulting mixture was concentrated at about 70° C. under vacuum (40 mm Hg or lower) in a 100 gal reactor. The distillation was stopped until that the distillate was about 148 L or the solid became visible in the batch. Cooled the reactor to 40° C., 72 Kg of acetone was added over 30-90 min. The slurry was stirred at ambient temperature for 1 h and the 0-5° C. for another 1 h. The solid was collected on a Rosenmund filter/dryer and the cake was washed with 10% methanol in acetone (made from 6 Kg of methanol and 57 Kg of acetone). The solid cake was dried until LOD<1%. A hot (80° C.) mixture of acetonitrile (27 Kg) and acetic acid (18 Kg) was charged into the filter to dissolve the cake and the hot solution was then transfer back to 100 gal reactor. The transfer line was washed with a mixture of acetic acid (0.9 Kg) and acetonitrile (1.4 Kg). After the solution was cooled to 40-45° C., acetone (65 Kg) was added within 10 min. The resulting slurry was stirred gently at 25° C. for 1 h and then 0-5° C. for another 1 h. The solid was filtered by the Rosenmund filter/dryer and the cake was washed with 10% methanol in acetone (prepared from 5.5 Kg methanol and 50 Kg of acetone). After drying the cake until LOD<0.1%, the product was obtained (Batch 1:6.3 Kg. Batch 2: 6.8 Kg). Heels from both batches in the Rosenmund filter/dryer were dissolved in acetonitrile and acetic acid and combined, which was crystallized in the Kilo lab to give additional 2.86 Kg of product.
EXAMPLE 3
(R)-methyl-3-[[[3-[4-[(acetyloxyimino)aminomethyl] phenyl]-4,5-dihydro-5-isoxazolyl]acetyl]amino]-N-(butoxycarbonyl)-L-alanine: Compound (IV-i)
To a suspension of (R)-Methyl-3-[[[3-[4-[amino (hydroxyimino)methyl]phenyl]-4,5-dihydro-5-isoxazolyl] acetyl]amino]-N-(butoxycarbonyl)-L-alanine (11.76 g) in acetic acid (50 mL) was added acetic anhydride (3.6 g) dropwise. After the completion of addition, the reaction mixture was stirred at room temperature 15 min. The reaction mass became clear. Ether (200 mL) was added slowly and a thick slurry formed. The resulting mixture was then stirred for another 1.5 h at room temperature and the solid was filtered. The cake was washed with ether (50 mL) and dried to give (R)-methyl-3-[[[3-[4-[(acetyloxyimino) aminomethyl] phenyl]-4,5-dihydro-5-isoxazolyl] acetyl]amino]-N-(butoxycarbonyl)-L-alanine (12.3 g).
EXAMPLE 4
(R)-methyl—N-(butoxycarbonyl)-3-[[[4,5-dihydro-3-[4-(5-methyl-1,2,4-oxadiazol-3-yl)phenyl]-5-isoxazolyl]acetyl] amino]-L-alanine: Compound (V-i)
To a suspension of (R)-Methyl-3-[[[3-[4-[amino (hydroxyimino)methyl]phenyl]-4,5-dihydro-5-isoxazolyl] acetyl]amino]-N-(butoxycarbonyl)-L-alanine (1.05 g) in acetic acid (7 mL) was added acetic anhydride (0.35 g) dropwise. After the completion of addition, the reaction mixture was refluxed for 3 h. The solvent was distilled under vacuum and the solid was dried to give (R)-methyl-N-(butoxycarbonyl)-3-[[[4,5-dihydro-3-[4-(5-methyl-1,2,4-oxadiazol-3-yl)phenyl]-5-isoxazolyl]acetyl]amino]-L-alanine (1.05 g).
EXAMPLE 5
(R)-Methyl-3-[[[3-[4-(aminoiminomethyl)phenyl]-4,5-dihydro-5-isoxazolyl]acetyl]amino]-N-(butoxy-carbonyl)-L-alanine monoacetate: Compound (I-i) Method B:
A mixture of (R)-methyl-N-(butoxycarbonyl)-3-[[[4,5-dihydro-3-[4-(5-methyl-1,2,4-oxadiazol-3-yl)phenyl]-5-isoxazolyl]acetyl]amino]-L-alanine (70 mg) and 3%Pd/C(30 mg) in methanol (3 mL) and acetic acid (0.5 mL) was stirred under hydrogen atmosphere for 3 h. The catalyst was filtered off and washed with methanol (4 mL). The combined filtrate and wash was concentrated to small volume. Acetone (2 mL) was added slowly and a slurry was formed. After stirred for 30 min, the solid was filtered and the cake was washed with 10% methanol in acetone (4 mL) and dried to give the product (25 mg).
HPLC CONDITIONS
Column: Eclipse XDB-C8 4.6×250 mm
Mobile Phase:
A: 0.1% trifluoroacetic acid/0.1% triethylamine in HPLC grade water
B: tetrahydrofuran (unstabilized-suitable for liquid chromatography)/0.l% trifluoroacetic acid
Gradient:
t=0 min 85% A 15% B
t=10 min 85% A 15% B
t=32 min 50% A 50% B
t=40 min 50% A 50% B
Flow Rate: 1.5 mL/min
Injection Volume: 10 microliters
Stop Time: 40 minutes
Post Time: 10 minutes
Oven Temp.: 40° C.
Detector: UV (280 nm, 230 nm, 260 nm)
Sample Prep.: Dissolve approximately 0.5 mg of sample (dry solids weight) per mL in 50% tetrahydrofuran 49.9% H 2 O/0.1% acetic acid. Filter any undissolved solids through an Acrodisc 0.45 micron Nylon filter. | The present invention relates to processes for the conversion of nitrites to amidines in the preparation of compounds which are antagonists of the platelet glycoprotein IIb/IIIa fibrinogen receptor complex. The compounds described herein are potent thrombolytics and useful for the inhibition of platelet aggregation in the treatment of thromboembolic disorders. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to printing apparatus, and more particularly to an ink recycling inking system for a rotary printing press wherein different ink colors are printed by a single plate cylinder.
2. Description of the Prior Art
In normal printing practice a single rotary plate cylinder is intended to print only a single ink color. For certain printing operations, e.g., in the printing of newspapers, it is often desired to apply ink in two or more different colors to a single plate cylinder at different positions along the axial length of the plate cylinder. For that purpose two or more doctor bars must be associated with the inking rollers and must be separated from each other so that ink of different colors can be applied to the inking roller in the desired portions and so that smearing or mixing of the different color inks will be avoided.
In German Patent Publication No. 1,224,327, there is disclosed an ink fountain which is intended for use in rotogravure printing machines and which includes separator walls to permit simultaneous printing with different color inks. The separator walls are spaced along the axis of the plate cylinder, and are in sliding contact with the periphery thereof. However, that structure does not include an ink fountain that is provided with two doctor blades, and the parts of the ink fountain that adjoin the separating wall and the highly elastic sealing bar provided on that wall are connected in a unit by means of screws, so that the separating wall cannot move relative to the adjoining doctor bars.
German Patent application Ser. No. 3,135,711 shows an ink recycling inking system that includes a doctor bar that has two doctor blades to define the walls of an ink chamber, but that is intended for applying ink of only a single color to an inking roller.
German Patent application Ser. No. 3,320,638 discloses an ink applying bar, which together with two doctor blades defines an ink trough and is divided by ink-separating plates into sections for different inks to be printed. The ink separating plates are guided in guide apertures in the ink applying bar, and are urged against a screen cylinder by means of leaf springs. However, if quick drying inks are employed, the movability of the ink separating plates can be adversely effected by ink that is drying in the guide apertures.
It is an object of the present invention to provide an ink recycling inking system that overcomes the shortcomings of the prior art identified above, and to provide an ink-recycling inking system that permits the application of printing inks of two or more different colors to a single plate cylinder at different positions along the axial length thereof without mixing of the inks.
SUMMARY OF THE INVENTION
Briefly stated, in accordance with one aspect of the present invention, an ink recycling inking system for a rotary printing press is provided. The printing press includes an inking roller and an adjacent plate cylinder that is in surface contact with the inking roller. The press includes supporting means that extends in the direction of the axis of the inking roller, for pivotally supporting against the inking roller at least two doctor bars, and an ink separator plate positioned between the two doctor bars. The ink separator plate extends at right angles to the axis of the inking roller and is pivotally supported on a pin that has an axis that is oriented to lie parallel to the axis of the inking roller. The pin is disposed above the center of gravity of the ink separator plate, and its axis is positioned between the axis of the inking roller and a vertical line that extends through the center of gravity of the ink separator plate. The ink separator plate has a concavely curved end face having the same radius of curvature as that of the inking roller, and is biased by gravity into sealing contact with the peripheral surface of the inking roller. The doctor bars each have opposed end faces that face the ink separator plate and are aligned with end faces of two doctor blades carried by each doctor bar, and engage with respective end faces of the ink separator plate. The doctor bars are mounted to be axially displaceable and are adapted to be urged into sealing contact with the adjacent side faces of the ink separator plate by suitable biasing means.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front elevational view, partially in section, showing an inking system in accordance with the present invention and including an ink separator plate positioned to engage the peripheral surface of an inking roller.
FIG. 2 is an end elevational view of the inking system, partially in section, and taken along the line II--II of FIG. 1.
FIG. 3 is an enlarged fragmentary view, partially in section, showing the area of contact between the separator plate and the inking roller, and taken along the line III--III of FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings, and particularly to FIGS. 1 and 2 thereof, only a portion of a flexographic printing machine is shown, for purposes of clarity, and it is to be understood that the machine includes a frame (not shown). A pair of spaced support members 1, 2, extend in opposed relationship from the printing machine frame. Each of support members 1, 2, includes an aperture, 1a and 2a, respectively, within which is positioned a cylindrical support bar 3, the axis of which defines a pivot axis. A pair of brackets 4, 5, which include a tubular body 4a, 5a, respectively, are mounted on support bar 3 in spaced relationship therealong. Brackets 4, 5 include an elongated extension, 6, 7, respectively, which extensions include an elongated slot 8, 9, respectively. Slots 8, 9 are in alignment with each other and each has a longitudinal axis that extends along the length of the slot and passes through an inking roller 17 (see FIG. 2) that has an axis parallel to the axis of support bar 3. Each of the tubular bodies 4a, 5a of brackets 4, 5, includes a longitudinal gap defining a split portion for clamping the brackets to support bar 3 by means of a clamping bolt (not shown), in order to securely affix each of brackets 4, 5, to support bar 3 at predetermined positions therealong.
Slots 8 and 9 slidably receive a pin 10 that extends through each of the slots. Pin 10 is carried in an ink separator plate 11 that is pivotally suspended relative to the axis of pin 10. The pin is mounted in ink separator plate 11 in such a manner that the axis of pin 10 is offset from the center of gravity of the plate 11, and lies between the center of gravity of the plate and the axis of rotation of inking roller 17. Separator plate 11 includes end faces 11a, 11b, and is pivotal about the axis of pin 10. Brackets 4 and 5 are spaced from each other a distance sufficient to permit free pivotal movement of ink separator plate 11 therebetween and about the axis of pin 10.
Extensions 6 and 7 of brackets 4 and 5, respectively, are interconnected and held against relative rotation by pin 12 that extends through opposed apertures in each of extensions 6 and 7. The portion of pin 12 that extends within the space between brackets 4 and 5 carries one end of a tension spring 13, the other end of which is carried by the end of an adjusting screw 14 that is in screw threaded engagement with a support block 15 that is attached to the ink separator plate 11. Separator plate 11 includes a concavely curved end face 16 that is adapted to bear against the outer periphery of inking roller 17, the radius of curvature of end face 16 being the same as the radius of inking roller 17.
In order to permit pivotal movement of ink separator plate 11 about the axis of pin 10 so that end face 16 is in contact with inking roller 17, ink separator plate 11 includes a U-shaped opening 19 that surrounds a part of support bar 3 and is spaced therefrom when end face 16 is in engagement with the outer periphery of inking roller 17. Additionally, the lower portion of ink separating plate 11 includes a bracket 20 that carries a thin scraping bar 21, the forward end of which is adapted to be in contact with the outer periphery of inking roller 17. Scraping bar 21 has a width, in the axial direction of inking roller 17, that exceeds the thickness of ink separator plate 11.
Referring now to FIG. 3, the end face 16 of separator plate 11 is shown in enlarged, sectional form, with the plate in contact with the surface of inking roller 17. As therein shown, the end face 16 of ink separator plate 11 includes a groove formed in the end face 16 to define a pair of end edges 16a in the form of knife edges that are adapted to contact the outer periphery of inking roller 17.
Referring once again to FIG. 1, a pair of tubular support members 22, 23, are carried on support bar 3 for rotational and translational movement relative thereto. Each of tubular supports 22, 23 is mounted on opposite sides of and adjacent to brackets 4 and 5, respectively. Tubular supports 22, 23, include respective outermost end flanges 22a, 23a, and also include a plurality of respective holders, 24, 25 that extend outwardly from the axis of respective tubular members 22, 23. Holders 24, 25, carry respective ink duct doctor bars 26, 27, which are elongated structures that extend in the direction of the axis of inking roller 17 and that have a generally rectangular cross section, as shown in FIG. 2, with an ink chamber 28 formed in the side thereof that faces inking roller 17. Additionally, each of ink duct doctor bars 26, 27, includes an ink recycling bore 29, 30, which is in communication with the respective ink chamber, and also includes a pair of oppositely inclined doctor blades 34, 35, that form part of the top and bottom walls of the chamber 28, and the outermost edges of which are in contact with the outer periphery of inking roller 17. The doctor blades lie in respective intersecting planes that are parallel to the axis of rotation of inking roller 17. Ink is supplied to ink chamber 28 from an ink source (not shown) and fills ink chamber 28 to provide contact between the ink and inking roller 17. Excess ink flows from ink chamber 28 through ink recycling bores 30, 31 into an ink collecting trough 33. As best seen in FIG. 1, ink collecting trough 33 includes a partition member 32 to divide the trough into two portions, for each of two ink colors, partition 32 being positioned along the axis of inking roll 17 to underlie ink separator plate 11.
Referring once again to FIG. 1, each of tubular members 22, 23, and consequently ink duct doctor bars 26 and 27, is biased in a direction toward separator plate 11 by means of compression springs 28', 29', respectively, that are positioned between support members 1, 2, and end flanges 22a, and 23a, respectively, of tubular members 22 and 23. Further, the axial length of each of tubular members 22, 23, is such that when the innermost ends of ink duct doctor bars 26, 27, are in contact with ink separator plate 11, there is a gap between the innermost ends of tubular members 22, 23, and the outermost ends of each of brackets 4, 5, respectively, to permit the compression springs to maintain the ink duct doctor bars in close contact with the outermost surfaces of ink separator plate 11.
The innermost ends of each of ink duct doctor bars 26, 27, is in close contact with the outer surfaces 11a, 11b, respectively, of ink separator plate 11, the latter of which defines one end wall of ink chamber 28. The outermost ends of each of ink duct doctor bars 26, 27, are closed by splash guards (not shown), to provide a closure for the outermost ends of ink chambers 28.
The respective ink duct doctor bars are urged in a direction toward the axis of inking roller 17, by suitable biasing means in order to maintain close contact between respective doctor blades 34, 35, and the outer periphery of inking roller 17. An example of such a biasing means is a pneumatic cylinder and pivot arm arrangement as shown and described in U.S. Pat. No. 4,461,211, the disclosure of which is hereby incorporated herein by reference. However, the end face 16 of ink separator plate 11 is maintained in contact with the outer periphery of inking roller 17 by means of gravity alone.
In operation, inking roller 17 is positioned in contacting relationship with plate cylinder 18, and ink is supplied to respective ink duct doctor bars 26, 27 to fill the ink chambers 28 therein, each of the chambers containing ink of a different color. Ink separator plate 11 is in contact with the peripheral surface of inking roller 17 so that the knife edges formed on end face 16 are in contact therewith. Further, because pin 10 is pivotable within and slidable along slots 8 and 9, there is uniform pressure contact along the entire surface of end face 16, which is not normally obtained if the axis of rotation of ink separator plate 11 were to be maintained fixed in relation to the axis of rotation of inking roller 17, in which case there would be a differential contact pressure in that the lowermost portion of end face 16 would be urged more strongly against the peripheral surface of the inking roller than would be the upper portion of the end face. In the present embodiment, that differential contact pressure is offset by tension spring 13 and because pin 10 is slidable in slots 8 and 9. The initial tension of spring 13 can be so adjusted that the end face 16 contacts the inking roller at a uniform pressure throughout the arc length of the end face.
Scraping bar 21 that is mounted on the lower portion of ink separator plate 11 applies only a low contact pressure to the periphery of the inking roller 17, and it ensures that no residual ink will reach the peripheral edge portion of the ink separator plate. Further, the length of the scraping bar 21 in the direction of the axis of inking roller 17 is slightly greater than the width of the ink separating plate, and the bar is sufficiently flexible so that it will not adversely affect the desired snug contact between the concave end face of the ink separating plate and the periphery of the inking roller.
Although particular embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit of the present invention. It is intended to encompass in the appended claims all such changes and modifications that fall within the scope of the present invention. | An inking system for a rotary printing press, such as a flexographic printing press, including a pair of axially spaced doctor bars each having a pair of doctor blades to define ink chambers between the doctor bars and an inking roller. An ink separator plate is positioned between and in contact with the innermost ends of the doctor bars and includes a curved concave end face for intimate surface contact with the inking roller, to prevent intermixing of the separate ink colors that are provided to the respective ink chambers. The ink separator plate extends at right angles to the axis of the inking roller, and is pivoted on a pin that has an axis that is parallel to the axis of the inking roller to permit the plate to be urged by gravity into surface contact with the outer periphery of the inking roller. | 1 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application Ser. No. 61/673,863, filed Jul. 20, 2013, titled “Composite Waste and Water Tubes (Transport Elements) For Use on Aircraft and Other Passenger Transport Vehicles,” the entire contents of which are hereby incorporated by reference.
FIELD OF THE INVENTION
Embodiments of the present invention relate generally to composite waste and water transport elements that can be designed having various unique shapes and methods for their manufacture.
BACKGROUND
There are generally two types of liquid delivery tubes used on board an aircraft or other aerospace vehicle—vacuum waste tubes and tubes used to carry potable water from a potable water tank to a hand washing station, sink, or other water-using apparatus. Both types of water tubes are typically made out of corrosion resistant steel (CRES) thin walled tubing. For example, current vacuum waste tubes are typically titanium thin walled (0.020″ to 0.028″) tubes of diameters from one to four inches in diameter. In some situations, corrosion resistant steel (CRES) thin walled tubing, which is about 0.020″ to 0.035″ in wall thickness, is used. These tubes are used because these metals meet all aerospace requirements for transport elements (temperature, chemical exposure, structural, impact, and other requirements). Tubes used for the vacuum waste system are primarily straight tubes, which also incorporate bends and wyes (manifolds, pullouts, tees, and so forth). FIG. 1 shows a waste tube which has a wye (pullout) and various bends. Typically, a straight wall titanium tube is bent as required and wyes are welded and fittings (AS1650 style) are swaged or welded to tube ends. In some cases, a beaded end is used per AS5131 in place of the welded fittings.
In the event that a hard object (such as a battery, a cell phone, or other flushable object that is not intended to traverse a vacuum sewer line) is flushed into the vacuum waste system, becoming a projectile, the impact at bends or wyes could break the tube and lead to system failure. Titanium waste tubes are generally used because they are lightweight and handle impact requirements and the vacuum pressure (typically 0 to −11 PSID) cycling of the vacuum waste system. CRES tubes also meet this requirement and while they are less costly, the weight of CRES increases over titanium. CRES (which has a density of about 0.29 lbs/in 3 ) is approximately 60% heavier than titanium (which has a density of about 0.163 lbs/in 3 ).
The other types of water tubes on an aircraft, potable water tubes (e.g., the tubes that for transporting potable water throughout the aircraft), are typically CRES thin walled (0.020″ to 0.035″) tubes of diameters from about a half inch to about 5 inches in diameter. Titanium may also be used when a lightweight system is required and higher cost is feasible. For areas where complex routing (bends) is required, flexible hoses (for example, AS4468, AS5420 or similar) are used. Water tubes do not have an internal impact requirement but must meet potability requirements (NSF/ANSI Standard 61 or equivalent) and have pressure requirements of 125 PSID proof and 188 PSID burst.
Potable water tubes used are primarily straights, wye (pullout, manifold, tee) and bends. FIG. 2 shows a typical water tube straight with a pullout. Typically, if a straight tube needs to be bent, wyes are welded and fittings (AS1650 style) are brazed or welded to tube ends. Since tube diameters are relatively small, CRES is used in place of titanium for cost savings. Titanium would decrease weight but increase cost.
However, it is desirable to provide waste and water tubes of other materials that are lightweight, that meet the required strength and impact requirements, and that can be manufactured in the desired configurations. In some instances, it is desirable to manufacture tubes with varying diameters, varying lengths, shapes, and curvatures. For example, because the aircraft or other passenger transport vehicle may demand a tortuous waste or water route, the tubes should be designed in such a way that they can have bends or turns easily formed therein. It is also desirable to reduce costs of the tubing, such that their manufacture does not require complicated and expensive tooling in order to manufacture the tubing.
BRIEF SUMMARY
Embodiments of the invention described herein thus provide waste and water tubes designed for particular use on board an aircraft of other passenger transport vehicle. The tubes are manufactured from alternate materials than those that are presently used and are intended to offer cost savings benefits, lower the weight of the system, and provide easier methods to provide tubes having varying curved radii and other shapes that are not typically available with the waste and water tube materials currently in use.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a side perspective view of a traditional waste tube.
FIG. 2 shows a side perspective view of a traditional water tube.
FIGS. 3-8 show steps for manufacturing a composite tube according to one embodiment of the invention. FIG. 3 shows an example of a mandrel. FIG. 4 shows a liner applied to the mandrel. FIG. 5 shows a pre-impregnated fiber wound around the liner. FIG. 6 shows a shrink tube placed over the tube. FIG. 7 shows the shrink tube sealed with vacuum tape. FIG. 8 shows a vacuum bag at each end.
FIG. 9 shows one embodiment of a wye/pullout tube.
FIG. 10 shows the tube of FIG. 9 with an impact pad positioned therein.
FIG. 11 shows a side perspective view of the impact pad of FIGS. 9-10 .
FIG. 12 shows a bent tube section.
FIG. 13 shows the tube of FIG. 12 with an impact pad positioned therein.
FIG. 14 shows a side perspective view of the impact pad of FIGS. 12-13 .
FIG. 15 shows an example of a typical constant radius bent tube, and illustrates the angle of impact of a potential projectile.
FIG. 16 shows a variable radius bend of a tube according to methods described herein, and illustrates the lower angle of impact of a potential projectile.
DETAILED DESCRIPTION
Embodiments of the present invention provide water and waste tubes that may be manufactured from alternate materials. The tubes are designed to meet the same requirements as the titanium, CRES, and hose equivalents but to also save additional weight, allow for more complex geometry, and potentially save cost. The alternate materials from which the waste and water tubes may be made include but are not limited to composite materials such as thermoplastic or thermoset materials, with or without reinforcing fibers.
The current bent water and waste tubes used on an aircraft are bent to standard radii (per manufacturing capabilities). The routing of tubes in an aircraft is designed for these limited radii. To create a more detailed bend or varying radii of CRES or titanium tubes is either expensive or not possible. The present inventers have determined that it would be desirable to manufacture waste and/or water tubes from composite materials. The composite tubes developed and described herein are generally not limited to the standard bend radii used for traditional metal waste and water tubes, but instead, they allow for more efficient routing by using variable radius bends, splines, multi-axial bends, corkscrews, and so forth. The complex geometry available will also allow for replacement of some hoses with composite tubes.
Materials. In one embodiment, one or more thermoplastic materials may be used to form the tube body. Such materials may include but are not limited to PVC-type piping, but would use engineered thermoplastic tube materials such as polyethylenimine (PEI), polyphenylene sulfide (PPS), polyphenylsulfone (PPSU), polyether ether ketone (PEEK), polyetherketone ketone (PEKK), polyvinylidene fluoride (PVDF), or any other appropriate thermoplastic material or any combination thereof, along with aerospace style connections (AS1650 or similar). In an alternate embodiment, thermoset material may be used, such as epoxy, vinyl ester, or any other appropriate thermoset material or any combination thereof. One non-limiting example of an epoxy that may be used is Aerotuf 275-34™.
The thermoplastic and/or thermoset materials may be used with fibers, such as carbon fiber, fiber glass, Kevlar, nomex, or any other appropriate fiber or any combination thereof. The fibers may be continuous or short fibers and may be uni-directional, woven, braided or a combination of these. Depending on the process selected, the fibers could be dry with resin (thermoplastic or thermoset) being introduced at the time of part lay up or pre-impregnated fiber(s) could be used.
The liner/interior surface of waste tubes may be a film adhesive (such as 3M AF30 or similar) to comply with chemical requirements. Water tubes may have a liner of polyethylene terephthalate (PETG), polytetrafluoroethylene (PTFA) or similar material in order to comply with potable water requirements.
Tooling/manufacturing process. In one embodiment, straight composite tubes may be manufactured by placing a liner 10 of 3M AF30™ (a thermosetting film adhesive) or similar material (for waste tubes) or PETG or similar material (for water tubes) on a metal or plastic mandrel 12 , as shown in FIGS. 3-4 . A pre-impregnated fiber 14 is then applied over the liner by filament winding or roll wrapping. In one specific embodiment, the fiber may be a fibeX™ fiber system. An example of a mandrel 12 is shown in FIG. 3 , and the liner 10 as applied is shown in FIG. 4 . FIG. 5 shows the pre-impregnated fiber 14 wound around the liner. The configuration is then vacuum bagged, shrink taped, or shrink tubed and cured in an oven or autoclave. As shown in FIG. 6 , a shrink tube 16 may then be placed over the tube lay up and shrunk at a temperature below the cure temperature of the pre-impregnated fiber. Once shrunk, the shrink tube 16 itself is sealed with vacuum tape 17 and a vacuum bag 18 at each end, as shown in FIGS. 7-8 . Thus, the shrink tube becomes the vacuum bag. The configuration is then cured in an oven or autoclave. Vacuum could be pulled from one of the vacuum bags 18 applied over the shrink tube onto the mandrel. After cure, the vacuum bag or shrink tube and any other process materials are removed from the part and discarded. The part can be pulled off the mandrel. If necessary, the part and mandrel can be placed in a freezer. The mandrel will shrink due to the temperature and the part can be removed. After part removal, the ends of the tube will be trimmed to length. End fittings (similar to AS1653 or other connection type) are bonded to the tube ends.
An alternative method is to use an inflatable silicone mandrel, apply the liner and composite and insert into a mold cavity. The silicone mandrel could be pressurized to press the composite into the tooled surface. This is similar to the SMART tooling described below but would not require the shape memory materials.
Other processes for making tubes could include resin transfer molding (RTM), vacuum assisted resin transfer molding (VARTM), structural reaction injection molding (SRIM), and/or high speed resin transfer molding (HSRTM). These are variations of wetting out reinforcing fiber with resin (thermoplastic or thermoset). A pre-impregnated fiber (woven, uni-direction, braid or a combination of these) may be used to lay up the tube instead of using a resin infusion.
However, bent tubes and/or tubes with a pullout cannot be made on a hard mandrel (interior tool), as the tooling will be trapped. The curvature of the tube makes removal of t the tooling difficult to impossible. Accordingly, a further manufacturing method is needed is order to provide the desired shapes, if they are other than straight—which is more often than not the case for water and waste tubes, which must curve with the aircraft architecture. One solution for making bent and wye tubes is to use SMART Tooling from Spintech Ventures, LLC or similar process, which uses shape memory materials to create an interior mold which is soft and conformable at high temperatures. A bladder is made and placed in a mold. As temperature is increased, the bladder is pressurized with air. When the bladder softens, it is pushed against the mold and then cooled. Once cooled, it is rigid in the shape of the mold. Composite materials can be laid up and then placed in a final part mold. Heat and air pressure are applied, and as the bladder softens, it pushes the composite against the exterior mold. Once the part is cured, the bladder (still soft at high temperatures) can be removed. This process could also be used to make straight tubes. However, SMART tooling can be expensive.
Accordingly, a second solution for making bent or wye tubes is to use 3D printing technology. One example of a system that may be used is the Fortus 3D Production System by Stratasys or similar. This system is used to actually first print a 3D model of the interior of the desired tube shape using a soluble material. The material is basic (i.e., it has a high pH). The desired shape can be printed in any diameter, shape, or configuration, depending upon the specifications of the particular water or waste tube to be used and its location for intended use on the aircraft. Post processing of the material is done to achieve a smooth surface of the 3D printed tool. The composite material can then be laid up on the exterior of the 3D printed tool (a pre-impregnated fiber, a braid, vacuum infusion, or any other option) and cured in an oven or autoclave. Once the composite material is cured, the tool/part is dipped in an acidic solution (low pH) which dissolves the 3D printed soluble material. When removed from the bath, only the composite tube remains. (This process could also be used to make straight tubes.) One primary benefit of this method is that there is not a need to create expensive tooling to form a curved or wye tube. By designing the 3D shape in advance, printing the 3D shape and then applying the desired material, any number of options can be designed and/or tested.
Because most long fiber composites do not have the impact strength of metals, consideration must be taken to meet impact requirements for waste tubes. In addition to variable radius bends as shown in FIG. 16 , impact areas (typically bends and sections where wyes or pullouts enter a straight section) can be made with thicker sections of the same material used in the rest of the tube. This increased strength and stiffness may help to minimize any damage from projectiles. In an alternate embodiment, a plate of impact resistant material is inlaid in the tube (once formed or during tube manufacture) to absorb this impact without damaging the material around it. Non-limiting exemplary materials for such a plate may include but are not limited to be plates formed from polyarylsulphones (PPSU), polycarbonates (PC), titanium, CRES, or any other appropriate material or combinations thereof. FIG. 9 illustrates a wye/pullout section 20 of a potential tube 22 . FIG. 10 shows a transparent view an impact pad 24 positioned in the wye/pullout tube 22 . FIG. 11 illustrates one example of a potential shape and size for an impact pad 24 . FIGS. 12-14 show similar views of a bent tube section 26 having a differently shaped impact pad 28 positioned therein.
One of the benefits of using composite materials for manufacturing waste and water tubes is that they allow various types of bends and radii, providing more design flexibility than the traditional current tubes that are available. They are also easier to manufacture, and provide the option of varying radii and more curvatures. These types of bends could also be used to lower the angle of impact (larger entry radii), thus reducing the impact energy. For example, FIG. 15 shows a typical constant radius bend for a tube. The incoming line represents the path of a projectile travelling into the bend. The impact angle of the projectile in this scenario is about 30°. FIG. 16 shows a variable radius bend. The impact angle of the project in this scenario is reduced to about 18°. One reason this is beneficial because composite materials do not have the impact resistance of the titanium or CRES tubes. The lower angle that can be formed, however, will translate to less impact energy being imparted onto the composite tube. Typical methods used for waste or water tube manufacturing are generally not able to provide such a variable radius bend without adding a great deal of cost to the manufacturing process.
Additionally, the thermal conductivity of the composite materials described herein is lower than CRES or titanium, which will make freezing of water in lines less likely. This is an important benefit for aircraft use, in particular, as the proper drainage of aircraft water tubes is of particular concern in order to prevent standing water from freezing and causing the tubes to burst. Further, heating foil or wires can be laid up integrally to the composite tubes described here, or inline heaters may also be installed.
The composite tubes described herein may also be manufactured with varying cross sections (such as circular or non-circular, including but not limited to oval, D-shaped, C-shaped, curved and flat surface, flat-sided, with a corkscrewed interior or exterior, or any combination thereof) in order to optimize air and waste flow through the system or to accommodate installation in the aircraft. For example, potential cross sections could be oval, triangular or rectangular. The tubes may even have varying shapes, such as corkscrews or other options. For example, internal fins or projections may be provided in the interior of the tubes in order to guide or assist with water and/or waste flow due to the ease of manufacturing options provided by 3D printing. In fact, this new use of the above-described 3D printing technology in order to form aircraft waste and water tubes is particularly useful in manufacturing tubes having these varied cross-sections and bends, curves, and non-straight alternate shapes.
Changes and modifications, additions and deletions may be made to the structures and methods recited above and shown in the drawings without departing from the scope or spirit of the invention and the following claims. | Embodiments of the present invention provide composite waste and water transport elements that can be designed having various unique shapes and methods for their manufacture. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention pertains to television information transmission and reception and more particularly to the transmission and reception of high definition television information.
2. Description of the Prior Art
Conventional color television systems transmit picture information at a rate of 59.94 picture fields per second, two constituting a frame, each frame consisting of 525 horizontal scan lines. To reduce the transmission and reception bandwidths required to reproduce the transmitted picture, these horizontal scan lines are interlaced from field-to-field with a ratio of two-to-one, that is only every other scan line is transmitted in each field. Scan lines omitted in one field are transmitted in the next succeeding field, thus all the odd numbered fields contain one set of scan lines and the even numbered fields contain the set of scan lines which interlace with the scan lines in the odd numbered fields. This arrangement permits the transmission, reception, and picture reproduction at bandwidths reduced from that required for every scan line to be transmitted in each field.
Television pictures reproduced in these conventional systems have aspect ratio of four to three, i.e. for every four units of horizontal width there are three units of vertical height. Thus, a picture tube 15 inches on the diagonal has a width of 12 and a height of 9 inches, while a picture tube 19 inches on the diagonal has a width of 15.2 inches and a height of 11.4 inches.
The above specifications provide television pictures of good commercial quality which, however, degrade as the size of the picture tube increases. The graininess of the the picture produced by the 2:1 interlace ratio is acceptable for small screen receivers, but becomes more apparent as the the size of the picture tube increases. Consequently, as the television screens continue to increase in size the graininess becomes increasingly more unacceptable. To counteract this and provide greater picture resolution high definition television systems having increased aspect ratios and 1:1 progressive scans are presently under consideration.
SUMMARY OF THE INVENTION
In accordance with the principals of the present invention, digital data encoded from RGB high definition television signals are coupled to bit rate reducing circuitry wherein they are converted to digital signals at bit rates that are reduced from the bit rates of the input digital signals. The digital signals at the reduced bit rates are then coupled to a multiplexer which sequentially positions the input data and provides a multiplicity of digital data streams having equal bit rates. The equal bit rate data streams are then coupled to modulating circuitry, employing spread spectrum techniques, to modulate a carrier signal for transmission.
At a receiver the modulated carrier is demodulated and the equal bit rate data streams are reestablished. The equal bit rate data streams are then coupled to a demultiplexer where they are sequentially positioned and rearranged to provide the bit rate reduced data streams which are then coupled to a decoder, wherefrom digital data streams emerge that are representative of the digital data streams coupled to the input terminals of the transmitter.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a representation of an augmented television picture screen showing thereon the left panel, the center panel, and the right panel.
FIG. 2 is a block diagram of a transmitter of a preferred embodiment of the invention.
FIG. 2ais a diagram showing the allocation of time to encoded signals over a four scan line interval.
FIG. 2b is a block diagram of a transmitter of a preferred embodiment of the invention indicating thereon the bit rates and frequencies at the input and output terminals of each of the processing circuits.
FIG. 3a is a diagram of a differential pulse code modulator encoder.
FIG. 3b is a block diagram of a differential pulse code modulator decoder.
FIG. 4a is a diagram of a direct sequence encoder.
FIG. 4b is a diagram of a direct sequence decoder.
FIGS. 5a, 5b, and 5c are spectral representations of finite pulse sequences useful in explaining the invention.
FIG. 6 is a block diagram of a receiver of a preferred embodiment of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In a high definition television system there is a 1:1 sequential transmission of the scan lines in each frame and the frames are transmitted at a 59.94 Hz rate, in contrast to the 2:1 interlacing of fields which are transmitted at a 59.94 Hz rate on conventional television transmission. In addition, the aspect ratio of the picture is increased from 4:3 to 5.83:3 as shown in FIG. 1, wherein the center panel 11 is representative of the conventional TV picture, while the left panel 12 and right panel 13 are augmented to increase the aspect ratio as shown in the Figure. The total scan time for each scan line remains constant from frame-to-frame, as does scan time allotted to the center panel, and the total scan time allotted to the left and right panels. Though the total scan time allotted to the left and right panels remains constant from frame-to-frame the distribution of this allotted time may vary from frame-to-frame depending upon the position of the center panel. The high definition television (HDTV) source signals provide the RGB color components with a 525 line progressive scan, a frame rate of 59.94 Hz, 16:9 aspect ratio, and a 16.8 MHz horizontal bandwidth for luminance. As shown in FIG. 2, these source signals are coupled to a HDTV encoder 15, which may be the encoder disclosed by Cavallerano, et al in co-pending U.S. patent application Ser. No. 122,148, filed Nov. 17, 1987, entitled "High Definition NTSC Compatible Television System with Increased Horizontal Bandwidth and Reduced Color Artifacts", which is assigned to the Assignee of the present invention. This application is hereby incorporated by reference into the present application. This encoder processes the source signals and provides a sum of the left panel data and the right panel data on a line 17, two line differential (LD) encoding signals, which are derived from every four source lines, on lines 19 and 21, high frequency luminance (Yh) on line 23, and the chrominance signals (Ih, Qh) on lines 25 and 27, respectively. A time budget for these signals over a four line encoding interval may be as shown in FIG. 2a. As indicated in this figure the time intervals of the encoded signals, with the exception of the encoded LD2 and LD4 signals are mutually exclusive. These mutually exclusive time interval signals are coupled to the input terminals of the present invention for transmission.
Signals at the output terminals of the HDTV encoder are coupled to a bit rate reduction unit 29 in the transmitter wherein each stream of digital data is converted to an analog signal in digital to analog (D A) converters 31a through 31f. Analog signals established from the data streams on line 17, 19, and 21 are baseband signals which are coupled to low pass filters 33a-c, while luminance and chrominance analog signals derived from the data streams on lines 23, 25, and 27 have bandwidths about a center frequency. These signals are coupled to filters 33d-f as baseband signals after being down converted in mixers 35a-c. The low pass filters 33a-f remove extraneous frequencies and serve as anti-aliasing filters for the reconversion of the analog signals to digital signals by the analog to digital (A/D) converters 37a-f wherefrom digital signals emerge at bit rates reduced from that of the bit rates at the output terminals of the HDTV encoder 15. These bit rates, as well as reduced bit rates mentioned below can be found in FIG. 2b. Additional bit rate reduction is achieved by coupling the reduced bit rate data streams from the A/D converters to differential pulse code modulators 39a-f (DPCM) wherefrom a digital signal representative of the difference between the actual digital data sample and a predicted sample for that data is provided.
Each input value V(i) to the DPCM is compared with a predicted value V(p) which is based on the history of the input data. This history is accumulated over many cycles of the highly redundant video image and may be provided in three dimensions; two spatial and one temporal. For example, pixel values in the horizontal and vertical directions and corresponding values from consecutive frames are combined to yield the initial value V(p). DPCM systems and the generation of predictive values are taught in the article "DPCM Picture Coding With Adaptive Prediction" IEEE Transactions on Communications, No. 11, Nov. 1977, by Wilmut Zschunke, predictors being discussed on page 1295. This article is incorporated by reference into the present application. The difference V(d) between V(i) and V(p) is provided by a difference circuit 41 and coupled to a non-linear quantizer 43 shown in FIG. 3a. Non-linear quantizer 43 has a non-linear input/output characteristic and a limited number of output values. This non-linear characteristic is based on the human eye's greater sensitivity to luminance/chrominance errors in fields exhibiting small or no changes in luminance/chrominance, than it is to errors in fields exhibiting large luminance/chrominance changes. The number and size of the quantitization steps are made functions of the value V(d), each increasing with the value of V(d). The output of the quantizer 43 is coupled to the output terminal of DPCM and to a sum circuit 45 wherein it is added to the previous predicted value from the n-dimensional predictor 47 and the sum, so produced, provided to the predictor 47 as a new prediction value.
FIG. 3b is a diagram of a circuit for recovering the actual digital sample value from the different value. DPCM data is coupled to a sum circuit 40 wherein it is added to the previously determined predicted value in an n-dimensional predictor 51. Sums resulting from this addition are coupled to the output terminal of the decoder and to the predictor 51 as an updated prediction.
Referring again to FIG. 2, six data streams with varying bit rates and mutually exclusive time intervals, with the exception of the data streams representative of the LD2 and the LD4 data from HDTV15, are coupled from the bit rate reducer 29 to a multiplexer/buffer memory 53. After a suitable delay of either the LD2 or LD4 data stream to provide a totality of mutually exclusive time intervals the data bit streams are sequentially stored in the memory of the multiplexer/buffer memory 53 wherein they are divided into N data streams of equal length that is the number of bits in each data stream are equal, and equal bit rate which are respectively and simultaneously coupled to N direct sequence encoders (DSE) 55-1 to 55-N.
A modulo-2 addition is performed on the low bit-rate streams by the DSE to provide a code sequence at a predetermined increased bit rate for each of the data streams emanating from the multiplexer/buffer memory 53. A circuit for accomplishing this bit rate conversion is shown in FIG. 4a. A pseudo-noise sequence generator 57(PNSG) having a sequence rating at the desired conversion bit rate is coupled to one terminal of an exclusive OR gate 59, the other terminal of which is coupled to receive the data stream. Exclusive OR gate 59 provides an encoded data stream at a bit rate determined by the bit rate of the pseudo noise sequence generator 59. Only a small percentage of the possible codes that may be generated by the PNSG are utilized to achieve a code repetition rate equal to the TV frame repetition rate. Each code has a defined start point synchronized to the TV frame start. Of all the possible codes available from the PNSG 57 only N codes are chosen and their start points are defined such that each source bit to be transmitted is represented by a unique sequence within the repetition time of the code sequences. For a 200K bit/sec data rate, as in a preferred embodiment of the invention, a 6M bit/sec rate for the sequencing bits may, for example, be adopted thus establishing an appreciable overhead to allow for an optimum selection of sequences.
Extracting the initial data stream from the encoded data stream may be accomplished with the same DSE circuitry, as shown in FIG. 4b. In this figure a PNSG 61 is coupled to one input terminal of an exclusive OR gate 63, the other terminal of which is coupled to receive the encoded data stream. PNSG 61 is in synchronism with the encoded data stream thereby providing the original data stream at the output terminal of exclusive OR gate 63.
To provide minimum sidelobes for the transmitted signals the N coded data streams at the PNSG bit rate are combined in pairs and provided at an intermediate frequency (IF) spectrum by minimum shift key (MSK) modulators 65-1 through 65-N/2, as shown in FIG. 2. These MSK modulators provide a sequence of pulses at the intermediate frequency which constitute the coded signals. These signals are not infinite sequences, existing only for a small fraction of a frame time. Signals of this type exhibit spectral lobes within a sin(x)/x envelope determined by the width of the pulses in the sequence. Such a spectrum is represented in FIGS. 5a and 5b. If the width of the pulses within the sequence is equal to T the nulls of the sin (x)/x are at frequencies spaced from the center frequency equal to the reciprocal of the pulse width. Spectral lobes within the envelope have frequency spacing that are equal to the repetition rate of the pulses of the sequence, as shown in FIG. 5b, which is an expanded view of the area 67 in FIG. 5a. The width of these lobes is a function of the number of pulses in the sequence and the repetition rate and is equal to twice the repetition rate divided by the number of pulses plus one. Though not shown in the Figure each spectral lobe has a number of side lobes associated therewith.
Each MSK modulator uses a different modulation carrier frequency. If the initial frequency is equal to K times the repetition frequency and each succeeding frequency is displaced from this initial frequency by [i/(N+1)]f (rep) it should be apparent that when i equals N the gap between two spectral lobes will be filled as illustrated in FIG. 5c. As shown in FIG. 2a summation network 69 is coupled to the output terminals of the MSK modulators to receive modulated signals and provide the summation thereof to a mixer 71 wherein they are converted and coupled via a bandpass filter 73 for transmission.
The combination of direct sequence encoding and minimum shift key modulation establishes a noise like spectral distribution for the radiated signal, spreading the signal energy over a relatively wide band of frequencies. This spread spectrum radiation has a very low power spectral density which would be deep in the noise of analog detectors operating in a finite band. Consequently these signals may radiate in the VHF and UHF taboo bands and not interfere with analog transmissions in these bands.
Referring to FIG. 6 the transmitted signal is received and heterodyned in mixer 75 and passed through band pass filter 77 to a bank of MSK demodulators 79-1 through 79-N/2. Each of these demodulators operates at a demodulation carrier frequency corresponding to a modulation carrier frequency used in the transmitter. As a result, N nearly identical baseband spectrum are generated. Each baseband signal is coupled to an associated comb filter in a bank of comb filters 81-1 through 81-N to suppress unwanted and unnecessary spectral components and improve interchannel isolation. These filtered signals are then coupled to N direct sequence decoders 83-1 through 83-N to restore the original equal length equal bit rate data streams. Synchronization for this decoding is provided on line 85 from the main channel TV signal. Each equal length, equal bit rate data stream is coupled to a demultiplexer/buffer memory 87 wherein the demultiplexing operation reestablishes the original six DPCM encoded signals. Decoding of the DPCM encoded signals is accomplished in decoders 89a through 89f as previously described with reference to FIG. 3b. Reestablishment of the high definition TV coded signals continues with the digital to analog conversion of the decoded DPCM signals in the digital to analog converters 91a through 91f. The enhancement signals, in analog form, corresponding to LD2, LD4, and the left and right channel enhancement signals are coupled through low pass filters 93a-93c, converted to digital signals in analog to digital converters 95a-95cwhereat the left and right panel encoded signals have been reestablished. The LD2 and LD4 are further processed by time compressing these digital signals by 4:3 in compressors 97a-97b.
The analog luminance and chrominance signals are frequency shifted in mixes 99a-99b, bandpass filtered in filters 101a-101c, converted to digital signals in digital computers 95d-95f wherefrom the reestablished encoded luminance and chrominance signals are provided.
While the invention has been described in its preferred embodiments it is to be understood that the words which have been used are words of description rather than of limitation and the changes within the purview of the appended claims may be made without departure from the true scope and spirit of the invention in its broader aspects. | High transmission and reception quality is achieved in a high definition television system, with minimum intra-channel interference, by digitally encoding the enhancement information and employing spread-spectrum modulation techniques. | 7 |
FIELD OF THE INVENTION
This invention concerns retractable propulsors for boats.
BACKGROUND OF THE INVENTION
Retractable propulsors for boats are known, for example, from the French patent No. 2.229.608.
This document describes an auxiliary propulsor in which the propeller is withdrawn into a cavity forseen under the hull. The propeller is fixed to a shaft which penetrates an upper hollow tube when the propeller is raised. The lifting is carried out by means of a hydraulic jack, one end of which is fast with to a fixed frame and the other to a horizontal plate placed under the propeller. For the rotation of the assembly telescopic elements are housed in another tube fixed to the craft on which the same rotate. The pressure oil contained in the transmission system is used for controlling the hydraulic jack and for rotating the driving shaft.
The main disadvantages which are noted in this embodiment are the lack of mechanical sturdiness, as well as the general kinematic complication due to the fact that the whole assembly must rotate, the possibility of using only hydraulic engines and on the whole the considerable size. Another disadvantage is that of finding the optimal application only on flat-bottomed boats.
OBJECTS OF THE INVENTION
The document DE-B-1 039 874 describes a propulsor unit for boats comprising: a main engine; a fixed tubular part; a main transmission which ends with a substantially vertical shaft which operates a bevel gear pair on the substantially horizontal outlet of which a propeller is placed; an auxiliary transmission which carries out the rotation around a vertical axis of the bottom end of the propeller; a movable assembly which moves vertically with respect to the fixed structure of the boat and is integral in this direction with the bevel gear pair and with the propeller. Said movable assembly is made of an inner part which can rotate with respect to a vertical axis which rests vertically on a movable carriage.
The disadvantage that is noted in said propulsor is that the transversal thrust generated by the propeller is supported by some elements of the hydraulic system, which may disturb their operation. A further disadvantage is that at least some of the elements of the hydraulic system come in contact with the external environment, therefore they may be fouled and consequently may function badly. Furthermore, said propulsor unit is remarkably bulky.
The main aim of this invention is to give the upmost stability to the moveable part bearing the propeller so that the horizontal thrust is well supported by the inner kinematic motion, acquiring on the whole a simple and compact construction.
A further aim is that of obtaining a shape of the hull of the boat as hydrodynamic as possible when the propeller is retracted.
SUMMARY OF THE INVENTION
The main aim is reached by a propulsor for boats as claimed in claim 1.
Preferably the tube is provided with a check tongue which, during its rotation, engages the full part of the tube discharging thereupon the horizontal component of the thrust of the propeller. This tube has a double function: it favours the centering of the carriage in the vertical movement and acts as a shelf when the assembly is in the functioning position, directly opposing the carriage (reverse gear) or the check tongue (forward gear).
Preferably the carriage is moved in a vertical direction by at least one fixed screw engaged with a nut screw integral to the carriage.
The carriage can be hydraulically moved by a piston concentric to the carriage. In such a case the main transmission shaft can be used as a piston. It is also possible to provide a toroidal piston which surrounds the transmission shaft, or else to sue the upper part of the carriage as a piston.
Preferably the power which rotates the propeller is transmitted to a lateral pinion which moves a crown integral with the main transmission shaft.
The pinion can have a horizontal axis and can be connected to a driving shaft with a horizontal axis.
The pinion can be hollow and capable of receiving the horizontal shaft only when the assembly is extracted, said shaft being provided with a front coupling.
Preferably an axial cavity is provided in the movable assembly which can allow the passage of engine exhaust fumes, in particular the crown gears can have holes to allow such a passage.
A preferred embodiment foresees that when the carriage moves vertically it is integral in this direction to the final transmission gears, said gears being internally hollow and sliding on fixed rotating shafts in a vertical direction, their external surfaces matching with said internal grooves of the gears.
BRIEF DESCRIPTION OF THE DRAWINGS
Exemplary embodiments of a propulsor according to this invention are illustrated in the attached drawings in which:
FIG. 1 shows a longitudinal sectional view of a propulsor with the movable part extended;
FIG. 2 shows a longitudinal sectional view of the assembly of FIG. 1 with the movable part retracted;
FIG. 3 shows a transversal sectional view of the assembly of FIG. 1;
FIG. 4 shows a transversal sectional view of the assembly of FIG. 2;
FIG. 5 shows an enlarged view of part of FIG. 3;
FIG. 6 shows a longitudinal sectional view of one embodiment, different from that in FIGS. 1 to 5, of the propulsor, with the movable part extended;
FIG. 7 shows a longitudinal sectional view of one embodiment of the propulsor assembly, different from that in the previous figures, with the movable part extended;
FIGS. 8, 9, 10 show transversal sectional views of various embodiments of a propulsor with the movable part extended;
FIGS. 11, 12, 13 show a longitudinal sectional view of embodiments of a propulsor, with a hydraulic translation system, with the movable part extended;
FIG. 14 shows a view from above of part of the assembly illustrated in FIG. 1;
FIG. 15 shows a detail of FIG. 1;
FIG. 16 shows a partially sectioned, longitudinal view of a further embodiment of a propulsor with the movable part extended;
FIG. 17 shows a partially sectioned, longitudinal view of the assembly of FIG. 16 with the movable part retracted.
DETAILED DESCRIPTION OF THE INVENTION
In FIGS. 1, 2, 3 and 4 a sectioned hull of a boat is shown. To the hull a supporting box element A1 is integrally fixed and partly contained therein. The box element A1 supports and houses a propulsor comprising a cylindric element A2, provided with an air space A4 and an open tube A7 which extends said cylinder A2. Between a flange A6 of the tube A7 and a flange A5 of the element A2 a sealing gasket A15 is placed which extends until it reaches the space between the supporting element A1 and a flange A16 bolted to it. On the inside of the cylindrical element A2 a hollow body is provided, which acts as carriage B1, the upper end of which is next to the inner wall of the cylindrical element A2 by means of a guiding ring B3. In the cavity of the carriage B1 a hollow shaft BC1 is housed, surrounded by two bearings B4, the hollow shaft being integral to a crown gear BC2. Above the crown gear BC2 a second crown gear BD2 is placed integral to a transmission shaft BD3, placed inside the hollow shaft BC1, a gear wheel BD12 being integral to its opposite end. The gear wheel BD12 engages (by a bevel gear pair) with a gear wheel BD13 integral to a shaft BD14 which supports the end opposite a propeller BD15 surrounded by a tubing cylinder BC7, provided with an element BC8 which acts as a closing door for the retracted box element A1. A hollow body BC5 houses the bevel gear pair BD12-BD13 forming the bottom end of the propeller; said bottom end BC5 is provided with a check tongue BC9 and an inner of the cylindric element A2 four threaded bars AE1 are also placed, the upper end of which is provided with a gear AE3, while the lower end is provide with a cylindrical head AE2 fixed between the flange A5 of the element A2 and the flange A6 of the tube A7 (as can be seen in FIG. 15). Said threaded bars AE1 are engaged with threaded bushing integral to the carriage 31. The gears AE3 are engaged, as planet gears, with a solar gear AE4 (as can be seen from FIG. 14). The crown gear BD2 engages a hollow pinion BD1 keyed on a broached shaft AD1--placed inside the cylindric element A2--which is provided with a crown gear AD4 at its upper end (moved by an appropriate transmission: chain or belt, if it is a pulley: gear of a bevel gear pair or hydraulic engine directly mounted). The crown gear BC2 instead engages a hollow pinion BC13 keyed on a broached shaft AC6, placed inside the cylindric element A2, which at the upper end is provided with a crown gear AC2 (moved for example by worm screws or a hydraulically moved rack).
The propulsor previously described comprises fixed positioned parts which slide vertically, in order to allow the extension of the assembly (FIGS. 1 and 3) for engine sailing and the retraction (FIGS. 2 and 4) for wind sailing, and a rotating part, in order to allow the orientation of the propeller BD15 for choosing the direction in a field of 360°. The fixed part comprises: a box (not visible in the drawings) containing the gears for the raising and rotating, the cylindric element A2, the tube A7, the threaded bars AE1. The part which can be moved by sliding vertically comprises: the carriage B1 and the entire rotating part. The rotating part comprises: the hollow shaft BC1, the bottom end BC5 with the tongue BC9 and with all what is housed therein and the tubing cylinder BC7 with the propeller BD15.
When one wants to sail by using the engine, by pressing a button, the extension of the assembly can be obtained, so that the propeller BD15 reaches the suitable depth from the retracted position when it was contained in the hull, not disturbing the wind sailing. The gear AE4, to which a rotation is transmitted (in a prestablished direction), moves the gears AE3 which make the threaded bars AE1 rotate. These engage the threaded bushing integral to the carriage B1 obliging it to extend downwards taking the whole vertically sliding part with it. At this point the propeller BD15 is positioned at the right depth, but in the reverse gear direction; if one wants to go ahead it is necessary to carry out with the appropriate button, a rotation of 180° of the propeller BD15. By use of an appropriate transmission the crown AC2 is made to rotate; the rotation is transmitted by the shaft AC6, integral to the crown AC2, to the hollow pinion BC13, which in turn, engaging the crown BC2, rotates the hollow shaft BC1 and with it all the rotating part. In the propeller's BD15 new position, during the propulsion thrust (forward movement) the check torque BC9 engages the tube A7, while the tube A7, in reverse gear, acts as a shelf directly contrasting the carriage B1. A rotation of less than 180° can also be transmitted in any direction, this allowing the boat to be directed as steering. As far as the operation of the propeller is concerned: a rotation is transmitted to the crown gear AD4 which, by means of the broached shaft AD1, rotates the hollow pinion ED1, which, engaging the crown gear BD2, moves the transmission shaft BD3 and consequently, by means of the bevel gear pair BD12-BD13, the shaft BD14, therefore the propeller BD15.
If one then wants to sail by wind, in order to retract the propeller BD15, the assembly is made to operate in analogous way, but in an inversed sequence and with the gears rotating in the opposite way.
In FIG. 5 an enlargement of one part of the assembly previously described is shown. In this figure the shaft AC6 has been removed by 90° to allow its section on the transversal plane.
The assembly illustrated in FIG. 6 differs from the one previously described for the fact that the movement of the shaft AD1 is provided, through the bevel gear pair AD9', with a horizontal transmission shaft AD8 placed under it.
The assembly illustrated in FIG. 7 is distinguished by the fact that the hollow pinion BD1", engaging the crown gear BD2", is keyed on a horizontal transmission shaft AD8" (there is no shaft AD1).
As shown in FIG. 7; AD8" is retractable past B1 to permit retraction of B1 from the extended position to a point past the casing A2.
The assembly illustrated in FIG. 8 is distinguished by the fact that the shaft AD1"', on the end of which a head AD7 is keyed, is axial and the transmission shaft BD3"' of the movement to the propeller is hollow.
The assembly illustrated in FIG. 9 is distinguished by the fact that the shaft AD1"" is axial and hollow, while it is the transmission shaft BD3"" which has a splined head BD8"".
The assembly shown in FIG. 10 is distinguished by the fact that the rotation shaft AC6* is coaxial to the couple of shafts AD1*-BD3*, similar to that in FIG. 9. In this drawing a splined bar AE1 is removed by 45°, to allow its section on a transversal plane.
The propulsors, which have been described from the mechanical point of view, can be moved in a vertical direction by a cylinder-piston device. In FIGS. 11, 12 and 13 different ways for carrying out said device are shown in assemblies in which the transmission shaft AD1, rotating shaft AC6 and transmission shaft BD3 are coaxial. In the assembly shown in FIG. 11 the shaft BD3a acts as a piston and the transmission shaft AD1a as a cylinder, in order to carry out a hydraulic jack. In the assembly shown in FIG. 12 a tubular element BC14b integral to the bottom end of the propeller acts as a piston and a chamber AC7b in the shaft AC6b acts as a cylinder. In this drawing a coaxial duct AC4b for the hydraulic oil and holes AC3b for the passage of the oil can be seen. In the assembly shown in FIG. 13, at the end, in the downwards thrust the carriage B1c and the air space between the shaft AC6b and the cylindric element A2c respectively act as piston and cylinder, while in the ascent the shaft AC6c acts as a piston and the inner part of the hollow shaft BD1c as a cylinder.
In the attached drawings, in order to understand the operation of the hydraulic jack the lubrication oil between the various elements and the hydraulic oil are respectively marked with OL and OI.
The engine exhaust fumes which go through the appropriate hollow parts inside the assembly are marked with F, the outlet of said fumes from the tubing cylinder BC7 of the propeller BD15 being provided in the propulsors illustrated.
In FIGS. 16 and 17 a propulsor is shown which is distinguished from the ones previously described by the fact that the closing door BC8** is hinged, by a pivot BC15, and subjected to the effect of a spring BC16. When the assembly is extended the door BC8** is held horizontally by the spring BC16, while when the assembly is retracted, due to the compression of the spring, it can rotate in order to restore the exact shaft of the hull. The propulsor also has a carriage B1** of a reduced size which does not cover the opening of the tube when the assembly is extended; in order to avoid that the fumes pass through said opening of the tube and are discharged in the boss, the hollow cylinder B6 is used which can slide and is provided with overhanging flanges towards the inside of its upper and lower ends. The carriage B1** runs on the inside of this cylinder B6 and during the ascent knocks the upper flange and takes a rest position (FIG. 17), while during the descent knocks on the lower flange and takes the position in which it closes the opening of the tube (FIG. 16). | The propulsor comprises a main engine, a fixed tubular part, a main transmission which ends with a substantially vertical shaft which operates a bevel gear on the substantially vertical shaft which operates a bevel gear pair on the substantially horizontal outlet of which a propeller is placed, an auxiliary transmission which carries out the rotation around a vertical axis of the bottom end of the propeller, a moveable assembly which moves vertically with respect to the fixed structure of the boat and is integral in this direction with the bevel gear pair and with the propeller. It is characterized by the fact that said moveable group is made of an inner part which can rotate with respect to a vertical axis which rests vertically, on a moveable carriage, the lower end of which extends downwards at least to the level of a fixed support integral with the structure of the boat. | 1 |
BACKGROUND OF THE INVENTION
(1) Field of the Invention
The present invention relates generally to printing cellulosic articles and, more particularly, to a new and improved method of screen printing fabrics, in which the fabric article is first selectively printed with a chemical system including a dye blocking print paste and a dye enhancing print paste and subsequently dyed to bring out the print.
(2) Description of the Prior Art
Traditional screen printing of garments is done by printing ink, binder, thickener and softener combinations on dyed or white prepared for print (PFP) garments. A detailed description of the screen printing process is published in the Encyclopedia of Textiles, Second Edition, 1972 Prentice-Hall, Inc., Englewood Cliffs N.J., the disclosure of which is hereby incorporated by reference in its entirety. The following discussion is taken from the above-referenced Encyclopedia of Textiles.
The screen printing method in textiles is basically a stencil process. A wooden or metal frame is covered with a bolting cloth, which may be made of silk, fine metal thread, or nylon. The fabric is covered with a film and the design areas are cut out of the film just as in stencil making. The frame is then laid on the fabric and color is brushed or squeezed through the open areas of the film by the use of a big rubber knife or squeegee.
Originally, the design was cut out of film and then adhered to the screen. Today the cutting is done mechanically by a photo-chemical process which reproduces the design exactly as it was painted in the art which is being reproduced.
In printing, one screen is used for each color and these are accurately registered one on the other by the use of fixed stops attached to an iron rail running the length of the table. The length of the table determines the number of yards which can be printed at one laying; this varies depending on the available space, though 30 yards is considered the smallest space which is practical for economic production.
While screen printing, either by hand or machine, is a slower and more expensive process than roller printing, it has several virtues. From the point of view of design, pattern repeats can be much larger than in roller printing. Also, since the process is slower, pigment colors can be laid on in heavy layers to produce a handicraft effect. From an economic point of view, it does not require as large an investment as roller printing because the runs can be shorter, especially in the hand operation. This has encouraged smaller converters to adopt the screen method and to experiment more with design than they would be able to do in the roller method, where they would be required to contract for a minimum of about 8000 yards per pattern.
One of the most important physical parameters for good screen printing is that the print paste is thick enough to stand in a gel state until it is dried and cured. This assures clean crisp definition of the print.
However, the print paste still must flow readily and evenly. These two properties are defined as the rheology of the print paste and the most desirable property is called pseudo-plastic or the ability of the paste to become less viscous when moved by pump or mechanical device and to thicken or become more viscous when it stills.
Because of the nature of the print paste, screen prints are generally opaque and rubbery to the touch. In addition, these prints are not very durable especially when washed. There has been much work done in developing softer prints that do not crack and peel after washing and these softened prints are called "plastisols," but they are still based on pigments, binder, thickener and are still a surface coating which can be "felt".
Thus, there remains a need for a new and improved method of screen printing in which the garment or fabric may be printed using traditional screen printing techniques while, at the same time, provides printed areas which can not be rubbed off or felt to the touch.
SUMMARY OF THE INVENTION
The present invention is directed to a dyeing system composition for use in printing articles or fabrics formed from cellulose prior to dyeing. In the preferred embodiment, the dyeing system composition includes the selective use of both a dye blocking print paste and a dye enhancing print paste to selectively decrease or increase the shade of the dyed portions of a cellulose article, such as a woven or knitted cotton or cotton/polyester article or fabric.
In the preferred embodiment, the dye blocking print paste includes a thickener and a dye blocking agent. The dye blocking agent includes a pre-catalyzed cross-linking glyoxal resin and a dye resist. Also, in the preferred embodiment, the dye enhancing print paste includes a thickener and an epoxy functional quaternary ammonium enhancing agent. The thickener for both print pastes, preferably, is an acid/alkali stable hydroxypropyl guar derivative, polyscaharride, dispersed in an invert emulsion.
Accordingly, one aspect of the present invention is to provide a dye blocking print paste for use in printing articles formed from cellulose prior to dyeing. The composition includes: (a) a thickener; and (b) a dye blocking agent, the dye blocking agent including a cross-linking resin and a dye resist.
Another aspect of the present invention is to provide a dye blocking print paste for use in printing articles formed from cellulose prior to dyeing. The composition includes: (a) a thickener; and (b) a dye blocking agent, the dye blocking agent including a pre-catalyzed cross-linking resin and a dye resist.
Still another aspect of the present invention is to provide a dyeing system composition for use in printing articles formed from cellulose prior to dyeing. The composition includes: (a) a dye blocking print paste, the dye blocking print paste including: (i) a thickener and (ii) a dye blocking agent, the dye blocking agent including a pre-catalyzed cross-linking resin and a dye resist; and (b) a dye enhancing print paste, the dye enhancing print paste including: (i) a thickener and (ii) an enhancing agent.
These and other aspects of the present invention will become apparent to those skilled in the art after a reading of the following description of the preferred embodiment when considered with the examples.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is performed in the reverse order of traditional garment or fabric screen printing. According to the present invention, the garment or fabric is print prepared (e.g. scoured and bleached white) or griege (unprepared) with a chemical system including a dye blocking print paste and a dye enhancing print paste.
The dye blocking print paste includes a wetting agent, a thickener paste; and a dye blocking agent, the dye blocking agent including a cross-linking resin and a dye resist to selectively decrease the shade of the dye. In the preferred embodiment, the dye enhancing print paste includes a wetting agent, thickener and a dye enhancing agent which is used to selectively increase the shade of the dye.
In the preferred embodiment, the thickener paste for both the dye blocking and the dye enhancing print paste is an acid/alkali stable hydroxypropyl guar derivative, polyscaharride, dispersed in an invert emulsion. Specifically, the polysaccharide concentrate includes about 35 weight percent water, 10 weight percent emulsifier, 10 weight percent polysaccharide and 45 weight of a petrol solvent.
Also, the cross-linking resin used in the dye blocking agent is preferably a pre-catalyzed glyoxal resin although it is believed that a self-catalyzed glyoxal resin might also work. In the preferred embodiment, the dye resist used in the dye blocking agent is a low molecular weight polyacrylic acid having a molecular weight of about 2000. One suitable dye resist is sold under the tradename BURCO® Dye Resist 118 by Burlington Chemical Company, Inc. of Burlington, N.C., the assignee of the present invention.
Finally, the enhancing agent used in the dye enhancing print paste is preferably an epoxy functional quaternary ammonium compound. One suitable dye resist is sold under the tradename BURCO® DCE by Burlington Chemical Company, Inc. of Burlington, N.C., the assignee of the present invention.
The cellulosic article, garment or fabric is then dyed to the desired shade with the blocking and enhancing print pastes selectively either reducing the amount of dye on the fabric or enhancing the dye on the fabric. If we measure the background and set it arbitrarily as 100%, the enhanced regions are 250% deeper in color and the blocked regions are 90% lighter than the background.
Further examples of the present invention can be seen in a camo print on 100% cotton knit fabric where various concentrations of the enhancer chemical are printed on and then dyed.
The present invention can be best understood by a review of the following examples:
EXAMPLES 1-2
A dye blocking print paste was prepared using both pre-catalyzed glyoxal resin and a conventional glyoxal resin according to the amounts in weight percent shown in Table 1. Cotton fabric was printed with the dye blocking print paste, the print paste was allowed to dry and cure and conventional reactive and direct dyeing were made. The results are shown in Table 1, below:
TABLE 1______________________________________ Pre- Catalyzed Poly- Glyoxal Glyoxal acrylic Wetting ShadeEx. Paste Resin Resin Acid Agent Difference______________________________________1 15 wt. % 15 wt. % -- 5 wt. % 0.1 wt. % -90%2 15 wt. % -- 15 wt. % 5 wt. % 0.1 wt. % No Effect!______________________________________
As can be seen, only the dye blocking print paste including a pre-catalyzed glyoxal resin was effective in blocking the dye.
EXAMPLES 3-6
A dye blocking print paste was prepared using pre-catalyzed glyoxal resin according to the amounts in weight percent shown in Table 2. Cotton fabric was printed with the dye blocking print paste, the print paste was allowed to dry and cure and conventional reactive and direct dyeing were made. The results are shown in Table 2, below:
TABLE 2______________________________________ Pre- catalyzed Poly- Glyoxal Glyoxal acrylic Wetting ShadeEx. Paste Resin Resin Acid Agent Difference______________________________________3 15 wt. % 15 wt. % -- 5 wt. % 0.1 wt. % -90%4 15 wt. % 10 wt. % -- 5 wt. % 0.1 wt. % -60%5 15 wt. % 5 wt. % -- 5 wt. % 0.1 wt. % -30%6 15 wt. % 2.5 wt. % -- 5 wt. % 0.1 wt. % -10%______________________________________
As can be seen, the dye blocking print paste having between about 5 to 15 wt. % pre-catalyzed glyoxal resin produced a linear relationship between the weight percent of resin and the shade difference in blocking the dye.
EXAMPLES 7-10
A dye blocking print paste was prepared using pre-catalyzed glyoxal resin according to the amounts in weight percent shown in Table 3 and both with and without polyacrylic acid. Cotton fabric was printed with the dye blocking print paste, the print paste was allowed to dry and cure and conventional reactive and direct dyeing were made. The results are shown in Table 3, below:
TABLE 3______________________________________ Pre- catalyzed Poly- Glyoxal Glyoxal acrylic Wetting ShadeEx. Paste Resin Resin Acid Agent Difference______________________________________7 15 wt. % 15 wt. % -- 5 wt. % 0.1 wt. % -90%8 15 wt. % 15 wt. % -- -- 0.1 wt. % -60%9 15 wt. % 2.5 wt. % -- -- 0.1 wt. % No Effect!10 15 wt. % -- -- 15 wt. % 0.1 wt. % No Effect!______________________________________
As can be seen, the addition of polyacrylic acid improved the effectiveness of the dye blocking print paste 50% when comparing Example 7 to Example 8. In addition, only the dye blocking print paste including a pre-catalyzed glyoxal resin was effective in blocking the dye even when the amount of polyacrylic acid was increase to 15 wt. %.
Dyeings were than made using the thickener of the present invention along with a conventional epoxy functional quaternary ammonium compound to form a dye enhancing print paste. This compound has been used in the past to react with cellulose to yield a permanent cationic site on the cellulose to improve dye yield. If we measure the background and set it arbitrarily as 100%, the enhanced regions were 250% deeper in color than the background when dyed with fiber reactive and direct dyes.
Finally, fabric was screen printed using a combination of the blocking print paste and enhancing print paste according to the present invention. Dyeing to the desired shade with the blocking and enhancing print pastes selectively either reduced the amount of dye on the fabric or enhanced the dye on the fabric. If we measure the background and set it arbitrarily as 100%, the enhanced regions were 250% deeper in color and the blocked regions were 90% lighter than the background!
Certain modifications and improvements will occur to those skilled in the art upon a reading of the foregoing description. By way of example, while the preferred embodiment of this invention is directed to printing cotton and cotton/polyester fabrics, it could be easily adapted to printing other cellulosic articles. Also, non-polymer organic acids, such as citric acid, maleic acid and BTCA, other cationics and other thickeners may work. It should be understood that all such modifications and improvements have been deleted herein for the sake of conciseness and readability but are properly within the scope of the following claims. | A dyeing system composition for use in printing articles formed from cellulose prior to dyeing. The dyeing system composition includes the use of both a dye blocking print paste and a dye enhancing print paste to selectively decrease or increase the shade of dyed portions of a cellulose article such as a woven cotton fabric. | 3 |
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Application Ser. No. 61/576,945, filed Dec. 16, 2011. The disclosure of the foregoing United States patent application is specifically incorporated herein by this reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates, in general, to methods and systems of wireless networks for determining and negotiating channel bandwidths to be used within the network. More particularly, the invention relates to, but is not limited to, wireless networks operating in the Sub 1 GHz band, especially networks using the emerging IEEE standard 802.11 ah.
2. Relevant Background.
In the well-established IEEE 802.11a/b/g/n standards for wireless local area networks, an access point (AP) is a radio communication device that communicates with several other devices, called stations (STAs), such as computers, cellphones, printers, etc. The AP typically acts as a hub through which messages between stations are relayed, and is often connected to larger networks, such as the internet, and provides the stations with access to the larger network. The standards establish procedures for how the APs and STAs are to transmit information, and how they are to coordinate the use of the radio transmission medium. Coordination of when a device can use the radio transmission channel is known as medium access control (MAC).
The 802.11a/b/g/n standards also specify fixed channel bandwidths (20 MHz or 40 MHz with /n). They further specify the procedures for MAC, by which the use of a channel is coordinated within a basic service set (BSS) comprising a central AP and a set of stations STAs, e.g., laptops, cellphones, etc. They also specify the main frequency bands in which the channels are located (2.4 GHz (/b/g/n), 3.7 GHz (/a) and 5 GHz (/a/n)).
A fundamental feature of such networks is that an entire message is digitized and the digital data is organized into separate blocks and transmitted in frames. The frames include separate header fields carrying further information necessary for synchronization, network coordination, and reformulation of the message data. FIG. 1 shows two examples of the header field structure used in data and management frames in the 802.11 standards. The detailed terminology of frames and frame-based communications are specified in the standard IEEE 802.11-2012. The standard is cited as a reference for terminology and background information about frame transmission, and does not imply that the communication networks of this disclosure necessarily use the physical wireless transmission methods described therein.
Two recent, emerging amendments to the IEEE 802.11 standard (/ac and /ah) specify new frequency bands for transmission: respectively 5 GHz and Sub 1 GHz (902 MHz to 928 MHz). In the case of 802.11ac, the goal is to provide very high data rates (more than 500 Mbps), whereas for 802.11ah the goal is to provide long range (up to 1 km) for networks (e.g., smart grids or other sensor networks) with many (e.g., 6000) stations needing only low data rates (e.g., 100 kbps), on an intermittent basis. The 802.11 ah standard takes advantage of not needing to be backwards compatible with other standards, and so can optimize how the transmitted data is organized into frames, and optimize the content and organization of the header fields of the MAC and physical layer frames. The 802.11ac standard needs to be backwards compatible with the 802.11a/n standards.
Both standards specify that an entire allowed frequency range be subdivided into a fixed number of relatively narrow bandwidth channels of equal bandwidth, called fundamental channels, and that the devices can transmit using channels of different bandwidths, herein called transmission channels, built from multiple fundamental channels. When the duplicate frames are transmitted in transmission channels, each duplicate frame is transmitted in a fundamental channel. In the case of 802.11ac, the possible channel bandwidths are 20/40/80/160/80+80 MHz. In the case of 802.11ah, the channel bandwidths are 1/2/4/8/16 MHz. FIG. 3 shows the 802.11 ah channelization for the United States. The advantage of channels with wider bandwidths is greater data transmission rates. An advantage of the Sub-1 GHz frequency range is that it allows greater range, and suffers less interference from intervening objects.
However, having unfixed channel bandwidths available can create challenges for coordinating channel access. A first challenge is for the devices (APs or STAs) to have conflict-free transmission opportunities (TXOPs), in which only one device transmits at a time, and the various devices know the bandwidth and channels to be used by a transmitting device. In the 802.11ac standard, bandwidth information can be carried by PPDUs; duplicate frames transmitted in multiple fundamental channels are used for TXOP bandwidth indication and negotiation and for TXOP protection. The methods of 802.11ac need to be compatible with legacy 802.11a/n stations in the 5 GHz band. The fundamental channel bandwidth is 20 MHz since legacy 802.11a devices only understand 20 MHz PPDUs. Since 802.11a PHY SIG does not include bandwidth indication, 802.11 ac needs to put the bandwidth information in another place in the PHY header.
The difference between the 802.11ah standard and the 802.11ac standard is that the former does not require backward compatibility with older standards, and so new methods for TXOP bandwidth indication and negotiation methods can be deployed. The 802.11 ah standards can put bandwidth information in the PHY SIG subfield for bandwidth indication and bandwidth negotiation. It is not necessary that 1 MHz is the fundamental channel bandwidth. Another option is that 2 MHz is the fundamental channel bandwidth once 1 MHz devices can decode 2 MHz frames.
Glossary and Acronyms
As a convenient reference in describing the invention herein, the following glossary of terms is provided. Because of the introductory and summary nature of this glossary, these terms must also be interpreted more precisely by the context of the Detailed Description in which they are discussed.
A-MPDU Aggregated MAC Protocol Data Unit
AP Access Point
BSS Basic Service Set
BLK_ACK Block Acknowledgement Signal
CF Coordination Function
CTS Clear To Send
EDCA Enhanced Distributed Channel Access
HT High Throughput
HT-LTF High Throughput, Long Training Field
HT-SIG High Throughput, Signal Field
L-LTF Legacy Long Training Field
L-STF Legacy Short Training Field
LTF Long Training Field
MAC Medium Access Control
MPDU MAC Protocol Data Unit
OBSS Overlapping Basic Service Set
PLCP Physical Layer Convergence Procedure
PPDU PLCP Protocol Data Unit
PSDU PLCP Service Data Unit
RTS Request To Send
SIG Signal [a field within PPDU]
STF Short Training Field
TXOP Transmission Opportunity
VHT Very High Throughput
SUMMARY OF THE INVENTION
The present invention discloses methods and systems for communicating or negotiating transmission channel bandwidths in wireless communication networks, and for protecting transmission opportunities of devices in those networks. In a first embodiment, the method comprises using the signal SIG field of PPDUs of duplicated RTS/CTS frames for TXOP channel width negotiation. In another embodiment, the SIG field of PPDUs of duplicated data frames, control frames, and management frames is used to perform TXOP protection.
In other embodiments, in systems using 1 MHz fundamental channels, 1 MHz duplicate frames are used for channel bandwidth negotiation and TXOP protection in a BSS that uses operating channels greater than 1 MHz. This can decrease power consumption of stations using 1 MHz channels. In another embodiment, 2 MHz channels are the fundament channels. In such an embodiment, all stations that use 1 MHz channels can understand 2 MHz and 1 MHz transmissions. When a STA in a BSS uses a wider than 2 MHz operating channel, 2 MHz duplicated frames are used. Once a 1 MHz STA receives a 2 MHz frame it needs to decode the Duration value in the received frame. Similarly, once a greater than 2 MHz station receives a 1 MHz frame, it needs to decode the Duration value in the received frame so that it does not try to transmit any frame during the time defined by the Duration value.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a known standard arrangement of fields in a frame according to the 802.11a/b/g/n standards.
FIG. 2 shows one known form of the physical header fields for PPDUs for the 802.11 ah standard.
FIG. 3 shows how fundamental channel widths are arranged (“channelization”) into transmission channels of progressively higher bandwidths, according to the 802.11 ah standard, in the United States.
FIG. 4 shows frame duplication across multiple 2 MHz fundamental channels of RTS/CTS signals for TXOP protection, using static mode, according to one embodiment of the present invention.
FIG. 5 shows duplication across multiple 2 MHz fundamental channels of RTS/CTS signals for TXOP negotiation, using dynamic mode, according to one embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the detailed description and claims that follow, the word “a” or “an” preceding an element does not exclude the presence of a plurality of such elements.
In the 802.11 standards, MAC is accomplished by carefully specifying fields of digital data in particular orders, arranged into a single frame. The fields incorporate information on the identity or addresses of the sending and receiving devices. There are three basic types of frames in the 802.11 standards: data, control and management. FIG. 1 shows the fields within standard data and management frames. The fields surrounding the Frame Body are called header fields.
In order for the radio transceiving hardware at each device to determine where a MAC frame begins and ends, and to coordinate timing and synchronization procedures, MAC frames themselves are enclosed in further physical layer header fields. The organization of these physical layer header fields depends on the particular type of digital signaling used. The physical header fields typically include preambles, short training fields (STF), and long training fields (LTF), which allow the radio transceivers to synchronize and to estimate the channel conditions (e.g., noise levels). The physical headers also include a signal (SIG) field to transmit PHY layer control information. The combination of the physical layer header fields together with the transmitted MAC frame is termed the Physical Convergence Procedure Protocol Data Unit (PPDU). FIG. 2 illustrates two examples for the arrangement of fields within a PPDU, for use with the 802.11ah standard.
Next, within the DATA part of a PPDU is a service field, which comprises a number of bits used as a seed of a scrambling sequence. The scrambling seed is used at the transmitter device to scramble (rearrange) the contents of the rest of the PPDU, and at the receiver for descrambling.
The 802.11 ah standard supports multiple use cases, such as smart grid applications, sensor networks, and network offloading. Such cases have different requirements: strict power saving requirements for sensor applications or higher bandwidth requirements for network offloading. The 802.11ah standard modifies the basic structures of 802.11a/b/g/n standards to create a variant optimized for networks containing hundreds, perhaps thousands, of stations which only need to transmit and receive comparatively limited amounts of data, for limited amounts of time. An example of such a network could be a smart grid wireless sensor network. One of the modifications is the organization of the physical layer header fields. An exemplary organization of the physical headers is shown in FIG. 2 . The entire MAC frames, such as those shown in FIG. 1 , are part of the shown DATA fields.
An important modification in the 802.11 ah standard is to allow a device in the communication network to use radio transmission channels of different bandwidths, built from varying numbers of relatively narrow bandwidth building block channels, herein called fundamental channels. Another important modification is to use the frequency band of 902 MHz to 928 MHz. FIG. 3 shows a proposed channelization of this frequency band according to the 802.11 ah standard, for the United States. In the case shown, the fundamental channel width is 1 MHz; and with this channelization the network is denoted a 1/2/4/8/16 MHz network. Some networks, for other regulatory regions, may have fewer available channels and analogously be denoted a 1/2/4/8 MHz network, or a 1/2/4 MHz network. One fundamental channel serves as the primary channel, that is, a common channel of operation of all devices in the communication network's basic service set (BSS). The primary channel is used for the transmission and reception of the beacon and other narrow bandwidth PPDUs.
With four available channel bandwidths (e.g., a 2/4/8/16 MHz network or a 1/2/4/8 MHz network) only 2 bits are needed for a source device to transmit the choice of bandwidth that it desires to use in its subsequent transmission during the current transmission opportunity. For a 1/2/4/8/16 MHz network, 3 bits may be needed. To ensure that the transmission will not interfere with other network devices (herein called alternate devices), and to ensure that its communication can be received, the source device transmits duplicate signals on all of the fundamental channels that comprise the combined channel it desires to use. The duplicated signals contain the bits needed to indicate the bandwidth of the source device's desired channel. Once a single signal is received, the received device can determine the bandwidth that source device uses for the duplicated signals.
In some embodiments, reception of the duplicated signals by the alternate devices allows them to send reply signals to indicate whether they are able to receive at that bandwidth and are free to do so. Once the replies have been received, the source device can adjust the channel bandwidth, if necessary, of its transmission.
In a regulatory region which allows 1 MHz channels, one issue that arises is the bandwidth of the fundamental channel. In one embodiment of the invention, when 1 MHz is the fundamental channel bandwidth, the system uses a 1 MHz duplicate mode. Under this mode, some stations may only be able to transmit and receive in 1 MHz bandwidths. Stations that can transmit with greater than 1 MHz bandwidths then transmit duplicate 1 MHz frames so the 1 MHz stations can decode the Duration field of the duplicate 1 MHz frames. This will simplify the 1 MHz operation mode since in this mode a station will not try to receive a 2 MHz frame.
In another embodiment, 2 MHz is the fundamental channel's bandwidth, and the system uses a 2 MHz duplicate mode. Under this mode, all stations can receive both 1 MHz and 2 MHz bandwidth transmissions. A 1 MHz station (one that can only transmit signals in a 1 MHz bandwidth channel) can transmit 1 MHz frames to another 1 MHz station. However, a 1 MHz station will still be able to receive and decode 2 MHz frames from a station that transmits at greater than 1 MHz bandwidth. These greater than 1 MHz bandwidth stations will transmit duplicate 2 MHz frames so that 1 MHz stations can decode the Duration field of the duplicate 2 MHz frames. The greater than 1 MHz stations will also be able to receive and decode 1 MHz frames from 1 MHz stations. A station can use the special PHY format of a 1 MHz PPDU to identify the 1 MHz transmission. In a BSS having transmission channels greater than 1 MHz, and using 2 MHz duplicate mode, two stations may use 1 MHz bandwidth channels to communicate with each other.
For 1/2/4/8/16 MHz channelization under 2 MHz duplicate mode, only 2 bits are needed for a source device to transmit the choice of bandwidth that it desires to use in its transmission; in one embodiment, 00, 01, 10 and 11 indicate 2 MHz, 4 MHz, 8 MHz and 16 MHz channels, respectively.
Once the communication system's channelization is known, the next issue is to determine a method for transmitting the bits used for channel bandwidth indication. A known method is to use the bits in the SERVICE field in PHY header (see FIG. 2 ) to carry the bandwidth indication. The remaining bits in SERVICE field are used for scrambling. In this method, to differentiate a SERVICE field carrying only bits for scrambling from a SERVICE field carrying bits for both bandwidth indication and scrambling, the Unicast/Multicast bit in address field TA in the MAC header is used. This method has several issues. The changed TA MAC address will influence the parts of the MAC protocol that are based on the TA, e.g., NAV setting and the responding frame creation. The scrambling algorithm is also influenced.
Instead, in one embodiment of the invention herein, another method is to use the bits in PHY SIG to carry the bandwidth indication. This method has no influence on the other parts of the MAC protocol, e.g., the responding creation or the NAV setting. The scrambling algorithm is not influenced. In one embodiment of the invention, another bit in the PHY SIG field is used for the TXOP bandwidth negotiation by combining with the bandwidth indication.
In one embodiment, the devices in the communication network use Request-To-Send (RTS) and Clear-To-Send (CTS) signals, contained in PPDUs, to coordinate an upcoming transmission. In this embodiment, the PPDUs contain a signal field (SIG) which is used by the source device to transmit the bits needed to indicate the bandwidth desired for the transmission. The alternate devices use the SIG field of the PPDU of the CTS signal to indicate the channel bandwidth they accept. This is accomplished by using 2 bits in the case that the network uses at most four channel bandwidths or five channel bandwidths under 2 MHz duplicate mode, or 3 bits if the network uses five channel bandwidths under 1 MHz duplicate mode.
There are two known methods by which a source device and a destination device decide the TXOP bandwidth: bandwidth static method and bandwidth dynamic method. In the bandwidth static method, the source station decides the TXOP bandwidth and the destination will not send the responding frame if the destination cannot support the bandwidth (e.g., busy medium detection) indicated by the source. In the bandwidth dynamic method, the source station and the destination station negotiate the TXOP bandwidth. An additional bit is needed to indicate whether the station that initiates the transmission is able to do bandwidth negotiation. When this bit is set to 1, the destination station can select a transmission bandwidth for the source station that is narrower than the source station selected. When this bit is set to 0, the source decides the transmission bandwidth and the destination follows the bandwidth selected by the source station. If the destination station cannot follow the bandwidth selected by the source station, the destination station will not transmit the responding frame, which means an unsuccessful transmission.
There are various methods for transmitting the bit needed to implement bandwidth dynamic/static indications. One method is to follow 802.11ac's method of using the bits in SERVICE field in PHY header to carry the bandwidth dynamic/static indication. The remaining bits in SERVICE field are used for scrambling. To differentiate between the SERVICE field only for scrambling from the SERVICE field for bandwidth dynamic/static indication and scrambling, the Unicast/Multicast bit in address field TA in MAC header is used. This method has several issues. The changed TA MAC address will influence part of the MAC protocol that is based on TA, e.g., NAV setting or the responding frame creation. The scrambling algorithm is also influenced.
One embodiment of the invention is to use the bits in PHY SIG to carry the bandwidth dynamic/static indication. This method has no influence to other parts of the MAC protocol, e.g., the responding creation or NAV setting. The scrambling algorithm is not influenced.
FIG. 4 shows an example of an embodiment of the bandwidth static method. An AP sends duplicate RTS signals on four fundamental channels, in this example with channel 0 being the primary channel, since the AP detects that all four fundamental channels are idle. In this example, the roles of AP1 and STA1 can be reversed (i.e., STA1 could be the device that initiates the duplicate RTS signals after detecting the idle channels, and AP1 could be the responding device). Duplication of the RTS signals on the four fundamental channels indicates the AP's intent to transmit using the bandwidth and frequencies of those four channels. STA1 responds with CTS signals on all four channels in the case that the STA1 detects that all four intended fundamental channels are idle. In the case that another STA is using one of the channels 0-3, the STA1 does not respond with duplicate CTS signals, and the RTS/CTS exchange fails. Upon receiving the four CTS signals the AP transmits the Aggregated MAC Protocol Data Unit (A-MPDU) in the four fundamental channels. STA1 then transmits a Block Acknowledgement (BLK_ACK) signal. Another embodiment is that a station sends duplicate RTS signals to an AP in static bandwidth mode and the AP responds with duplicate CTS signals after it receives the duplicate RTS signals, or the AP does not respond if it detects a busy channel. Another embodiment is that a first station sends duplicate RTS signals to a second station in static bandwidth mode and the second station responds with duplicate CTS signals after it receives the duplicate RTS signals.
FIG. 5 shows an example of an embodiment of TXOP bandwidth negotiation. In this method, the TXOP holder and the TXOP responder can negotiate the channel bandwidth of the TXOP. Though for definiteness FIG. 5 shows AP1 initiating the negotiation method, and STA1 responding, the method applies analogously when STA1 is the initiator, and AP1 the responder. As shown, an 8 MHz channel (ch0+ch1+ch2+ch3, each a 2 MHz fundamental channel) is the operating channel of AP1. AP1 sends duplicate RTS signals on all four of its operating channels. STA1, however, detects that a 1 MHz subchannel of ch2 is in use by STA2 (in the BSS of AP2, which overlaps the BSS of AP1). So STA1 responds with CTS signals only on channels ch0 and ch1 (4 MHz total bandwidth). Upon reception of the reduced number of CTS signals, AP1 reduces the bandwidth and channels that it uses to send the A-MPDU.
Although the invention has been described and illustrated with a certain degree of particularity, it is understood that the present disclosure has been made only by way of example, and that numerous changes in the combination and arrangement of parts can be resorted to by those skilled in the art without departing from the spirit and scope of the invention, as hereinafter claimed. | Methods and systems are disclosed for the operation of wireless communication networks, in which communication channels can have possibly overlapping bandwidths of different sizes, including sensor networks operating by the IEEE 802.11ah standard. A first method of signaling to negotiate the channel bandwidth conveys the needed information in the SIG field of the PPDUs of duplicate RTS/CTS frames, and uses the SIG field of PPDUs of duplicated data, control and management frames to perform transmit opportunity protection. A second method of signaling to negotiate the channel bandwidth conveys the needed information in the scrambling sequence field of PPDUs of duplicate RTS, and uses the scrambling sequence field of PPDUs of duplicated data, control and management frames to perform transmit opportunity protection. | 7 |
BACKGROUND OF THE INVENTION
This invention relates to a power supply system for an electronic apparatus incorporating a volatile memory and, particularly, to a power supply system suitable for use with a data processing system.
A conventional power supply circuit for a volatile memory is disclosed in Japanese Patent Unexamined Publication No. 57-23123. This prior art circuit arrangement is intended to automatically switch the supply of electric power from the main power supply to the battery in response to the turn-off operation of the main power supply. However, this system needs a battery of large capacity depending on the expected turn-off duration of the main a.c. power supply, since the battery is used continuously during the "power-off" state regardless of the presence or absence of the a.c. power input.
Another prior art technique disclosed in Japanese Patent Unexamined Publication No. 56-168246 is the use of a battery in response to the detection of a.c. power failure. However, this system operates in response to two conditions, i.e., the output voltage of a main power supply has built up or a.c. power failure exists, and there is no description in the publication on the "power-off" operation of the main power supply. Accordingly, when the main power supply is turned off, battery back-up is started as in the case of power failure, resulting in over-discharging of the battery.
Another technique similar to that of the above patent publication 56-168246 is discribed in Japanese Patent Unexamined Publication No. 59-24323. This publication does not describe the "power-off" operation of the main power unit and power failure and power-off can not be distinguished, resulting in over-discharging of the battery.
Still another technique disclosed in Japanese Patent Unexamined Publication No. 56-116134 is intended to operate such that the battery back-up for the volatile memory is suspended upon expiration of a certain time length after the state of power failure has been detected so as to prevent over-discharging of the battery. Also in this publication, no description is given for the power-off operation for the main power supply, and the system treats the power failure in the power-off state in the same way as the power failure in the power-on state, resulting in over-discharging of the battery.
SUMMARY OF THE INVENTION
An object of this invention is to prevent over-discharging of a back-up battery during the power-off state of the main power supply.
Another object of this invention is to prevent over-discharging of a back-up battery through the setup of different battery back-up time lengths for the power failure occuring in the power-on state and for the power failure occuring in the power-off state.
Generally, a memory device consumes a relatively large power when it is accessed, while it needs little power for holding information. In view of this property of memory devices, the present invention contemplates to supply power to the apparatus from a main power source during the power-on state in which power consumption is high due to memory access, from an auxiliary power source during the power-off state, i.e., standby mode, and from a battery only in the event of power failure. In consideration of the battery service life which is deteriorated by over-discharging, the battery back-up time is set longer for the case of occurrence of power failure during power-on state at which occurrence no time is available for evacuating important information to a non-volatile memory such as a floppy disk, and a shorter battery back-up time is set for the case of occurrence of power failure during power-off state in which power-off state important information has already evacuated, so that the over-discharging of the battery is prevented.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of the power supply circuit embodying the present invention; and
FIG. 2 is a timing chart explaining the operation of the circuit arrangement shown in FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENT
An embodiment of this invention will now be described with reference to FIG. 1. Only a power supply section and a memory section of a data processing system are illustrated in FIG. 1. In the figure, reference numeral 1 denotes a plug for receiving the external a.c. input power supply voltage Vin, and 2 denotes a power unit incorporating rectifiers for converting the a.c. input voltage into d.c. voltages. The power unit 2 includes a main power source 8 which provides a d.c. output V M when the switch 7 in the unit is set to "power-on" and an auxiliary power source 9 which provides an d.c. output V A even if the switch 7 is set to "power-off" so long as the a.c. power supply Vin is received. The main output power voltage V M is distributed to other control circuits (not shown) and all circuit sections of the data processing system can operate normally once the voltage V M builds up. The auxiliary power voltage V A is supplied to the dynamic random access memory (DRAM) when the power unit 2 is in the power-off state, and it is also used as a power source for controlling the power-on and power-off operations.
The main power output V M is fed through a diode D1 to a voltage regulator 3, which provides the stabilized power voltage to a DRAM 4. The main power output V M has a serial connection of a zener diode ZD1 and resistor R1 for detecting the rise and fall of the voltage.
The auxiliary power output V A is fed through a diode D2 to the emitter of a pnp transistor Q1, which has its collector connected to the input of the d.c. voltage regulator 3. The diode D2 has its cathode connected to a battery charging circuit 5, with a battery V B connected between the output of the charging circuit 5 and ground. The positive terminal of the battery is also connected through a diode D3 to the emitter of the transistor Q1. The transistor Q1 is driven in switching mode by being connected at its base through a resister R2 to an npn transistor Q2 which is biased through a resistor R3 by the battery V B . The base of the transistor Q2 is connected to a pnp transistor Q3, which has its base connected to the anode of the zener diode ZD1 so that the transistor Q2 is cut off in response to the build-up of the main power output voltage V M . To detect the presence or absence of the auxiliary power output voltage V A , the output line is connected through a zener diode ZD2 to a resistor R4.
Reference numeral 20 denotes a CMOS logic circuit operating under the battery voltage and it produces an output signal for terminating the battery back-up for the DRAM 4 upon expiration of two hours, for example, in the case where the power failure has occurred during the power-on state, or for terminating the battery back-up upon expiration of 15 minutes, for example, in the case where the power failure has occurred during the power-off state.
Reference numeral 26 denotes a clock generator which supplies the clock signal to the CL terminal of a clock counter 27. The counter 27 is reset to the initial state by receiving at its R terminal the reset signal which is produced by a driver 28 in response to the detection of the build-up of the auxiliary power output voltage V A at the node of the zener diode ZD2 and resistor R4. The clock counter 27 further has output terminals C1 and C2 for providing output pulses when certain counts are reached. In this embodiment, the counter 27 is designed to produce an output pulse at C1 upon expiration of a shorter time length, e.g., 15 minutes, and another output pulse at C2 upon expiration of a longer time length, e.g., two hours. A flip-flop 29 is set by the C2 output of the clock counter 27 and is reset by the output of the driver 28.
A console 30 provides the P.OFF-N signal 25 indicating the power-off state, but the signal is not produced when the power unit 2 is deactivated without through the power-off operation as in the case of power failure. The P.OFF-N signal is fed to one input of a logical AND gate 22, which has another input connected to the C1 output of the clock counter 27. The AND gate 22 has its output connected to the set terminal of a flip-flop 23. The console 30 provides another output signal P.ON-P indicating the power-on state, and it is fed to the reset terminal of the flip-flop 23. A logical OR gate 24 has two inputs from the flip-flops 29 and 23, and supplies its output to the base of the transistor Q2 so that it is forced to cut off.
Reference numeral 6 denotes a static random access memory (SRAM) operating under the battery voltage V B . The reason for the provision of the DRAM 4 which is battery backed-up for a limited time length and the SRAM 6 which is battery backed-up unlimitedly is as follows. The DRAM is larger in storage capacity, smaller in size and cheaper in bit price as compared with the SRAM. Accordingly, a large-capacity and compact memory can be realized by solely employing DRAM devices, but with a drawback of greater power dissipation which allows battery back-up for a shorter time length. On the other hand, the SRAM is higher in bit cost and thus disadvantabeous for constructing a large-capacity memory, but it can hold information using extremely small power. On this account, this embodiment uses both of DRAM and SRAM, the former storing information which can be reloaded from a non-volatile memory (not shown) after battery back-up has terminated, while the latter storing information which cannot be recovered once battery back-up is suspended.
The DRAM is provided with the battery back-up for a limited duration in the occurrence of power failure so as to spare much battery power for the SRAM which is battery backed-up continuously so that information is retained. Information stored in the DRAM includes program preset data, and information stored in the SRAM includes input data received consecutively in the power-on state.
Next, the operation of the foregoing circuit arrangement will be described in connection with FIG. 2 showing the timing relationship between the major signals.
As initial conditions, it is assumed that the battery V B is fully charged, the program is loaded in the DRAM 4, the power unit 2 is in the "power-on" state, and the flip-flops 29 and 23 are in the reset state. The d.c. output voltages are set to be V M ≧V A ≧V B . The power unit 2 in the power-on state provides the main power output V M for the d.c. voltage regulator 3, which supplies the voltage Vcc to the DRAM. The main power output V M supplies a current through the zener diode ZD1 to the resistor R1, causing the transistor Q3 to become conductive, resulting in the cut-off of the transistors Q2 and Q1. Therefore, the auxiliary power output V A and battery V B are not loaded, and the DRAM 4 is powered by the main power output V M in the power-on state.
Next, when the power unit 2 is brought to the power-off state, the main power output V M falls, causing the zener diode ZD1 to be deactivated and then the transistor Q3 to be cut off. Consequently, the transistor Q2 becomes conductive and then the transistor Q1 also becomes conductive, causing the d.c. voltage regulator 3 to be supplied with the auxiliary power output V A which is lower than the main power output V M , and a voltage enough to retain the memory contents is supplied to the DRAM 4.
In the case where power failure occurs in the a.c. power input Vin during the normal power-off state, the auxiliary power output V A goes off and the battery V B which has been charged by the battery charging circuit 5 becomes to supply power through the diode D3 to the d.c. voltage regulator 3, allowing the DRAM 4 to retain its contents.
The loss of the auxiliary power output V A due to power failure causes the zener diode ZD2 to be deactivated, and the output of the driver 28 releases the reset condition of the clock counter 27 and flip-flop 29. The clock counter 27 starts counting the clock signal from the clock generator 26, and if the main a.c. power does not recover in 15 minutes it produces the output signal on the terminal C1. Because of power failure after the normal power-off operation, the P.OFF-N signal produced in response to normal power-on is present on the terminal 25, and the AND gate 22 is enabled by the P.OFF-N signal and the output at C1 of clock counter 27 sets the flip-flop 23. The power-on indication signal P.ON-P 21 is absent at the reset terminal of the flip-flop 23 in the power-off state, and it is not reset. The set output at 1's terminal of the flip-flop 23 enables the OR gate 24 to bypass the base bias of the transistor Q2, causing it to become cut-off and then the transistor Q1 to become cut-off, and the back-up power supply from the battery V B is terminated. Accordingly, a 15-minute battery back-up takes place in the case of power failure in the normal power-off state.
If power failure occurs abruptly during the normal power-on state, the power-off indication signal P.OFF-N 25 is not produced, causing the AND gate 22 to stay disabled even if the clock counter 27 provides the output at C1 on expiration of 15 minutes, and the flip-flop 23 is not set. In the case of the main a.c. power not recovering on expiration of two hours, the clock counter 27 produces the output signal on its terminal C2, causing the flip-flop 29 to set, and the OR gate 24 is enabled. The OR gate output forces the transistor Q2 to cut off, resulting in the cut-off of the transistor Q1, and the battery back-up is terminated. Accordingly, a 2-hour battery back-up takes place for the a.c. power failure during the power-on state.
Generally, information in the volatile memory is saved in a non-volatile memory such as a floppy disc unit or fixed disc unit prior to the power-off operation. When the internal memory is powered by the auxiliary power source to retain the contents during the power-off state, the time spent for reloading the saved information following the power-on operation can effectively be minimized. The auxiliary power source for this purpose is preferably backed up by the battery so as to avoid the risk of power failure during the power-off state. However, a greater battery power consumption needs a longer charging time, and based on the fact that important data has been saved in the non-volatile memory before power failure occurs in the power-off state, the internal memory is battery backed-up for a relatively short time (15 minutes in this embodiment) so as to minimize the discharging of the battery. Namely, it cannot be distinguished during the power-off state as to whether the loss of a.c. power is caused by an accidental power failure, disconnection of the power plug, or turning-off of the a.c. power switch, and a shorter time is allowed for the battery back-up of these cases so that the battery power is spared for a long term power failure after power is turned on. On the other hand, power failure during the power-on state allows no time for saving the memory contents in the non-volatile memory, and therefore the internal memory is battery backed-up for a longer time (two hours in this embodiment) in expectation of a.c. power recovery.
According to this invention, the internal memory is supplied with power uninterruptedly irrespective of the a.c. power condition, and the battery is operated to discharge only in the event of accidental power failure for different time lengths depending on the operating condition of the apparatus, whereby the battery can be protected from over-discharging. | A power supply system includes a main power unit for supplying power necessary for the operation of an electronic apparatus including a memory, an auxiliary power unit for supplying power necessary for retaining the memory contents, and a battery serving as a back-up of said main and auxiliary power units for supplying power necessary for retaining the memory contents. The memory is supplied with power from the main power unit when it is in the power-on state, from the auxiliary power unit when the main power unit is in the power-off state, and from the battery in the event of a.c. power failure. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser. No. 13/210,175 entitled “Quilted Fabric Towel Steam Pocket for a Steam Appliance”, filed Aug. 15, 2011, now published as U.S. Patent Application Publication No. U.S. 2011/0296633, which is a continuation of U.S. application Ser. No. 12/467,057, entitled “Quilted Fabric Towel Steam Pocket for a Steam Appliance”, filed May 15, 2009, which is now issued as U.S. Pat. No. 7,996,948, and which claims the benefit under 35 U.S.C. §119(e) of provisional Application No. 61/172,523 filed Apr. 24, 2009, entitled “Fabric Towel Pocket for a Steam Appliance”, each of which are herein incorporated by reference in their entireties.
BACKGROUND OF THE INVENTION
[0002] The invention relates generally to a fabric pocket for a steam appliance, and more particularly to a quilted fabric towel in the form of an envelope to form a steam pocket when installed on a steam frame of a steam appliance.
[0003] Steam cleaners and/or devices used to apply steam to household objects are well known. The uses of the devices vary widely, and may include the application of steam to drapes or other fabrics to ease wrinkles, and the application of steam to objects to assist in cleaning the objects. Steam cleaners also have been used for cleaning carpeted floors, but usually overly saturate the carpet and require long period of time to dry.
[0004] Typical steam devices have a reservoir for storing water that is connected to an electrical water pump with an on/off switch. The exit from the electric water pump is connected to a steam boiler with a heating element to heat the water. The heated water generates steam, which may be directed towards its intended destination through a nozzle which controls the application of the steam. Variation of the shape and size of the nozzle allows for preferred distribution of generated steam to an object to be cleaned. The nozzles may be disconnectable from the steam generator to allow different nozzles to be utilized, based on the object to be steamed. The nozzle may be either closely coupled to the steam generator, or located at a distance from the steam generator, requiring tubing or other steam transfer structures to be interconnected between the steam generator and the discharge nozzle. Typically, it is beneficial to provide suitable connectors between the steam generator and the nozzle to allow either the nozzle to be connected to the steam generator, or to allow the interpositioning of transfer tubes or hoses between the steam generator. and the nozzle.
[0005] In general, the nozzles used with the steam cleaners do not have large surface areas. A cloth or towel is placed on a steam frame coupled to the steam nozzle to distribute the steam.
[0006] Notwithstanding the wide variety of steam generating appliances and cleaning towels available, there exists the need to provide improved accessories for use with a steam cleaner.
SUMMARY OF THE INVENTION
[0007] Generally speaking, in accordance with the invention, a quilted fabric in the form of an envelope with one open edge for mounting onto a steam frame of a steam generating device to form a steam pocket is provided. The quilted fabric towel has improved steam distribution properties. The fabric layers of the steam pocket have a terry outer layer and an inner knit fabric lining material that includes a base mesh layer, a padding layer and a jersey layer facing the outer terry layer. The surface of the towel is diagonally quilted from the open edge at 45 degrees to the closed front in geometric pattern with quilt lines crossing at 90 degrees. A slot along the open back edge is provided to accommodate a connection to the appliance and allow for unlimited steering of the steam pocket and use of both sides of the towel for cleaning.
[0008] The fabric envelope is formed from two substantially planar layers of fabric configured to fit over a steam frame with fasteners to lock the pocket closed about the frame. The surface layers are joined around their perimeter along the sides and leaving an open edge for mounting onto the steam frame. A pair of fastening strips are secured to the inner side of one layer along the open edge and on the outer side of the other layer with one set of strips extending beyond the edge. When placed on the frame and secured the fabric edges of both layers are butting each other along a closure line. This locks the steam pocket closed to prevent the escape of steam out the open edge of the fabric envelope. In another embodiment, the fabric may include a pull ribbon for assisting installation on to the frame.
[0009] Accordingly, it is an object of the invention to provide an improved fabric steam towel to form a steam pocket in a steam appliance.
[0010] Another object of the invention is to provide a steam towel for a steam appliance with improved cleaning performance.
[0011] Yet another object of the invention is to prove a fabric towel with a closure to lock the pocket closed in the back of the steam frame for improved steaming.
[0012] A further object of the invention is to provide a steam towel for a steam appliance with improved push/pull performance. Yet another object of the invention is to provide a steam towel for a steam appliance having improved durability.
[0013] Still other objects and advantages of the invention will in part be obvious and will in part be apparent from the specification.
[0014] The invention accordingly comprises a product possessing the features, properties, and the relation of components which will be exemplified in the product hereinafter described, and the scope of the invention will be indicated in the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] For a fuller understanding of the invention, reference is made to the following description taken in connection with the accompanying drawing(s), in which:
[0016] FIG. 1 is a perspective view of a steam mop including a steam pocket constructed and arranged in accordance with the invention;
[0017] FIG. 2 is a front view of the mop housing in section showing a reservoir, a pump and a boiler in the mop of FIG. 1 ;
[0018] FIG. 3 is a perspective view of the steam mop frame and universal connector in the steam mop of FIG. 1 ;
[0019] FIG. 4 is a perspective view of the universal connector for connecting the steam frame to the appliance housing as shown in FIG. 1 ;
[0020] FIG. 5 is a rear perspective view of the steam frame showing the details of the steam frame of FIG. 3 ;
[0021] FIG. 6 is a plan view of a rectangular quilted fabric steam towel suitable constructed and arranged in accordance with the invention for use with the steam appliance of FIG. 1 ;
[0022] FIG. 7 is a plan view of a triangular quilted fabric steam towel in accordance with the invention that may be used with a triangular shaped steam frame and connector for the mop of FIG. 1 ;
[0023] FIG. 8 is a rear perspective view of a triangular steam frame showing for use with the quilted fabric steam towel of FIG. 7 ;
[0024] FIG. 9 is a schematic in section showing the terry and lining layers of the fabric towel in accordance with the invention;
[0025] FIGS. 10 a and 10 b are schematics showing the position of hook and loop fasteners on the top and bottom layers of the steam towel in accordance with the invention; and
[0026] FIG. 11 is a rear elevation schematic view of the towel closure constructed and arranged in accordance with the invention; and
[0027] FIG. 12 is a partial rear elevational view of the installed steam towel with a pull ribbon on a steam frame in accordance with the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0028] FIG. 1 is a perspective view of a steam mop 10 constructed and arranged in accordance with the invention. Mop 10 includes an elongated housing 11 with a water reservoir 21 and a boiler 23 shown in FIG. 2 and an upper tube 12 a and a lower tube 12 b connected to one end of housing 11 . A handle 13 is attached to the end of upper tube 12 a. A steam frame 14 with a receiving slot 20 with an installed steam pocket 15 is operatively connected to the other end of housing 11 by a connector 16 . In this embodiment, connector 16 and frame 14 may be removed from housing 11 by pressing a release button 17 at the base of housing 11 . Water is introduced into a reservoir 21 at a water inlet or opening 18 a. The level of water present in a reservoir 21 in housing 11 can be viewed through a sighting window 19 . The specifics of fabric steam pocket 15 will be described below.
[0029] FIG. 2 is a front plan view in section showing the location of elements in housing 11 . Water container 21 is positioned adjacent and surrounds boiler 23 . A one-way pump 22 pumps water from reservoir 21 to boiler 23 in response to the push-pull movement of mop 10 . This movement of handle 13 activates operation of pump 22 and one way inlet and outlet valves.
[0030] FIGS. 3-5 show the details of construction of universal connector 16 and steam frame 14 used with steam mop 10 of FIG. 1 . Frame 14 is substantially rectangular in shape, open at the top and bottom with plurality of baffles as will be described in detail below.
[0031] Universal connector 16 includes and upper connection piece 26 with pivot plates 26 a and 26 b and a lower connection piece 27 with two pivot arms 27 a and 27 b coupled at a pivot pins 28 on upper piece 22 that allows steam frame 14 and housing 11 to pivot side to side.
[0032] Lower connection piece also includes two side arms 29 a and 29 b with a central opening 29 c for passage of a flexible steam hose 32 to feed steam to frame 14 . Frame 14 includes connector receiving slot bushings 33 a and 33 b for receiving side arms 29 a and 29 b . Two mounting plates 34 a and 34 b secure arms 29 a and 29 b in place to allow for up and down pivoting of arms 29 a and 29 b. This configuration allows for both sides of frame 14 and steam towel 15 to be used for steaming a surface to cleaned and for unlimited steering of the steam pocket during use.
[0033] As shown in FIGS. 3 and 5 steam frame 14 includes a rear wall 14 a with connector receiving opening 20 in the center, a front wall 14 b and a right side wall 14 c and a left side wall 14 d. A plurality of baffles 38 extend within the walls of frame 14 . Frame 14 also includes a central steam passageway or manifold 36 that runs from the rear of frame 14 at a receiving slot 20 to a front border 14 e. A plurality of steam release openings 37 are formed on both sides of manifold 36 along the top and bottom thereof. These release openings 37 are positioned between each baffle 38 . Baffles 38 are substantially orthogonal to manifold 33 in the center of frame 14 and extend sideways and curve rearward to the side edges and rear wall of frame 14 .
[0034] Steam hose 32 is connected to manifold 36 at a hose plate 39 mounted at the entrance to manifold 36 . Short fins 41 extend from the sides of manifold 36 and edges 14 c and 14 d approximately at the mid-height of manifold 36 and side walls 14 c and 14 d to assist in distribution of steam to the upper and lower surfaces of steam towel 15 installed on frame 14 to form the steam pocket when in use.
[0035] Universal connector 16 provides many advantages for ease of use because it easily connect and disconnect to mop frame while providing a user with universal pivoting and steering capability. The user has more control of the appliance and frame by the universal connection to clean whatever areas that need to be clean and allows use of both sides of steam frame 14 for cleaning. In addition, the universal connector may be attached to any variety of differently shaped mop frames, such as rectangular frame 14 or a triangular frame shown in FIG. 7 a for use with towel as shown in FIG. 7 .
[0036] FIG. 6 shows a rectangular towel envelope 46 with a “U” shaped slot 47 and is configured to slip over frame 14 to form a steam pocket 15 . Steam towel 46 is formed of a first quilted fabric layer 48 and an opposed second quilted fabric 49 . Quilted fabric 48 and 49 each have a substantially rectangular shape with a rear edge 51 in sections about slot 47 , a front edge 52 and two short edges 53 and 54 . The steam pocket formed by frame 14 and towel 46 is joined at edges 54 , 52 and 53 by stitching to form fabric steam towel 15 . As shown in FIG. 7 a steam pocket fabric 56 may be triangular in shape or any shape with an open rear mounting edge 57 about a gap 58 for mounting over a steam frame 59 as shown in FIG. 8 . Triangular frame 59 includes a slot 60 for receiving connector 16 as described in detail above in connection with frame 14 .
[0037] Steam pocket fabric envelopes 15 , 46 and 56 are open at rear edges 15 a, 51 and 57 . The fabric along the opening may be closed with a hook and loop fastener, buttons or snaps. Here, steam towels 15 and 46 have slots 20 , 47 and 57 to fit around the width of connector 16 . This allows for vertical rotation of housing 11 without bending the fabric of fabric steam towel 15 . It also allows use of both sides of steam towel 15 , 46 and 56 for cleaning without having to remove and re-install the steam towel 15 .
[0038] As shown, the steam pocket fabrics are quilted in accordance with the invention. In the illustrated embodiments quilting stitches 55 extends from rear edges 15 a, 51 and 57 at a 45 degree angle in two directions to the opposed fabric edges forming 2″ squares. The size of the squares may vary from about 1″ to about 3″. It has been found that providing a quilted fabric surface improves cleaning performance of steam mop 11 when used on a variety of different stains. Quilting makes it easier to push and pull mop 11 compared to steam towels of terry material. In addition, steam towels including quilting in accordance with the invention are more durable after as many as twenty washing and drying cycles along with usage between each wash cycle.
[0039] Each fabric surface of the fabric towels are formed of two separate fabric layers. The outer layer is a woven terry of 100 percent polyester with a loop height of 3 mm of 0.72 denier yarn having a weight of 295 g/sq.m. The loops may vary from 2.5 to 3.5 mm with between 260 to 280 loops/sq. in. and the weight may vary from 280 to 310 g/sq.m.
[0040] The inner lining material has three components. These are an outer jersey layer facing the outer terry layer, padding and an inner mesh layer. The total weight of the lining materials is between 130 to 156 g/sq.m, preferably 140 g/sq.m. and between 0.065 to 0.085 inch in thickness, preferably 0.076 inch thick. The mesh has between 3 to 3.75 wales per inch and the jersey between 12 and 15 wales per inch with between 20 to 27 courses per inch, preferably 23 courses per inch.
[0041] The combined fabric layers have an overall thickness of between 0.15 to 0.17 inch, preferably 0.16 thick. The overall weight is between 435 to 485 g/sq.m., or preferably 460-461 g/sq.m. A schematic sectional showing of this fabric construction is set forth in FIG. 9 . The fabric surfaces include an outside terry layer 61 , and inner lining material 62 that includes a mesh layer 63 facing outside layer 61 , a padding layer 64 and an inside jersey layer 66 . All open edges of each surface of the steam towels are stitched along the rear edge and around slots 20 , 47 and 58 .
[0042] It is desirable to seal the open edge of the steam towels 46 when installed on a steam frame to lock the pocket closed and prevent steam escape as shown in schematic in FIGS. 10 a and 10 b . One quilted surface 61 includes a first length of a hook and loop fastener 63 secured to an inside open edge 64 on both sides of slot 62 . Second quilted surface 66 with a complimentary slot 67 along open edge 68 in FIG. 10 b includes a complimentary hook and loop fastener 69 is secured to the opposed inside edge and extending beyond edge 68 a. This will allow edges 64 and 68 on each surface to abut and form a seal 71 along rear edge of frame 14 as shown in FIG. 12 .
[0043] Fabric steam towels in accordance with the invention may be formed of any suitable fabric, such as cotton or a synthetic fabric, such as polyester or polyolefin fiber. Preferably, the fabric of steam towels is a microfiber. Most preferably, the microfiber is a synthetic 100% polyester microfiber. Typical dimensions for a rectangular steam pocket are about 13 inches wide and 7 inches deep and one inch thick. To close the open edge about 4 to 5 inches of fasteners are used on each side of the slots in the rear edges.
[0044] When closure of edges 64 and 68 is complete and pocket 15 is sealed, the rear view is as shown in FIG. 11 . Hook and loop fasteners 63 and 69 are not visible when installed. It is desirable to have fabric steam pocket 15 fit snugly about frame 14 for improved distribution of steam. In order to facilitate mounting fabric pocket 15 on frame 14 , a pull ribbon 76 is attached to one side of edge opening with two strips of elastic 72 that allows a user to mount pocket 15 on one side of back edge of frame 14 and then pull on ribbon 76 to complete the installation of fabric pocket 15 . Then hook and loop fasteners are secured to seal the envelope prior to use.
[0045] It will thus be seen that the objects set forth above, among those made apparent from the preceding description, are efficiently attained and, since certain changes may be made in the above product without departing from the spirit and scope of the invention, it is intended that all matter contained in the above description and shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense.
[0046] It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween.
[0047] The present invention may be embodied in other specific forms without departing from the spirit or essential attributes of the invention. | A fabric steam towel for mounting onto a steam frame of a steam appliance is provided. The pocket includes two complimentary substantially planar layers of fabric joined at their peripheral edge with an open section for mounting onto the steam frame and allowing the open edges to butt against each other. The fabrics are constructed of an outer terry layer and inner material with an upper jersey layer, padding and a lower mesh layer with a 45 degree quilting pattern to improve performance. The fabric is sealed about the frame a first length of a fastener is secured to the inside face along the open edge of one layer with a complimentary length of fastener secured to the inside face of the second layer and extending beyond the edge to allow the open edges of each layer to abut each other and for the fasteners to engage and secure the fabric pocket about the edge of the frame. | 0 |
BACKGROUND OF THE INVENTION
In one aspect the present invention relates to a method for the metered delivery of microbubbles for admixture with other components in the production of explosive compositions. In another aspect, the present invention relates to apparatus for handling and feeding microbubbles on a continuous basis which is highly accurate and can be employed to deliver microbubbles either on the basis of weight or on the basis of volume. In a further aspect the present invention relates to a control system for insuring that a deaerating holding vessel for microbubbles contains a constant volume thereof by providing for automatic delivery and shut off of microbubbles from a storage source thereof.
In the manufacture of explosive compositions which are based upon water in the form of oxidizing salt solutions, for example, it is well known in the art that the density of a composition plays a major role in the ultimate sensitivity of the explosive. Thus, in the past, occluded air has been employed in gel type explosives in order to attain the desired density. Recently however the use of glass or resin microbubbles to obtain desired densities of explosive compositions has gained wide acceptance in the explosives art. For example, it has recently been discovered that microbubbles, or other void containing materials, can be employed with a fuel component, an emulsifier and an oxidizing salt solution to form cap sensitive explosive emulsion products. Commercial manufacture of explosives employing closed cell void materials in the form of microbubbles entail the metered introduction of such materials for admixture with the other components of the explosive composition and because of the very low density of the microbubbles themselves the amounts which are added to known quantities of explosive compositions must be carefully controlled if the desired density of the final composition is to be achieved.
The microbubbles employed in explosive compositions can be produced from a variety of materials but they all are generally of a bubble or spherical shape and are hollow and either contain a gas such as air, or can be evacuated, or partially evacuated. In the preparation of cap sensitive explosive emulsion compositions the preferred types of microbubbles are discrete glass spheres having a particle size within the range of from about 10 to about 175 microns. In general, the bulk density of such particles can be in the range of about 0.10 to about 0.40 g/cc. Some preferred glass microbubbles which can be utilized in the preparation of cap sensitive explosive emulsions are the microbubbles sold by 3M Company and which have a particle size distribution in the range of from about 10 to about 160 microns, and a nominal size in the range of from about 60 to 70 microns, and densities in the range of from about 0.10 to about 0.4 g/cc. Other types of glass microbubbles are sold under the trade designation of Eccospheres by Emerson & Cumming, Inc., and generally have a particle size range from about 44 to about 175 microns and a density of about 0.15 to about 4.0 g/cc. Still other suitable microbubbles for use in cap sensitive explosive emulsions include the inorganic microspheres sold under the trade designation of Q-CEL by Philadelphia Quartz Company.
In addition to glass microbubbles, phenoformaldehyde microbubbles are available and can be utilized in the production of cap sensitive emulsion explosives. Further, microbubbles are available which are manufactured from saran. These saran microbubbles have a diameter of about 30 microns and a density of about 0.032 g/cc.
All of the above types of microbubbles are similar in that they have very small diameters and low bulk densities. The result is that the handling and accurate metering of such materials presents problems on a commercial scale. The physical characteristics of the microbubbles are such that an aerated quantity thereof has flow characteristics similar to Newtonian liquids, for example, water (under standard conditions). However, the handling characteristics of the microbubbles change drastically once they have become settled and deaerated so that handling them as liquids by the use of pumps or the like is not feasible. Furthermore, because of the low bulk density of the microbubbles, and their peculiar physical characteristics, precise measurement of a quantity thereof is difficult. For example, because of the highly particulate nature and low density of the microbubbles normal level indicators, such as floats and the like, which could be employed in a holding tank of liquid to determine the volume of liquid contained therein, cannot be successfully employed for the same purpose in a holding tank for microbubbles. Further, the very low bulk density of the microbubbles would require very sensitive weighing apparatus in order to determine the volume of microbubbles held in a holding tank by measuring variances in the total weight of the tank and microbubbles.
Because the accurate addition of known quantities of microbubbles to the other chemical constituents of explosive compositions in order to control the sensitivity thereof, as well as in other applications, is desirable, an automatic feeding system for the metered addition of microbubbles, having the difficult handling characteristics described above, would be advantageous. Further, a method for determining accurately the amount of microbubbles held in a holding tank thereof, for example, the hopper connected with a feeding apparatus, would also be highly advantageous.
SUMMARY OF THE INVENTION
In accordance with the present invention I have discovered that the peculiar handling characteristics of microbubbles which have caused problems in the accurate metering of these materials in the production of emulsion explosive compositions, for example, can be overcome by allowing the microbubbles to deaerate so as to change their flow characteristics from those similar to a Newtonian fluid to those of particulate matter, such as sand, for example. The term "aerated" as used herein refers to microbubbles which because of transportation, or other agitation, have become admixed with air and behave much like a Newtonian liquid under standard conditions. Thus, an aerated quantity of microbubbles will tend to flow like water through the outlets of containers and behave generally like a liquid. The bulk density of an aerated quantity of microbubbles will be very low compared to the particle density of the individual microbubbles. The term "deaerated" as used herein refers to a quantity of microbubbles which have settled significantly such that the fluidizing characteristics of admixed air have dissipated and the microbubbles have attained the handling characteristics of a particulate material such as sand, for example. Thus, a deaerated quantity of microbubbles will have an angle of repose during storage whereas an aerated quantity will tend to flow into the shape of the container in a manner analogous to liquids. Generally, it has been discovered that the change in handling characteristics (between aerated and deaerated microbubbles) occurs when the bulk density of a quantity of microbubbles approaches from about 80 to about 95% of the bulk density of an uncompacted deaerated quantity thereof.
Thus, by providing a system which insures that a holding vessel for microbubbles will always have a substantial quantity deposited therein while metered quantities are being withdrawn therefrom, the desirable flow characteristics can be obtained because of the deaeration which occurs during settling.
The apparatus of the present invention basically comprises a microbubble holding vessel to which a quantity of microbubbles can be delivered and allowed to deaerate so as to obtain the desired flow characteristics similar to caked particulate matter. The outlet end of the holding vessel communicates with a dual screw feed mechanism which provides for a constant volumetric output of microbubbles at any given rotational speed employed. The dual screw type feed mechanism, which basically comprises two parallel shafts having screw flights mounted thereon which mesh along a portion thereof is necessary because a single screw feed may allow the particulate microbubbles to flow along the flights of the single screw even when rotation thereof has ceased. At the outlet end of the screw feed mechanism a weigh-belt feed mechanism is provided which delivers a uniform flow rate, based on the weight of microbubbles, to a delivery point such as a blender in an emulsion explosive processing line. Thus, by allowing the weigh-belt apparatus to merely act as a conveyor (that is, deactivating the weight control mechanism) a steady volumetric flow rate of microbubbles can be delivered to a desired processing point by operating the dual screw feed mechanism at a constant rotational speed. On the other hand, if desired, a known flow rate, based on the weight of microbubbles, can be delivered to a processing point by operating the dual screw feeder to deliver a constant volumetric flow rate of microbubbles onto the weigh-belt feeder and allowing the weight sensing mechanism of the weigh-belt feeder to speed or slow the belt as is necessary in order to deliver the constant flow rate, by weight, of microbubbles to the processing point.
In order to facilitate the above process I have discovered an accurate means for determining the level of microbubbles contained in a holding vessel which can be employed as a control signal such that microbubbles can be delivered to the holding tank when the volume therein drops below a predetermined level. The sensing mechanism of the present invention comprises a tuning fork means which is electronically vibrated at a known frequency. Frequency sensing means are functionally connected with the tuning fork such that when the frequency changes an electrical signal is generated. The tuning fork will have a steady frequency while vibrating in air and will have a changed frequency when the particulate microbubbles are present between the prongs of the tuning fork. Thus, this sensing mechanism can be employed by installing the tuning fork at a known level within a vessel of known dimensions and causing the tuning fork to vibrate at a known frequency with microbubbles present between the prongs thereof. When a sufficient quantity of microbubbles have left the holding vessel, via the screw feeder described above, causing the level of microbubbles to drop in the holding vessel and air to replace microbubbles between the prongs of the tuning fork, the change in frequency which occurs will generate an electric signal which can be used to operate a delivery source of microbubbles to the holding vessel to restore the quantity therein to the desired level. In this manner the quantity of microbubbles in a holding tank will always be kept at a level sufficient to allow deaeration of the microbubbles to occur before passing into the screw-type feeder discussed above.
BRIEF DESCRIPTION OF DRAWING
The drawing is a schematic representation of one embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The apparatus and process of the subject invention will now be described in detail with relation to the drawing which schematically depicts a processing arrangement of apparatus useful in the present invention.
Thus, referring to the drawing a storage container 2 for microbubbles, which can be the drum or box-like containers in which microbubbles are sold on a commercial basis, is depicted with a vacuum delivery conduit 4 inserted therein. Interconnected with vacuum delivery conduit 4 is a vacuum source 6 which creates a vacuum downline thereof to pull microbubbles in container 2 through vacuum delivery conduit 4 and creates an airflow upline thereof to deliver the microbubbles through vacuum delivery conduit 4 to holding vessel 8. Holding vessel 8 can comprise any of a number of known configurations for particulate material such as hoppers, and the like, preferably having conical-shaped surface 10 at the bottom thereof communicating with an outlet 12. Of course any of a number of holding vessels having decreasing cross sections can be employed.
Mounted at a preselected level within holding vessel 8 is a tuning fork level indicator mechanism 14. Basically, the tuning fork level indicating mechanism 14 comprises a vibrating tuning fork 15 having two or more prongs which can be vibrated by piezocrystals, for example, with electronic frequency sensing apparatus contained in the housing 17 from which the tuning fork 15 extends. In operation, if the vibrating tuning fork is free of material, the system begins to vibrate at its resonant frequency and within a predetermined time frame an internal relay is energized. In the system of the present invention, the internal relay is connected with vacuum source 6 (via electrical conduit 16) such that when air is present between the prongs of the tuning fork 15 vacuum source 6 is activated and microbubbles are delivered from storage container 2 to holding vessel 8 via vacuum delivery conduit 4. Once the prongs of the tuning fork 15 become covered with microbubbles, the change in frequency of oscillation causes the internal relay to be deenergized after a predetermined interval of the time. In the present system, deenergizing the relay causes vacuum source 6 to cease delivery of microbubbles to holding vessel 8, the electric signal being communicated to vacuum source 6 along electrical conduit 16. A suitable tuning fork level indicating mechanism is manufactured by Endress & Hauser, Inc., Greenwood, Ind., and is sold under the trade name VIBRATROL. Thus, by employing the above type of level indication system, in combination with a vacuum source (or other delivery systems), the delivery of microbubbles to holding vessel 8 is accomplished in a manner which insures that the level of microbubbles contained therein is kept at a relatively constant level.
The configuration and capacity of holding vessel 8 is constructed such that at the maximum rate of output of microbubbles from outlet 12 thereof the residence time of microbubbles within holding vessel 8 will be sufficient to allow deaeration to occur. For example, on a commercial scale a minimum residence time of about 7 minutes may be employed. The mode of delivery of microbubbles shown in the drawing necessarily causes them to be delivered to holding vessel 8 in a state of aeration in which the flow properties thereof will be similar to a Newtonian fluid such as water. Thus, by providing for a minimum residence time such as that set forth above, the microbubbles delivered to holding vessel 8 are allowed to deaerate and become settled to an extent that the flow characteristics thereof at outlet 12 will more nearly approach that of a caked particulate material. As schematically shown in the drawing, the microbubbles contained in the lower portion of holding vessel 8 will be in a more compacted state than will those which have just entered holding vessel 8 via vacuum delivery conduit 4.
Different microbubbles will have different settling qualities depending upon the material from which they are manufactured, their density, and shape. Furthermore, the residence time required will vary with the configuration of the holding vessel 8 being employed. However, it has been discovered that the flow characteristics of the microbubbles changes from those of a liquid to those similar to more easily handled and metered particulate material when a quantity thereof obtains about 80 to about 95% of the bulk density of a substantially deaerated uncompacted quantity thereof. For example, glass microbubbles sold under the trade designation B-15-250 by 3M Corporation were found to have a bulk density of about 0.084 g/cc in a deaerated state. The initial aerated density of a quantity of these microbubbles (obtained by shaking a graduated cylinder about two-thirds full to thereby entrap air between the microbubbles) is approximately 0.055 g/cc. When allowed to settle (and thereby deaerate) and handling characteristics changed from a fluidized to a non-fluidized state at approximately 0.078 g/cc. Thus, the change in handling characteristics occurred once about 92% of the final deaerated bulk density had been achieved. Similar experiments showed that when using microbubbles sold by 3M Corporation under the trade designations B-38-4000 and B-28-750 the change in handling characteristics occurred at 87% and 92% of bulk density, respectively.
Returning to the drawing the outlet 12 of holding vessel 8 is shown communicating with dual screw feed mechanism 18. Basically, dual screw feed mechanism 18 comprises two auger feed screws 20 and 22, aligned in parallel such that the flights thereof intermesh. Drive means 21 for feed screws 20 and 22 are shown as an alternate embodiment. The parallel auger screw arrangement provides for a controlled volumetric flow through dual screw feed mechanism 18 at any given rotational speed of the screw augers 20 and 22. This is so even though the inlet end of the screw feed mechanism communicates with the outlet 12 of holding vessel 8 since the settled, deaerated microbubbles will not be allowed to free-flow along the flights of the augers because the path of flow will be blocked by the intermeshing flights of the parallel augers. Therefore, upon rotation of the parallel auger screws of screw feed mechanism 18, a controlled volumetric flow rate of microbubbles will be deposited on weigh-belt apparatus 24.
Basically, weigh-belt apparatus 24 comprises an endless conveyor track 26 driven by conventional drive means 25 about suitable roller mechanisms 28. Located under a portion of endless conveyor track 26 on the upper side thereof is weight sensing apparatus 30. This weight sensing apparatus 30 is interconnected by electrical conduit 33 with the drive means 25 of weigh-belt apparatus 24 and is electronically controlled such that, depending upon the weight of the particulate material deposited on conveyor track 26, the drive means 25 operates slower or faster, thus rotating conveyor track 26 at a varying rate in order to deliver a constant weight flow-rate of microbubbles to processing point 32.
The weigh-belt feed mechanism 24 and screw feed apparatus 18 can be used together to deliver flow-rates of microbubbles to a processing point 32 either on the basis of a constant volumetric flow-rate or, in the alternative, on the basis of a constant weight flow-rate. Thus, when it is desired to deliver a constant weight flow-rate of microbubbles to a processing point 32, the microbubble delivery system of the present invention can be operated in the following manner. Screw feed mechanism 18 is operated to delivery a substantially constant volumetric flow-rate of microbubbles from holding vessel 8 to the conveyor track 26 of weigh-belt apparatus 24. While the volumetric flow-rate issuing from the outlet of screw feed mechanism 18 is relatively constant the specific gravity of the microbubbles being delivered may vary widely. For example, the specific gravity of microbubbles specified as having a density of 0.15 g/cc may actually range in density from about 0.12 g/cc to about 0.18 g/cc. Thus, in order to insure that a constant weight flow-rate, based on weight of microbubbles, is delivered to processing point 32 weight sensing apparatus 30 is activated to sense the weight of microbubbles contained along that portion of conveyor track 26 passing over weight sensing apparatus 30 at any given time. The weight sensing apparatus 30 will compare the desired weight flow-rate of microbubbles to the weight of microbubbles deposited on conveyor track 26 and will adjust the rate of rotation of conveyor track 26 either faster or slower as is necessary in order that a steady flow rate, based on weight, is delivered to processing point 32. Further, in order to insure that the apparatus can handle even wide variances in the density of microbubbles the weight sensing apparatus 30 can be interconnected by electrical conduit 34 (shown as an alternate embodiment) with the drive means 21 (also shown as an alternate embodiment) for screw feed mechanism 18 thus slowing or speeding the rate of volumetric delivery of microbubbles to conveyor track 26. Thus, in the manufacture of water-based explosive compositions, for example, it is highly desirable to have a means by which a constant flow-rate based on weight, of microbubbles will be delivered to a processing apparatus for admixture with the other components of the water-based explosive composition. The apparatus described above can be used, in conjunction with other processing equipment, to insure that water-based explosive compositions being prepared on a continuous basis comprise the specified weight percent of microbubbles according to a preferred formula.
Alternatively, in some cases, particularly where very sensitive explosive compositions are desired, it has been determined that the density of the final explosive composition is much more important than the specific weight percent of microbubbles contained therein. Therefore, in some instances it is desirable to add a constant volumetric amount of microbubbles which will result in a final density of the explosive composition within a predeterined range. Thus, in order to achieve a constant addition of microbubbles so as to obtain an explosive composition having a specified density the apparatus of the subject invention can be operated by running the screw feed mechanism 18 at a constant rate to deliver a relatively constant volumetric flow of microbubbles to the conveyor belt 26 of weigh-belt apparatus 24. Weight sensing apparatus 30 can be deactivated such that weigh-belt apparatus 24 essentially acts as a conveyor belt for the delivery of the constant volumetric flow of microbubbles from screw feed mechanism 18 to processing point 32. This constant volumetric flow is combined with a known volumetric amount of explosive materials to form the sensitized explosive having the preferred density.
While this invention has been described in relation to its preferred embodiments, it is to be understood that various modifications thereof will now be apparent to one skilled in the art upon reading the specification and it is intended to cover such modifications as fall within the scope of the appended claims. | A method and apparatus are provided for the metered delivery of microbubbles, used for example, in the production of explosive compositions. Disclosed is a holding vessel with sufficient residence time to deaerate the microbubbbles with a level indicating device for sensing the quantity of microbubbles deposited therein, the outlet of the holding vessel communicating with a dual screw feed apparatus for delivering a constant volumetric flow of deaerated microbubbles from the holding vessel and a weigh-belt, upon which the microbubbles ae deposited as they exit the screw feeder, for providing a constant flow of microbubbles by weight for delivery to processing apparatus. | 2 |
This application is a continuation of application Ser. No. 792,122, filed Oct. 28, 1985, now abandoned.
This invention relates to collapsible frames for portable display panels, walls, podiums, tables and the like, and more particularly to a self-supporting reflexively collapsible support and attachment structure for such frames.
Known collapsible self-supporting display panel or wall frames of the type capable of supporting display panels or sheets vertically hung thereon are illustrated by U.S. Pat. Nos. 4,276,726 and 4,471,548. These particular frames characteristically have a network of support rods or spokes which are pivotally joined together at hub assemblies for movement between a collapsed compact position for storage or transportation and an open erect position for usage. Once erect, they may have hardware attached thereto for hanging sheets or panels for either masking the frame or for simply displaying graphic presentations such as for advertising.
Other general types of portable display frames with planar display panels may be seen in U.S. Pat. Nos. 1,408,079; 2,902,239; and 4,325,197. All of these display panel frames are particularly useful for window displays and backdrops or portable walls for trade shows and the like.
However, such frames distinctively have complex mechanical joints and require manual attachment of the display panels to the frames once they have been erected thereby making their assembly and disassembly somewhat time consuming and tedious. They also typically lack vertical supportive strength rendering them generally incapable of supporting more than a vertically hung sheet or panel of material. Furthermore, there are generally no places on the covered frames to mount or attach display accessories such as shelving and lighting customarily used at trade shows.
Portable film projection screen frames are also generally known in the art such as those disclosed in U.S. Pat. Nos. 3,002,557; 2,403,661; 2,357,819; and 1,662,586. Such frames are of limited use because they also lack in vertical supportive strength and connectable attachment hardware for purposes other than film projection.
Still other types of collapsible frames may include frames for portable sound shells such as the frame disclosed in U.S. Pat. No. 3,180,446. Such frames do exhibit vertical supportive strength. However, they are generally complex, bulky and heavy. They also have limited uses and their assembly and disassembly are quite time consuming. Once assembled, they additionally require manual hanging of panels onto the frame and also require panel removal to permit complete disassembly for storage or transportation.
Folding frames for speaker stands or podiums are also known in the art as disclosed in U.S. Pat. No. 2,598,128. But still, such frames are bulky, heavy, complex in nature, and not readily adaptable for other purposes.
SUMMARY OF THE INVENTION
A reflexively collapsible support and attachment structure for use in portable self-supporting frames for display panels, walls, podiums, tables and the like. The structure includes a horizontal elongate foot having front and back ends forming the base of the structure. A first elongate brace is provided having top and bottom ends. The bottom end of the first brace is pivotally connected to the front end of the foot and is suitably adapted to permit the brace to swing upwardly from a collapsed position adjacent the foot to an upright inclined position.
A slidably collapsible support strut is pivotally connected to the foot and slidably connected to the first brace. The strut is biased to an upright extended position between the foot and the first brace to support and hold the first brace in its upright inclined position. The strut is also adapted to be slidably moved at its end connected to the first brace from its extended position to a collapsed position adjacent the foot to permit the first brace to swing downwardly to its collapsed position.
A second elongate brace is provided also having top and bottom ends. An interlocking hinge has its lower leaf attached to the top end of the first brace and its upper leaf attached to the bottom end of the second brace. The hinge is adapted to permit the second brace to swing upwardly from a collapsed position adjacent the first brace to an upright generally vertical position. The hinge has a releasable interlocking latch constructed to hold the braces stationary with respect to each other when they are in their respective upright positions.
To complete the assembly of a portable self-supporting frame uptilizing the structure of the inventory, a second like reflexively collapsible support and attachment structure is aligned in parallel fashion to the first structure. The first and second structures are appropriately adapted to be releasably interconnected to each other by at least two horizontal structure connecting rods, with display panels or sheets appropriately connected therebetween, so that the frame may be collapsed or erected as a unit without disassembly.
When the frame is in its reflexively collapsed compact position, it may be easily erected by lifting or swinging the interconnected pair of first braces from their collapsed positions to their upright inclined positions. The biased struts will slide to their upright extended positions and supportively hold the first braces stationary. The interconnected pair of second braces are then lifted and swung upwardly from their collapsed position to their upright generally vertical positions.
The frame may be eaily collapsed to its compact position for storage or transportation by releasing the interlocking latch of the hinges to swingably lower the first braces to their collapsed positions. The struts are then slidably moved to their collapsed position thereby collapsing the first braces to their collapsed positions adjacent the horizontal feet.
The height of the frame may be advantageously increased by adding parallel pairs of elongate braces (like the second braces) to the frame with additional interlocking hinges to easily construct a frame of desirable height.
Additional horizonal connecting rods, with suitable panels or sheet therebetween, may be releasably interconnected between the first and second structures to add further vertical supportive strength and rigidity to the frame.
The collapsible frames may be beneficially interconnected to one another to make display panels or walls of virtually any substantial width. Additional horizontal connecting rods, with fabric panels appropriately connected therebetween, are suitably connected between pairs of self-supporting frames for simple assembly of portable upright display panels or walls of desirable width.
Still further, the first and second parallel support and attachment structures of the frame may be advantageously adapted for mounting a flat rectangular top with conventional brackets to the top ends of the second braces of the first and second structures to thereby form a table, podium or the like.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a portable display panel or wall;
FIG. 2 is a perspective view of a portable podium (and table in broken outline);
FIG. 3 is a broken away side elevational view of the table of FIG. 2;
FIG. 4 is a side elevational view of the erect support and attachment structure;
FIG. 5 is a cross-sectional view of the erect structure taken along lines 5--5 of FIG. 1;
FIG. 6 is a side elevational view of an interlocking hinge of the structure;
FIG. 7 is a front elevational view of the interlocking hinge;
FIG. 8 is a rear elevational view of the interlocking hinge;
FIG. 9 is a cross-sectional view of the interlocking hinge taken along lines 9--9 of FIG. 7;
FIG. 10 is a side elevational view of the structure with its fourth brace in its collapsed position;
FIG. 11 is a side elevational view of the structure with the third and fourth braces in their respective collapsed positions;
FIG. 12 is a side elevational view of the structure with the second, third, and fourth braces in their respective collapsed position;
FIG. 13 is a side elevational view with the structure in its collapsed compact position for easy storage or transportation; and
FIG. 14 is a perspective view of a pair of interconnected portable self-supporting display panel frames.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIGS. 1 and 2, portably self-supporting display panel frame 10 and portable self-supporting podium frame 110 may generally be seen. Frames 10 and 110 each include a like parallel pair of interconnected support and attachment structures 12.
Structure 12 generally includes a horizontal elongate foot 14 pivotally connected to first elongate brace 22. A biased slidably collapsible support strut 30 is connect between the foot 14 and first brace 22. The top end of first brace 22 has an interlocking hinge 42 attached thereto which is in turn attached to the bottom end of a second elongate brace 80. Horizontal structure connecting rods 98, which preferably have fabric panels 100 appropriately connected therebetween, releasably interconnect the like parallel pair of support and attachment structures 12 of frames 10 and 110.
In display panel or wall frame 10 (FIG. 1) additional pairs of elongate braces 86 and 94 are added to expand structures 12. Second braces 80 have a second like interlocking hinges 84 attached to their top ends and to the bottom ends of third elongate braces 86. Second hinges 84 are aligned in reverse pivotal orientation compared to first hinges 42. Third interlocking hinges 92 are attached to the top ends of third braces 86 and to the bottom ends of fourth elongate braces 94. Third hinges 92 are pivotally oriented similarly to first hinges 42 and in reverse orientation compared to second hinges 84 to thereby permit reflexive movement between the pairs of parallel braces 22, 80, 86 and 94.
Portable podium frame 110 (FIG. 2) similarly includes the pair of parallel like structures 12 each having horizontal foot 14, first brace 22, biased slidably collapsible support strut 30, interlocking hinge 42, second brace 80 and horizontal structure connecting rods 9B with panels 100. All are similarly connected as in portable display panel frame 10. The top ends of second braces 80 are suitably adapted for mounting a planar rectangular top 112 in either a horizontal position for a table 120 (FIG. 3) or in an inclined position for a podium 110 (FIG. 2).
Referring to FIGS. 4 and 5, more intricate detail of support and attachment structure 12 may be seen. Horizontal elongate foot 14 is preferably U-shaped in cross-section to add strength to foot 14, with minimal material usage. Foot 14 suitably has two pairs of transversely aligned pivot holes 16 and 20 and a pair of transversely aligned horizontal structure connecting rod mounting holes 18.
First elongate brace 22 is also suitably U-shaped in cross-section for strength and to permit overlap of brace 22 over foot 14 for compact collapse of structure 12. Brace 22 has a pair of transversely aligned holes 24 to be aligned with holes 20 of foot 14 wherethrough pivot pin 27 is suitably located and retained. First brace 22 also has a pair of transversely aligned connecting rod mounting holes 26 (similar to holes 18), a pair of transversely aligned elongate strut mounting slots 28 and a plurality of transversely aligned accessory attachment slots 40.
Slidably collapsible support strut 30 is preferably rigid and has a transversely aligned pivot pin 32 ad]acent its lower end. Pivot pin 32 passes through and is retained in pivot holes 16 of foot 14. Strut 30 also has transversely aligned sliding pin 34 adjacent its top end. Sliding pin 34 passes through and is retained in strut mounting slots 28 of first brace 22. By this arrangement, strut 30 pivots on font 14 and will slide upwardly in mounting slots 28 to its extended support position as first brace 22 is swung upwardly to its upright inclined position. Coil spring 36 is suitably connected between sliding pin 34 and spring retaining pin 38 which is mounted in first brace 22. Spring 36 biases strut 30 towards its upright inclined position thereby automating the erection of structure 12 and preventing inadvertent collapse of first brace 22. When structure 12 is in its erect position, angle "A" between foot 14 and first brace 22 is approximately 65°.
The top end of first brace 22 has lower leaf 44 of first interlocking hinge 42 suitably attached thereto such as by rivets or screws. The upper leaf 46 of hinge 42 is also suitably attached to the bottom end of second elongate brace 80 which is preferrably U-shaped in cross section.
The novel construction of interlocking hinge 42 may be more clearly seen in FIGS. 6, 7, 8, and 9. Interlocking hinge 42 has lower leaf 44, which is comprised of parallel plates 44a and 44b, and upper leaf 46, which is comprised of parallel plates 46a and 46b. Lower leaf 44 and upper leaf 46 are pivotally interconnected by hinge pin 50 which has a threaded passage therethrough. Conventional screws 56 threadable within hinge pin 50, suitably hold lower and upper leafs 44 and 46 on hinge pin 50. Hinge pin 50 preferably supports spacer roller 52 and friction washers 54 which are between respective plates 44a, 46a and 44b, 46b of lower and upper leafs 44 and 46.
Upper leaf plates 46a and 46b appropriately have retaining flanges 48, latch pivot pin 58 therebetween, which also has a threaded passage therethrough, and traversely aligned hinge mounting holes 70. Lower leaf plates 44a and 44b appropriately support notch pin 60 therebetween, which also has a threaded passage therethrough, transversely aligned hinge mounting holes 70 and connecting rod mounting holes 72 which are to be aligned with rod mounted holes 26 on first braces 22. Pins 58 and 60 are preferably parallel to hinge pin 50.
Elongate latch 62, which is suitably U-shaped in cross-section, is pivotally mounted on latch pin 58 in transverse alignment with hinge pin 50. Latch 62 has a tapered end adjacent lower leaf 44 with notch 64 thereat. Latch 62's tapered end is constructed to be slidable over notch pin 60 and to cooperatively permit notch 64 to interlock with notch pin 60. A pair of retaining ears 66 are on the other end of latch 62 and are constructed to strike retaining flanges 48 to prevent further outward rotational movement of latch 62 beyond flanges 48. Conventional coil spring 68 with extending ends is suitably mounted on latch pin 58 under tension with its ends appropriately confined between the inside of latch 62 and roller 52 thereby biasing latch 62 for outward rotational movement thereby cooperatively holding notch 64 in contact with notch pin 60 in an interlocking relationship. This relationship may be released by pressing or moving latch 62 adjacent ears 66 in an inward rotational direction towards pin 50 thereby disengaging notch 64 and notch pin 60 to permit the collapse of second brace 80 to a position adjacent first brace 22.
The interlocking hinges 42, 84 and 92 within vertically expanded structure 12 are of similar construction. They may be easily attached to the ends of braces 22, 80, 86 and 94 by rivits passing through the respective braces and mounting holes 70 and by conventional screws 56 passing through the respective braces and into interiorly threaded latch and notch pins 58 and 60.
Again referring to FIGS. 4 and 5, second brace 80 has its lower end attached to upper leaf 46 of interlocking hinge 42. Second brace 80 has two pairs of transversely aligned connecting rod mounting holes 82 (which also suitably may be used for mounting retangular top 112 discussed hereinafter) and a plurality of tranversely aligned accessory attachment slots 40. Angle "B" between first brace 22 and second brace 80 is approximately 150° when structure 12 is in its erect upright position. Angles "A" and "B" are such to permit foot 14 and first brace 22 to add vertical supportive strength to structure 12 while yet requiring minimal materials and spatial requirements.
To vertically expand structure 10, second brace 80 at its top end suitably has a second interlocking hinge 84 attached thereat with its pivotal swing orientation in reverse direction as first interlocking hinge 42 to permit reflexive collapse and erection of structure 12. Third brace 86, also preferably U-shaped in cross-section, has a pair of transversely aligned connecting rod mounting holes 88 along with a plurality of transversely aligned accessory attachment slots 40.
Latch release button 90 is appropriately adjacent to the top end of third brace 86. When latch 62 of second hinge 84 is released from engagement with latch pin 60, third brace 86 will swing downwardly and permit aligned release button 90 to cooperatively depress latch 62 of first interlocking hinge 42 inwardly against biasing spring 68 to release the interlocking relationship of pin 60 and notch 64 to thereby unlock hinge 42 and automate the collapse of expanded structure 12.
Third interlocking hinge 92 is suitably attached to the top of third brace 86 and has its pivotal swing oreintation in the same direction as first hinge 42 while being in reverse direction compared to second hinge 84 to permit reflexive collapse and erection of expanded structure 12. Fourth brace 94, preferably U-shaped in cross-section, has its lower end suitably attached to third interlocking hinge 92. Fourth brace 94 suitably has a plurality of traversely aligned accessory attachment slots 40 and a pair of transversely aligned connecting rod mounting holes 96. Another latch release button 90 is appropriately adjacent to the top end of fourth brace 94. When latch 62 of third hinge 92 is manually released from engagement with latch pin 60, fourth brace 94 will swing downwardly and permit aligned release button 90 or fourth brace 94 to cooperatively depress latch 62 of second interlocking hinge 84 inwardly against its biasing spring 68 to release the interlocking relationship of pin 60 and notch 64 to thereby unlock hinge 84 and further automate the collapse of expanded structure 12.
As shown in FIGS. 1 and 2, horizontal structure connecting rods 98, preferably having fabric sheets or panels 100 conventionally connected therebetween. Panels 100 suitably may have graphic presentations printed thereon for display or advertising purposes. Aternatively, panels 100 may simply be blank to visibly mask frame 10 or 110 from a viewer's eye for aesthetic appeal.
Rods 98 suitably interconnect a like pair of parallel support and attachment structures 12 by having opposing ends of rods 98 passing through transversely aligned connecting rod mounting holes 18, 26, 82, 88, and 96 respectively located in foot 14 and braces 22, 80, 86 and 94 of like parallel structures 12. Mounting holes 18, 26, 82, 88 and 96 are preferably adequately spaced apart to hold panels 100 tautly when frame 10 is in its erect position. The ends of rods 98 are releasably held thereat in a conventional manner such as by retaining clips, threaded caps, etc. The ends of rods 98 also rotate within holes 18, 26, 82, 88 and 96 to permit the reflexive collapse of frame 10 without disconnection of rods 98 from parallel structures 12.
In FIGS. 1 and 14, conventional light fixtures 102 may be suitably mounted to structures 12 by mounting brackets with holes cooperatively aligned with mounting holes 96 in fourth braces 94. The ends of rods 98 may then suitably pass through mounting brackets of light fixtures 102 and mounting holes 96 in a manner that will preferably will permit pivotal movement of light fixtures 102. Shelves 104 (FIG. 14) with conventionally known brackets may be appropriately mounted on display panel frame 10 in a releasable interlocking relationship with horizontally aligned pairs of accessory attachment slots 40 in parallel structures 12.
Referring to FIGS. 10, 11, 12 and 13, the reflexive collapsing operation of vertically expanded structure 12 may illustratively be seen in several stages. However, it should be noted that the entire panel frame 10 may be collapsed as a unit because horizontal structure connecting rods 98 with fabric panels 100 (not shown) are adapted to cooperatively permit the collapse and erection operations of complete panel frame 10 without disassembly.
As fourth brace 94 is swung downwardly to its collapsed position adjacent third brace 86, latch release button 90 on brace 94 cooperatively depresses interlocking hinge latch 62 of second hinge 84 to thereby permit third brace 86 to reflexively swing downwardly in the direction of arrow "C" its collapsed position (FIGS. 10 and 11). As third brace 86 swings downwardly, latch release button 90 on brace 86 cooperatively depresses interlocking hinge latch 62 of first hinge 42 thereby permitting second brace 80 to reflexively swing downwardly in the direction of arrow "D" to its collapsed position adjacent first brace 22 (FIGS. 11 and 12). Manually depressing strut 30 in the direction of arrow "E" will move sliding pin 34 downwardly in elongate slot 28 against biasing spring 36 and will permit first brace 22 to swing downwardly to its collapsed position adjacent foot 14 (FIGS. 12 and 13).
Referring to FIG. 14, a pair of portable display panel frames 10 are shown supporting additional horizontal structure connecting rods 98 with fabric panels 100 suitably adjacent connecting rods 98 of frame 10. By this arrangement, interconnected portable display panel frames 10 may be quickly assembled to any desirable width.
Referring to FIGS. 2 and 3, portable podium frame 110 has an adjustable planar rectangular top 112 with removable pencil/paper retaining bar 114 and parallel top mounting brackets 116 (FIG. 3). Brackets 116 have aligned mounting holes 118. Top 112 may be mounted on second braces 80 by suitably aligning mounting holes 118 with holes 82 on second braces 80 and appropriately passing conventional pins therethrough. One such alignment may permit an inclined position of top 112 to create a portable podium 110. Alternatively, mounting holes 118 and 82 may be aligned to permit top 112 to be in a horizontal position thereby creating a portable table 120.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore desired that the present embodiment be considered in all respects as illustrative and not restrictive, reference being made to the appended claims rather than to the foregoing description to indicate the scope of the invention. | A first reflexively collapsible support and attachment structure for use in portable self-supporting frames for display panels, walls, podiums and tables. A horizontal elongate foot having front and back ends forms the base. Connected to the front end of the foot is a first brace adapted to swing to an inclined position. A biased support strut is provided between the foot and the first brace. The support strut is slidably collapsible and supports the first brace in the inclined position. Second and subsequent braces are interlockingly hinged such as to swing to generally vertical positions. Aligned in parallel fashion is a second like reflexively collapsible structure. The first and second structures are interconnected by at least two horizontal connecting rods. Display panels or sheets are connected between the first and second structures. | 8 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of prior filed International Application, Serial No. PCT/US2012/025028 filed Feb. 14, 2012, which claims priority to U.S. Provisional Patent Application 61/422,561, entitled, “Organic Photovoltaic Array and Method of Manufacture”, filed 14 Feb. 2011, the contents of which are herein incorporated by reference.
FIELD OF INVENTION
[0002] This invention relates to spray-manufactured organic solar photovoltaic cell. Specifically, the invention provides a novel method of manufacturing organic solar photovoltaic cells using spray-deposition and the organic solar photovoltaic cell resulting therefrom.
BACKGROUND OF THE INVENTION
[0003] In recent years, energy consumption has drastically increased, due in part to increased industrial development throughout the world. The increased energy consumption has strained natural resources, such as fossil fuels, as well as global capacity to handle the byproducts of consuming these resources. Moreover, future demands for energy are expected in greatly increase, as populations increase and developing nations demand more energy. These factors necessitate the development of new and clean energy sources that are economical, efficient, and have minimal impact on the global environment.
[0004] Photovoltaic cells have been used since the 1970s as an alternative to traditional energy sources. Because photovoltaic cells use existing energy from sunlight, the environmental impact from photovoltaic energy generation is significantly less than traditional energy generation. Most of the commercialized photovoltaic cells are inorganic solar cells using single crystal silicon, polycrystal silicon or amorphous silicon. Traditionally, solar modules made from silicon are installed on rooftops of buildings. However, these inorganic silicon-based photovoltaic cells are produced in complicated processes and at high costs, limiting the use of photovoltaic cells. These silicon wafer-based cells are brittle, opaque substances that limit their use, such as on window technology where transparency is a key issue. Further, installation is an issue since these solar modules are heavy and brittle. In addition, installation locations, such as rooftops, are limited compared to the window area in normal buildings, and even less in skyscrapers. To solve such drawbacks, photovoltaics cell using organic materials have been actively researched.
[0005] The photovoltaic process in OPV first starts from the absorption of light mainly by the polymer, followed by the formation of excitons. The exciton then migrates to and dissociates at the interface of donor (polymer)/acceptor (fullerene). Separated electrons and holes travel to opposite electrodes via hopping, and are collected at the electrodes, resulting in an open circuit voltage (Voc). Upon connection of electrodes, a photocurrent (short circuit current, Isc) is created.
[0006] Organic photovoltaic cells based on it-conjugated polymers have been intensively studied following the discovery of fast charge transfer between polymer and carbon C 60 (Sariciftci, et al., Science 1992, 258, 1474; Yu, et al., Science 1995, 270, 1789; Yang and Heeger, Synth. Met. 1996, 83, 85; Shaheen, et al., Appl. Phys. Lett. 2001, 78, 841; Padinger, et al., Adv. Funct. Mater. 2003, 13, 85; Brabec, et al., Appl. Phys. Lett. 2002, 80, 1288; Ma, et al., Adv. Funct. Mater. 2005, 15, 1617; Reyes-Reyes, et al., High-efficiency photovoltaic devices based on annealed poly(3-hexylthiophene) and 1-(3-methoxycarbonyl)-propyl-1- phenyl-(6,6)C 61 blends. Appl. Phys. Lett. 2005, 87, 083506-9; Chen, et al., Polymer solar cells with enhanced open-circuit voltage and efficiency. Nat. Photonics, 2009, 3(11), 649-53). Conventional organic photovoltaic devices use transparent substrates, such as an indium oxide like indium tin oxide (ITO) or IZO, as an anode and aluminum or other metal as a cathode. A photoactive material including an electron donor material and an electron acceptor material is sandwiched between the anode and the cathode. The donor material in conventional devices is poly-3-hexylthiophene (P3HT), which is a conjugated polymer. The conventional acceptor material is (6,6)-phenyl C 61 butyric acid methylester (PCBM), which is a fullerene derivative. Both the ITO and aluminum contacts use sputtering and thermal vapor deposition, both of which are expensive, high vacuum, technologies. In these photovoltaic cells, light is typically incident on a side of the substrate requiring a transparent substrate and a transparent electrode. However, this limits the materials that may be selected for the substrate and electrode. Further, a minimum thickness of 30 to 500 nm is needed to increasing conductivity. Moreover, the organic photoelectric conversion layer is sensitive to oxygen and moisture, which reduce the power conversion efficiency and the life cycle of the organic solar cell. Development of organic photovoltaic cells, has achieved a conversion efficiency of 3.6% (P. Peumans and S. R. Forrest, Appl. Phys. Lett. 79, 126 (2001)).
[0007] The photovoltaic process in OPV first starts from the absorption of light mainly by the polymer, followed by the formation of excitons. The exciton then migrates to and dissociates at the interface of donor (polymer)/acceptor (fullerene). Separated electrons and holes travel to opposite electrodes via hopping, and are collected at the electrodes, resulting in an open circuit voltage (V oc ). Upon connection of electrodes, a photocurrent (short circuit current, I sc ) is created.
[0008] These polymeric OPV holds promise for potential cost-effective photovoltaics since it is solution processable. Large area OPVs have been demonstrated using printing (Krebs and Norman, Using light-induced thermocleavage in a roll-to-roll process for polymer solar cells, ACS Appl. Mater. Interfaces 2 (2010) 877-887; Krebs, et al., A roll-to-roll process to flexible polymer solar cells: model studies, manufacture and operational stability studies, J. Mater. Chem. 19 (2009) 5442-5451; Krebs, et al., Large area plastic solar cell modules, Mater. Sci. Eng. B 138 (2007) 106-111; Steim, et al., Flexible polymer Photovoltaic modules with incorporated organic bypass diodes to address module shading effects, Sol. Energy Mater. Sol. Cells 93 (2009) 1963-1967; Blankenburg, et al., Reel to reel wet coating as an efficient up-scaling technique for the production of bulk heterojunction polymer solar cells, Sol. Energy Mater. Sol. Cells 93 (2009) 476-483), spin-coating and laser scribing (Niggemann, et al., Organic solar cell modules for specific applications—from energy autonomous systems to large area photovoltaics, Thin Solid Films 516 (2008) 7181-7187; Tipnis, et al., Large-area organic photovoltaic module—fabrication and performance, Sol. Energy Mater. Sol. Cells 93 (2009) 442-446; Lungenschmied, et al., Flexible, long-lived, large-area, organic solar cells, Sol. Energy Mater. Sol. Cells 91 (2007) 379-384), and roller painting (Jung and Jo, Annealing-free high efficiency and large area polymer solar cells fabricated by a roller painting process, Adv. Func. Mater. 20 (2010) 2355-2363). ITO, a transparent conductor, is commonly used as hole collecting electrode (anode) in OPV, and a normal geometry OPV starts from ITO anode, with the electron accepting electrode (cathode) usually a low work function metal such as aluminum or calcium, being added via thermal evaporation process.
[0009] There are two different approaches in inverted geometry. One approach is ITO-free wrap through by Zimmermann et.al., (Zimmermann, et al., ITO-free wrap through organic solar cells—A module concept for cost-efficient reel-to-reel production. Sol. Energy Mater. Sol. Cells, 2007, 91(5), 374) another approach is to add an electron transport layer onto ITO to make it function as cathode. Inverted geometry OPVs in which the device was built from modified ITO as cathode first have been studied both in single cells (Huang, et al., A Semi-transparent Plastic Solar Cell Fabricated by a Lamination Process. Adv. Mater. 2008, 20(3), 415; Bang-Ying Yu, et al., Efficient inverted solar cells using TiO 2 nanotube arrays. Nanotechnology, 2008, 19(25), 255202; Li, et al., Efficient inverted polymer solar cells. Appl. Phys. Lett. 2006, 88, 253503; Jingyu Zou, et al., Metal grid/conducting polymer hybrid transparent electrode for inverted polymer solar cells. Appl. Phys. Lett. 2010, 96, 203301; Waldauf, et al., Highly efficient inverted organic photovoltaics using solution based titanium oxide as electron selective contact. Appl. Phys. Lett. 2006, 89(23), 233517; Zhou, et al., Inverted and transparent polymer solar cells prepared with vacuum-free processing. Sol. Eng . & Sol. Cells 2009, 93(4), 497) and solar modules (Krebs and Norman, Using Light-Induced Thermocleavage in a Roll-to-Roll Process for Polymer Solar Cells. ACS Applied materials & interfaces, 2010, 2, 877-87; Krebs, et al., A roll-to-roll process to flexible polymer solar cells: model studies, manufacture and operational stability studies. J. of Mater. Chem. 2009, 19, 5442-51; Krebs, et al., Large area plastic solar cell modules. Mater. Sci. Eng. B, 2007, 138(2), 106-11).
[0010] In addition, to improve efficiency of the organic thin film solar cell, photoactive layers were developed using a low-molecular weight organic material, with the layers stacked and functions separated by layer. (P. Peumans, V. Bulovic and S. R. Forrest, Appl. Phys. Lett. 76, 2650 (2000)). Alternatively, the photoactive layers were stacked with a metal layer of about 0.5 to 5 nm interposed to double the open end voltage (V oc ). (A. Yakimov and S. R. Forrest, Appl. Phys. Lett. 80, 1667 (2002)). As described above, stacking of photoactive layer is one of the most effective techniques for improving efficiency of the organic thin film solar cell. However, stacking photoactive layers can cause layers to melt due to solvent formation from the different layers. Stacking also limits the transparency of the photovoltaic. Interposing a metal layer between the photoactive layers can prevent solvent from one photoactive layer from penetrating into another photoactive layer and preventing damage to the other photoactive layer. However, the metal layer also reduces light transmittance, affecting power conversion efficiency of the photovoltaic cell.
[0011] However, in order for solar cells to be compatible with windows, issues with the transparency of the photovoltaic must first be addressed. The metal contacts used in traditional solar modules are visibility-blocking and has to be replaced. Another challenge is to reduce cost for large scale manufacturing in order for organic solar cells to be commercially viable, a much lower manufacturing cost to compensate for the lower efficiency than current photovoltaic products. OPV modules fabricated by other large scale manufacturing techniques such as printing (Krebs and Norman, Using Light-Induced Thermocleavage in a Roll-to-Roll Process for Polymer Solar Cells. ACS Applied materials & interfaces, 2010, 2, 877-87; Krebs, et al., A roll-to-roll process to flexible polymer solar cells: model studies, manufacture and operational stability studies. J. of Mater. Chem. 2009, 19, 5442-51; Krebs, et al., Large area plastic solar cell modules. Mater. Sci. Eng. B, 2007, 138(2), 106-11; Jung and Jo, Annealing-free high efficiency and large area polymer solar cells fabricated by a roller painting process, Adv. Func. Mater. 20 (2010) 2355-2363) and spin-coating (Tipnis, et al., Large-area organic photovoltaic module—Fabrication and performance. Sol. Energy Mater. Sol. Cells, 2009, 93(8), 442-6; Lungenschmied, et al., Flexible, long-lived, large-area, organic solar cells. Sol. Energy Mater. Sol. Cells, 2007, 9(5), 379-84) have been demonstrated, however, all these still involve the use of metal in certain way. For example, a solution-based all-spray device, which was opaque, showed a PCE as high as 0.42% (Lim, et al., Spray-deposited poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) top electrode for organic solar cells, Appl. Phys. Lett. 93 (2008) 193301-4). Large-scale manufacturing techniques, such as printing, have lowered the cost of manufacture, but still involve the use of metal in certain way, and therefore affect the transparency of the photovoltaic cell.
[0012] Therefore, what is needed is a new method of manufacturing organic photovoltaic cells without the use of metal, to allow for novel photovoltaic cells with enhanced transparency. The art at the time the present invention was made did not describe how to attain these goals, of manufacturing less expensive and less complex devices, having enhanced transparency.
SUMMARY OF THE INVENTION
[0013] Comparing with conventional technology based on spin-coating and using metal as cathode contact, which greatly limits transparency of solar cells and posts difficulty for large scale manufacturing, the new spray technology solves these two problems simultaneously. A thin film organic solar array is fabricated employing this layer-by-layer spray technique onto desired substrates (can be rigid as well as flexible). This technology eliminates the need for high-vacuum, high temperature, low rate and high-cost manufacturing associated with current silicon and in-organic thin film photovoltaic products.
[0014] The organic solar photovoltaic cell is manufactured on an ITO-coated substrate, such as cloth, glass, plastic or any material known in the art for use as a photovoltaic substrate. Exemplary plastics include any polymer such as acrylonitrile butadiene styrene (ABS), acrylic (PMMA), cyclic olefin copolymer (COC), ethylene-vinyl acetate (EVA), ethylene vinyl alcohol (EVOH), fluoroplastics, such as PTFE, FEP, PFA,CTFE, ECTFE, and ETFE, Kydex (an acrylic/PVC alloy), liquid crystal polymer (LCP), polyoxymethylene (POM or Acetal), polyacrylates (acrylic), polyacrylonitrile (PAN or acrylonitrile), polyamide (PA or nylon), polyamide-imide (PAI), polyaryletherketone (PAEK or ketone), polybutadiene (PBD), polybutylene (PB), polychlorotrifluoroethylene (PCTFE), polycyclohexylene dimethylene terephthalate (PCT), polycarbonate (PC), polyhydroxyalkanoates (PHAs), polyketone (PK), polyester, polyetherketoneketone (PEKK), polyetherimide (PEI), polyethersulfone (PES), chlorinated polyethylene (CPE), polyimide (PI), polymethylpentene (PMP), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polypropylene (PP), polystyrene (PS), polysulfone (PSU), polytrimethylene terephthalate (PTT), polyurethane (PU), polyvinyl acetate (PVA), styrene-acrylonitrile (SAN). The ITO layer was optionally patterned onto the first face of the glass, forming an anode, by obtaining an ITO-coated substrate, patterning the ITO using photolithography, etching the ITO, and cleaning the etched ITO and substrate. The ITO may be etched with a mixed solution of HCl and HNO 3 . The etched ITO and substrate was then optionally cleaned by at least one of acetone, isopropanol, or UV-ozone. The cleaning step may be performed at 50° C. for 20 min each, followed by drying with N 2 .
[0015] A layer of Cs 2 CO 3 was prepared and sprayed onto the etched ITO substrate. In some variations, the layer of Cs 2 CO 3 was prepared by dissolving Cs 2 CO 3 in 2-ethoxyethanol at a ratio of 2 mg/ml, and stirred for 1 hour. After the Cs 2 CO 3 layer was sprayed onto the OPV cell, the layer was annealed to the OPV cell inside a glovebox. Optionally, the annealing step occurred at 150° C. for 10 min inside the N 2 glovebox. The Cs 2 CO 3 layer has an optional thickness of about 5 Å to about 15 Å.
[0016] After the Cs 2 CO 3 layer was annealed, an active layer of P3HT and PCBM was prepared and sprayed onto the OPV cell. The active layer solution was optionally prepared my mixing P3HT and PCBM with a weight ratio of 1:1 in dichlorobenzene. The active layer was then optionally stirred on a hotplate for 48 h at 60° C. prior to spraying. After spraying, the OPV cell was dried in an antechamber under vacuum for at least 12 hours. The the active layer of has an optional layer thickness of about 100 nm to about 500 nm, depending on the organic photovoltaic cell materials and transparency requirements. A layer comprising poly(3,4)ethylenedioxythiophene:poly-styrenesulfonate and 5 vol. % of dimethylsulfoxide was then disposed on the active layer, providing the cathode for the photovoltaic cell. Optionally, the poly(3,4)ethylenedioxythiophene:poly-styrenesulfonate mixed with 5 vol. % of dimethylsulfoxide was prepared diluting the poly(3,4)ethylenedioxythiophene:poly-styrenesulfonate filtering the diluted poly(3,4)ethylenedioxythiophene:poly-styrenesulfonate through a 0.45 μm filter, and mixing the dimethylsulfoxide into the diluted poly(3,4)ethylenedioxythiophene:poly-styrenesulfonate. In some variations, this cathodic layer has a thickness of about 100 nm to about 700 nm, and may be 600 nm in some variations. Exemplary thicknesses include 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 550 nm, 600 nm, 650 nm, and 700 nm.
[0017] The OPV cell was placed into high vacuum for 1 h, such as at 10 −6 Torr. The OPV cell was then annealed at 120° C., 160° C., or at 120° C. for 10 minutes followed by high vacuum for 1 hour and annealing at 160° C. for 10 minutes and encapsulated with a UV-cured epoxy.
[0018] The photovoltaic cells may also be in electrical connection, thereby forming an array. For example, a series of organic solar photovoltaic cells disposed into an array of 50 individual cells having active area of 12 mm 2 . The array comprises 10 cells disposed in series in one row, and 5 rows in parallel connection in some variations.
[0019] The inventive device and method has solved the costly and complicated process currently used to make crystalline and thin film solar cells, namely, high-vacuum, high temperature, low rate and high-cost manufacturing. Furthermore, this technology could be used on any type of substrate including cloth and plastic. This new technology enables all solution processable organic solar panel on with transparent contacts. This technique has great potential in large-scale, low-cost manufacturing of commercial photovoltaic products based on solutions of organic semiconductors. The use of self assembled molecules (SAM) modify the work function of ITO, and SAM was used in place of the previous Cs 2 CO 3 improving the device efficiency and reproducibility.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] For a fuller understanding of the invention, reference should be made to the following detailed description, taken in connection with the accompanying drawings, in which:
[0021] FIG. 1 is a diagram showing a perspective view of the novel inverted OPV cells containing sprayed-on layers.
[0022] FIGS. 2(A) and (B) are images of the device structure of an inverted test device. (A) top view; (B) side view.
[0023] FIG. 3 is a graph showing the I-V characteristics of three test devices without Cs 2 CO 3 layer (black solid line), and with Cs 2 CO 3 layer at difference thickness (black line with empty triangle and line with filled triangle).
[0024] FIGS. 4(A) and (B) are graphs showing the comparison of (A) transparency and (B) resistance between ITO and the anode (modified PEDOT:PSS) at different thickness.
[0025] FIG. 5 is a graph showing the transmission spectra of an active layer (P3HT:PCBM) of 500 nm (black line with filled square), and with a m-PEDOT:PSS layer of 600 nm (gray line with filled circle).
[0026] FIG. 6 is a top-view image of the device architecture of an inverted array having 50 cells in the array.
[0027] FIG. 7 is a side-view image of the device architecture of an inverted array.
[0028] FIG. 8 is a graph showing the IV of four test cells measured with AM1.5 solar illumination under various annealing conditions: 1-step annealing at 120° C. (light grey filled circle), or 160° C. (black filled square), and 2-step annealing (dark grey filled triangle).
[0029] FIG. 9 is a graph showing the IPCE of four test cells measured under tungsten lamp illumination at various annealing conditions: 1-step annealing at 120° C. (light grey filled circle), or 160° C. (black filled square), and 2-step annealing (dark grey filled triangle).
[0030] FIG. 10 is a graph showing the IV of 4 inverted spray-on array measured with AM1.5 solar illumination under various annealing conditions: 1-step annealing at 120° C. (dashed line), or 160° C. (light grey thin line), and 2-step annealing (black filled square). These 3 arrays use m-PEDOT 500 as anode. The 4 th array (thick dark grey line) uses m-PEDOT 500 as anode and was annealed at 160° C.
[0031] FIG. 11 is a graph showing the improvement of IV of an inverted array under continuous AM1.5 solar illumination. The first measurement was done right after the array was fabricated and encapsulated.
[0032] FIG. 12 is an image showing the transparency of manufactured sprayed solar array using using the disclosed methods.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0033] The present invention for the fabricatation of a see-through organic solar array via layer-by-layer (LBL) spray may be understood more readily by reference to the following detailed description of the preferred embodiments of the invention and the Examples included herein. However, before the present compounds, compositions, and methods are disclosed and described, it is to be understood that this invention is not limited to specific compounds, specific conditions, or specific methods, etc., unless stated as such. Thus, the invention may vary, and the numerous modifications and variations therein will be apparent to those skilled in the art. It is also to be understood that the terminology used herein is for the purpose of describing specific embodiments only and is not intended to be limiting.
[0034] As used herein, “about” means approximately or nearly and in the context of a numerical value or range set forth means ±15% of the numerical.
[0035] As used herein, “substantially” means largely if not wholly that which is specified but so close that the difference is insignificant.
[0036] All masks for spray are custom made by Towne Technologies, Inc. The airbrush sets for spray was purchased from ACE hardware.
EXAMPLE 1
[0037] The indium tin oxide (ITO) was patterend onto a Coming® low alkaline earth boro-aluminosilicate glass having a nominal sheet resistance of 4-10 Ohm/square (Delta /Technology, Inc.) using standard photolithography method and cleaned following the procedure described elsewhere (Lewis, et al., Fabrication of organic solar array for applications in microelectromechanical systems. Journal of Renewable and Sustainable Energy 2009, 1, 013101-9). The substrate is then exposed to a UV-lamp for 1.4 seconds in a constant intensity mode set to 25 watts. The structure was developed for about 2.5 minutes using Shipley MF319 and rinsed with water. The substrate was then hard-baked, at 145° C. for 4 minutes and any excess photoresist cleaned off with acetone and cotton. After cleaning, the substrate was etched from about 5-11 minutes with a solution of 20% HCl-7% HNO 3 on a hotplate at 100° C. The etched substrate was then cleaned by hand using acetone followed by isopropanol and UV-ozone cleaned for at least 15 minutes.
[0038] An interstitial layer was formed on top of the patterned ITO layer. A solution of 0.2% wt. Cs 2 CO 3 (2 mg/mL; Sigma-Aldrich Co. LLC, St. Louis, Mo.) in 2-ethoxyethanol was prepared and stirred for one hour at room temperature. Cs 2 CO 3 was chosen to reduce ITO work function close to 4.0 eV to be utilized as cathode. The Cs 2 CO 3 solution was sprayed onto the clean ITO substrate through a custom made shadow mask with an airbrush using N 2 set to 20 psi from a distance of about 7-10 centimeters. The product was then annealed for 10 minutes at 150° C. in an N 2 glovebox (MOD-01; M. Braun Inertgas-Systeme GmbH, Garching German).
[0039] The active layer solution was prepared by mixing separate solutions of a high molecular weight poly(3-hexylthiophene (P3HT with regioregularity over 99% and average molecular weight of 42K; Rieke Metals, Inc., Lincoln, Nebr.) and 6,6-phenyl C61 butyric acid methyl ester (PCBM, C 60 with 99.5% purity; Nano-C, Inc., Westwood, Mass.) at a weight ratio of 1:1 in dichlorobenzene at 20 mg/mL and stirred on a hotplate for 48 hours at 60° C. The active coating was then spray coated onto the Cs 2 CO 3 coated substrate using an airbrush with N 2 set to 30 psi. The airbrush was set at about 7-10 cm away from the substrate and multiple light layers of active layer were sprayed, resulting in a layer thickness of about 200 to about 300 nm. The device is then left to dry in the antechamber under vacuum for at least 12 hours. After drying, excess active layer solution was wiped off of the substrate using dichlorobenzene (DCB)-wetted cotton followed by isopropanol-wetted cotton.
[0040] A kovar shadow mask was aligned in position with the substrate and held in place by placing a magnet underneath the substrate. The series connection locations were wiped using a wooden dowel to expose the cathode for later electrical connection. The original aqueous poly(3,4)ethylenedioxythiophene:poly-styrenesulfonate (PEDOT:PSS, Baytron 500 and 750; H. C. Starck GmbH, Goslar Germany) was diluted and filtered out through a 0.45 μm filter. This filtered solution of PEDOT:PSS is mixed with 5 vol. % of dimethylsulfoxide to increase conductivity (Lim, et al., Spray-deposited poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) top electrode for organic solar cells. Appl. Phys. Lett. 2008, 93, 193301). The solution was then stirred at room temperature followed by 1 h of sonification. The m-PED coating was prepared by placing a substrate/mask on a hotplate (90° C.). The m-PED layer was spray coated using nitrogen (N 2 ) as the carrier gas, set to 30 psi, with the airbruch positioned about 7-10 cm from the substrate. Multiple light layers were applied until the final thickness of about 500 nm to about 700 nm was reached. The substrate was then removed from the hotplate and the mask removed. Care was taken to avoid removing the mPED with the mask. The substrate was placed into high vacuum treatment (10 −6 Torr) for 1 h, followed by a substrate annealing at 120-160° C. for 10 min. The modified PEDOT:PSS (m-PEDOT) was then sprayed onto the substrate using a custom made spray mask.
[0041] The finished device was placed into high vacuum (10 −6 Torr) for 1 h. This step was shown to improve the device performance with sprayed active layer (Lim, et al., Spray-deposited poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) top electrode for organic solar cells. Appl. Phys. Lett. 2008, 93, 193301). The final device was annealed at various conditions, including 120° C., 160° C., and step step annealing comprising 120° C. for 10 minutes followed by high vacuum for 1 hour and annealing at 160° C. for 10 minutes. The annealed device was encapsulated using a UV-cured encapsulant (EPO-TEK 0G142-12; Epoxy Technology, Inc., Billerica, Mass.) was applied to the edge of the encapsulation glass, and the glass is placed into the glovebox for at least 15 min, with UV exposure. The device was then flipped upside down, and the epoxy applied on top of the encapsulation glass. The device was finally exposed to 15 min of UV to cure the encapsulant epoxy.
EXAMPLE 2
[0042] Inverted organic photovoltaic cell 1 , seen in FIG. 1 , was created using the method described in Example 1, using pre-cut 4″×4″ ITO glass substrates with a nominal sheet resistance of 4-10 Ohm/square and Corning® low alkaline earth boro-aluminosilicate glass (Delta Technology, Inc., Tallahassee, Fla.). Inverted photovoltaic cell 1 was composed of different layers of active materials and terminals (anode and cathode) built onto substrate 5 . Anode 10 , comprised of ITO in the present example, was sprayed onto substrate 5 forming a ‘¦¦’ pattern extending from a first set of edges of substrate 5 . Interstitial layer 40 covers anode 10 , except for the outermost edges, as seen in FIG. 2(A) , and permits ITO to be used as an anode as discussed in Example 1. The components of the SAM layer were chosen to provide a gradient for charges crossing the interface, approximating a conventional p-n junction with organic semiconductors, thereby providing an increased efficiency of heterojunctions. Active layer 30 is disposed directly on top of interfacial buffer layer 40 , and was prepared using poly(3-hexylthiophene) and 6,6-phenyl C61 butyric acid methyl ester. Anode 20 was disposed on the active layer in a pattern, similar to the cathode, but perpendicular to the cathode. Exemplary anode materials include PEDOT:PSS doped with dimethylsulfoxide. The fully encapsulated 4 μm×4 μm array was found to possess over 30% transparency.
EXAMPLE 3
[0043] An inverted single-cell test device was used as a starting point to ensure a good reference point for the multi-cell array, which consists of four identical small cells (4 mm 2 ) on a 1″×1″ substrate, as seen in FIG. 2(B) . The cell is sandwiched between two cross electrodes, designated as 50 and 51 . The test device was fabricated using the same procedure described in Example 1, with m-PEDOT 500 as anode.
[0044] ITO normally has a work function of ˜4.9 eV. The function of ITO in a traditional OPV device is as an anode. There have been previous reports on tuning the work function of ITO by adding an electron transport layer such as ZnO (Jingyu Zou, et al., Metal grid/conducting polymer hybrid transparent electrode for inverted polymer solar cells. Appl. Phys. Lett. 2010, 96, 203301), TiO 2 (Huang, et al., A Semi-transparent Plastic Solar Cell Fabricated by a Lamination Process. Adv. Mater. 2008, 20(3), 415; Bang-Ying Yu, et al., Efficient inverted solar cells using TiO 2 nanotube arrays. Nanotechnology, 2008, 19(25), 255202; Li, et al., Efficient inverted polymer solar cells. Appl. Phys. Lett. 2006, 88, 253503), PEO (Zhou, et al., Inverted and transparent polymer solar cells prepared with vacuum-free processing. Sol. Eng . & Sol. Cells 2009, 93(4), 497) and Cs 2 CO 3 (Huang, et al., A Semi-transparent Plastic Solar Cell Fabricated by a Lamination Process. Adv. Mater. 2008, 20(3), 415; Bang-Ying Yu, et al., Efficient inverted solar cells using TiO 2 nanotube arrays. Nanotechnology, 2008, 19(25), 255202; Li, et al., Efficient inverted polymer solar cells. Appl. Phys. Lett. 2006, 88, 253503) in inverted OPV single cells. In this work, Cs 2 CO 3 was chosen for its economic cost and easy handling. By spin coating a solution of 2-ethoxyethanol with 0.2% Cs 2 CO 3 at 5000 rpm for 60s, a very thin layer (˜10 Å) of Cs 2 CO 3 is formed over the ITO. It was reported that a dipole layer would be created between Cs 2 CO 3 and the ITO. The dipole moment helped to reduce the work function of ITO, allowing ITO to serve as the cathode (Huang, et al., A Semi-transparent Plastic Solar Cell Fabricated by a Lamination Process. Adv. Mater. 2008, 20(3), 415; Bang-Ying Yu, et al., Efficient inverted solar cells using TiO 2 nanotube arrays. Nanotechnology, 2008, 19(25), 255202; Li, et al., Efficient inverted polymer solar cells. Appl. Phys. Lett. 2006, 88, 253503).
[0045] FIG. 3 shows how the Cs 2 CO 3 layer affects the performance of the inverted cell. The control cell without Cs 2 CO 3 (black solid line) performed almost like a resistor and had negligible V oc (0.03V). Without being bound to any specific theory, the difference between the present invention and previous work (Zhou, et al., Inverted and transparent polymer solar cells prepared with vacuum-free processing. Sol. Eng. & Sol. Cells 2009, 93(4), 497) can be explained by the use of an electron transport layer to alleviate non-ohmic contact with the cathode (PEDOT in this case) in their work. For a better controlled thickness, Cs 2 CO 3 was spin coated on to the cleaned ITO substrate in these devices. As shown in FIG. 3 , the optimal thickness of Cs 2 CO 3 layer was achieved at a spin rate of 5000 rpm. At higher rate of 7000 rpm, the device was less efficient owing to the fact of a discontinuous Cs 2 CO 3 layer. The optimal thickness was later determined to be around 15 Å.
[0046] Previous reports showed Cs 2 CO 3 can lower the ITO work function to as low as 3.3 eV (Huang, et al., A Semi-transparent Plastic Solar Cell Fabricated by a Lamination Process. Adv. Mater. 2008, 20(3), 415; Bang-Ying Yu, et al., Efficient inverted solar cells using TiO 2 nanotube arrays. Nanotechnology, 2008, 19(25), 255202; Li, et al., Efficient inverted polymer solar cells. Appl. Phys. Lett. 2006, 88, 253503). In order to get an estimate of the effective work function of ITO/Cs 2 CO 3 , a control device with aluminum (100 nm in thickness) as cathode was fabricated. Since aluminum is not transparent, the I-V was measured by shining light from m-PEDOT side. The device was analyzed by exposing the cell to continuous radiation. The current-voltage (I-V) characterization of the solar array was performed with a 1.6 KW solar simulator under AM1.5 irradiance of 100 mW/cm 2 (Newport Corp., Franklin Mass.). No spectral mismatch with the standard solar spectrum was corrected in the power conversion efficiency (PCE) calculation. The incident photon converted electron (IPCE), or the external quantum efficiency, of the device was measured using 250 W tungsten halogen lamp coupled with a monochromator (Newport Oriel Cornerstone ¼ m). The photocurrent was detected by a UV enhanced silicon detector connected with a Keithley 2000 multimeter. The transmission spectrum of active layer was performed on the same optical setup. V oc of such control device was 0.24V, whereas Voc of the inverted cell in FIG. 3 was 0.36V measured under the same illumination condition. Since aluminum has work function of 4.2 eV, this means in the present invention, the effective work function of ITO/Cs 2 CO 3 is close to 4.1 eV.
EXAMPLE 4
[0047] An inverted single-cell test device was prepared, as discussed in Example 1, but using different thicknesses of m-PEDOT to determine cell characterisctics at different cell thicknesses. ITO was chose as a reference for comparison. At thickness of about 100 nm, the transparency of m-PEDOT is about 80%, comparable with ITO, as seen in FIG. 4(A) . As expected, the resistance decreases as thickness increases, which is consistent with the bulk model, seen in FIG. 4(B) . The trade-off between transparency and resistance is another important fabrication parameter. The current array was fabricated with thickness of about 600 nm, which has moderate resistance of 70 ohm/square, and transparency about 50%. A comparison between transmission spectra of the active layer (P3HT:PCBM, 200 nm) and m-PEDOT anode of 600 nm showed the total transparency over the spectra range shown decreases from 73% to 31% after spraying on the m-PEDOT anode, as seen in FIG. 5 .
[0048] A solar array was prepared, as disclosed above, comprising 50 individual cells each has active area of 12 mm 2 , seen in FIG. 6 . The array was configured with 10 cells in series to increase in one row to increase voltage, and 5 rows in parallel connection to increase current, seen in cross section in FIG. 7 . The arrays were prepared with have m-PEDOT 750 or m-PEDOT 500 as semitransparent anode.
EXAMPLE 5
[0049] Annealing has shown to be the most important factor to improve organic solar cell performance (Shaheen, Brabec, Sariciftci, Padinger, Fromherz, and Hummelen, Appl. Phys. Lett. 2001, 78, 841; Padinger, et al., Effects of Postproduction Treatment on Plastic Solar Cells. Adv. Funct. Mater. 2003, 13(1), 85-88). Cells were exposed to a 1.6 KW solar simulator under AM1.5 irradiance of 100 mW/cm 2 (Newport Corp., Franklin Mass.). Current-voltage (IV) and incident photon converted electron (IPCE) were compared between three inverted test cells at different annealing conditions, as seen in FIG. 8 : 1-step annealing at 120° C. (gray filled circle), or 160° C. (black filled square); 2-step annealing at 120° C. for 10 minutes, followed by high vacuum for 1 hour and annealing at 160° C. for 10 minutes. One-step annealing at 120° C. gives the best result in test cell, as seen in FIG. 8 , with V oc =0.48V, I sc =0.23 mA, FF=0.44, and a power conversion efficiency (PCE) of 1.2% under AM1.5 solar illumination with intensity 100 mW/cm 2 . The second annealing step at 160° C. worsens the device performance, mainly due to unfavorable change of film morphology, which was confirmed in AFM images (data not shown). The PCE of 1-step annealing at 160° C. was in between that of 1-step annealing at 120° C. and 2-step annealing, yet the device has the worst FF. Table 1 listed the details of the IV characteristics of these three test cells.
[0000]
TABLE 1
Test cell I-V characteristics comparison at various annealing conditions.
Test cell
Annealing
number
I sc (mA)
V oc (V)
FF
η (%)
condition
1
0.28
0.48
0.26
0.86
160° C. 10 min
2
0.23
0.48
0.44
1.2
120° C. 10 min
3
0.16
0.30
0.35
0.43
2-step
[0050] IPCE measurement shows 2-step annealing was worse than 1 step annealing, seen in FIG. 9 , which was consistent with IV measurements (data not shown). There is some inconsistency between PCE and IPCE for the cells annealed at 160° C. and 120° C.: the cell annealed at 160° C. has higher IPCE yet lower PCE than that at 120° C. IPCE measurement was done under illumination from Tungsten lamp, whereas IV was done under solar simulator which has different spectrum than that of the tungsten lamp. Nevertheless, the integration of IPCE should be proportional to Isc. The device made by 1-step annealing at 160° C., though having smaller power conversion efficiency, actually has larger Is, (0.28 mA) than the one at 120° C. (0.23 mA). The ratio between integral of IPCE at 160° C. vs. 120° C. is about 1.3, and the ratio of Isc of the same devices was 1.2. The slight discrepancy might also come from the fact that the cells behave differently under strong (IV) and weak (IPCE) illuminations. Usually bi-molecular (BM) recombination sets in under high light intensity (solar simulator) (Shaheen, Brabec, Sariciftci, Padinger, Fromherz, and Hummelen, Appl. Phys. Lett. 2001, 78, 841) meaning the cell which has more prominent BM recombination will perform poorer with high intensity illumination such as that from the solar simulator. It might be that the cell annealed at 160° C. was affected by BM recombination more than the cell annealed at 120° C., due to more traps associated with rougher morphology serving as recombination centers. Further investigation of this discrepancy is under study.
[0051] AFM images of topography and phase of 4 different test arrays at different annealing conditions; an as-made cell, made using the method of Example 1 without annealing, having a roughness of 7.41 nm, 1-step annealing at 120° C. having a roughness of 6.60 nm, annealing at 160° C. having a roughness of 3.68 nm, and (d) 2-step annealing having a roughness of 9.76 nm. The 1-step annealing at 120° C. showed the improved film roughness and the best phase segregation of P3HT and PCBM, which explains why the device performance was the best, seen in FIGS. 8 and 9 . Device by 2-step annealing has the smoothest film, however, the phase segregation was much less distinct. This indicates that P3HT chains and PCBM molecules are penetrating through each other more after the second annealing at 160° C., and form much smaller nano-domains, which are favorable for charge transport between the domains (Kline and McGehee, Morphology and Charge Transport in Conjugated Polymers. J of Macromol Sci, Part C: Polymer Reviews, 2006, 46(1): 27-45). However, recombination of photogenerated carriers might be enhanced due to the lack of separate pathways for electron sand holes, and that was why the device after 2-step annealing performed worse than after the 1 st annealing at 120° C., seen in FIGS. 8 and 9 . 1-step annealing at higher temperature of 160° C. results in the roughest film (even rougher than the as-made device), and the P3HT phase and PCBM phase are hardly distinguishable. This rough film also further affects the interface between active layer and m-PEDOT, resulting in poor FF of the device, seen in FIGS. 8 and 9 .
[0052] IV analysis was performed on 4 arrays under different annealing conditions measured with AM 1.5 solar illumination, seen in FIG. 10 . It is clear that 1-step annealing at the low temperature, i.e. 120° C., gives the worst result, 2-step annealing showed improved IV characteristics (V oc , J sc , FF and PCE) after the second high temperature annealing at 160° C. 1-step annealing at high temperature, i.e. 160° C., gives the best V oc , and 2-step annealing yields the highest J sc . In terms of anode, m-PEDOT 500 seems to give higher V oc than PEDOT 750, seen in Table 2. However, there is not much difference in PCE between 2-step annealing and 1-step annealing at 160° C., which is in contrast with the result of test device, seen in FIGS. 8 and 9 . It is believed the annealing duration is probably too short for the array, since it has much larger area and contains much more materials.
[0000]
TABLE 2
Array I-V characteristics comparison at various annealing conditions.
Array
Annealing
number
I sc (mA)
V oc (V)
FF
η (%)
condition
m-PEDOT
1
17.0
3.9
0.30
0.68
2 step
750
2
11.5
4.0
0.39
0.62
2 step
750
3
6.30
2.8
0.37
0.22
2 step
750
4
13.0
4.0
0.33
0.56
160° C. 10 min
750
5
15.0
5.2
0.33
0.86
160° C. 10 min
500
6
12.0
5.8
0.30
0.70
160° C. 10 min
500
7
11.1
5.2
0.35
0.67
160° C. 10 min
500
[0053] A very interesting phenomenon which was termed ‘photo annealing’ was observed, as seen in FIG. 11 . Under constant illumination from the solar simulator, a sudden change of IV occurs after certain amount of time which is device dependent, ranging from 10 minutes to several hours. The device takes about 15 minutes, and reaches maximum PCE after 2.5 hours under illumination. The drastic change is mostly Ise, which more than doubles from 17 mA to 35 mA after 2.5 hours. The change of V oc was marginal from 4.0V to 4.2V. The maximum PCE of the array was 1.80%. Table 3 listed the changes of other IV characteristics.
[0000]
TABLE 3
Change of Array IV characteristics under solar illumination.
Time
I sc (mA)
V oc (V)
FF
η (%)
1 st day
0 min
17
4.0
0.30
0.68
12 min
28
4.2
0.35
1.40
150 min
35
4.2
0.37
1.80
2 nd day
0 min
18
4.2
0.35
0.88
[0054] Furthermore, this sudden increase of I sc is also accompanied by a characteristic ‘wiggles’ on the IV curve. This cannot be due to encapsulation related change of light distribution inside the active layer, since these ‘wiggles’ have also been observed with the IV of test devices which are not encapsulated. ‘Wiggles’ only appear with the sprayed OPV device, both array and test device, not with spin-coated device. Without being bound to any specific theory, the phenomenon may be a result of the porosity of sprayed film being much larger than the spin-coated film, and polymer chains have much more loose arrangement in sprayed device, with the heat from solar illumination, the polymer chains relax more and the film nanomorphology was improved, with possibly PCBM penetrating into the voids between polymer chains and causing better phase segregation (Geiser, et al., Poly(3-hexylthiophene)/C 60 heterojunction solar cells: Implication of morphology on performance and ambipolar charge collection. Sol. Eng . & Sol. Cells 2008, 92(4), 464). This effect is similar to thermal annealing performed on hot plate. As temperature drops down, the polymer chains go back to its original configuration, and IV curve is back to its original one, manifesting certain kind of hysteresis. It also might be due to thermal activation of the previous deeply trapped carriers (i.e., polarons), which results in increased photocurrent at higher temperature (Graupner, Leditzky, Leising, and Scherf, Phys. Rev. B 1996, 54, 7610; Nelson, Organic photovoltaic films. Current Opinion in Solid State and Materials Science 2002, 6(1), 87-95). The wiggles indicate the nonuniformity of film morphology, and the overall boost of device performance is the result of ‘photo annealing’.
[0055] This observation is against the conventional picture of organic solar cell, which normally shows degradation under solar illumination (Nelson, Organic photovoltaic films. Current Opinion in Solid State and Materials Science 2002, 6(1), 87-95; Dennler, et al., A new encapsulation solution for flexible organic solar cells. Thin Solid Films 2006, 511-512, 349-53). It was also found out that the performance enhancement under illumination only happened with sprayed devices, not the device made by spin coating. This means that solar cells made with our spray-on technique performs better under sunlight, which is beneficial for solar energy application. Further study of photo annealing dynamics and solar array lifetime is ongoing to unveil the optimal condition for solar array in field operations.
EXAMPLE 6
[0056] A large area organic array was fabricated using the all spay technique described in Example 1. A fully encapsulated 4″×4″ array was prepared and found to have over 30% transparency, with power conversion efficiency (PCE) as high as 1.80% under constant illumination of simulated sunlight. Thermal annealing has proven to be essential to improve device PCE, and the optimal annealing conditions are not the same with small single cell and large solar array consisting of 50 cells. Systematic studies of optical, electronic and morphologic properties of the device reveals the influence of nanomorphology over device power conversion efficiency. Moreover, the discovery of photo annealing, i.e., more than 2-fold increase of solar cell PCE under solar irradiance and with hysteresis pattern, is in contrary to the normal understanding of organic solar cell degradation under sunlight. The fact that photo annealing was only observed with sprayed solar cell or arrays places underscores the novel advantageous solution for large scale, low-cost solution based solar energy applications. Analysis of the device showed that the solar array provided useful device transparency, as seen in FIG. 12 .
[0057] In the preceding specification, all documents, acts, or information disclosed do not constitute an admission that the document, act, or information of any combination thereof was publicly available, known to the public, part of the general knowledge in the art, or was known to be relevant to solve any problem at the time of priority.
[0058] The disclosures of all publications cited above are expressly incorporated herein by reference, each in its entirety, to the same extent as if each were incorporated by reference individually.
[0059] While there has been described and illustrated specific embodiments of an organic photovoltaic cell, it will be apparent to those skilled in the art that variations and modifications are possible without deviating from the broad spirit and principle of the present invention. It is intended that all matters contained in the foregoing description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense. It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described, and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween. | The fabrication and characterization of large scale inverted organic solar array fabricated using all-spray process is disclosed, consisting of four layers; ITO-Cs 2 CO 3 -(P3HT:PCBM)-modified PEDPT:PSS, on a substrate. With PEDPT:PSS as the anode, the encapsulated solar array shows more than 30% transmission in the visible to near IR range. Optimization by thermal annealing was performed based on single-cell or multiple-cell arrays. Solar illumination has been demonstrated to improve solar array efficiency up to 250% with device efficiency of 1.80% under AM1.5 irradiance. The performance enhancement under illumination occurs only with sprayed devices, indicating device enhancement under sunlight, which is beneficial for solar energy applications. The semi-transparent property of the solar module allows for applications on windows and windshields, indoor applications, and soft fabric substances such as tents, military back-packs or combat uniforms, providing a highly portable renewable power supply for deployed military forces. | 7 |
BACKGROUND OF THE INVENTION
For a variety of reasons, it is useful to affix identification labels to tires. For instance, such identification labels could be used to determine the tire's date of manufacture, the plant in which it was built and even the tire building machine on which it was constructed. Identification labels could also be used in tracking the tire through its line of distribution to the ultimate purchaser.
It is important for a tire identification label to be highly durable. This is because it may be important to read the identification label after the tire has been in service on a vehicle for many years. Truck tires are frequently retreaded on multiple occasions and it is important for the identification label to be capable of surviving such retreading operations. It is also important for the identification label to be capable of being easily read. In many cases it will be important for the identification label to be capable of being read by a computer as well as human readable.
Identification labels are a tool which can be used to reduce delays and errors associated with transcribing information. Besides increasing productivity through automated factory sorting, identification labels make it possible to collect more detailed information with greater accuracy and minimal effort.
Conventional systems for affixing labels to tires have proven not to be totally satisfactory. For instance, labels are often affixed to the tread area of tires utilizing standard adhesives. However, such labels are not durable and are not intended to survive pass the point at which the tire is sold to the ultimate customer. Even though current technology exists for permanently affixing identification to tires, such techniques have not been widely implemented. For instance, serial numbers can be molded into tire sidewalls but such a procedure is highly labor intensive and costly. In any case, current technology does not provide an inexpensive means of applying durable identification labels to tires.
SUMMARY OF THE INVENTION
The present invention provides a relatively inexpensive means for permanently affixing identification labels to tires. These identification labels are capable of functioning over the entire life of a tire. These identification labels can contain standard numbers and/or letters which can be visually read by humans. The identification label can also be in the form of a bar code which is capable of being scanned and read by a computer. Another alternative is for the identification label to contain a dot matrix code which can either be read visually by humans or electronically via a computer.
The present invention specifically discloses a method of preparing a pneumatic rubber tire having an outer circumferential tread, a supporting carcass therefor, two-spaced beads, two rubber sidewalls connecting said beads, and a rubber innerliner having an identification label affixed thereto, said process comprising (a) applying the identification label to the rubber innerliner of an uncured tire, wherein the identification label is comprised of about 35 to about 90 weight percent syndiotactic 1,2-polybutadiene having a melting point which is within the range of about 70° C. to about 160° C. and about 10 to about 65 weight percent of at least one polydiene rubber which is cocurable with said syndiotactic 1,2-polybutadiene, sulfur, zinc oxide and at least one pigment or colorant; and (b) curing the tire.
The subject invention further reveals a pneumatic tire having an identification label affixed thereto which is comprised of an outer circumferential tread, a supporting carcass therefor, two-spaced beads, two rubber sidewalls connecting said beads, and a rubber innerliner: wherein the identification label is affixed to the rubber innerliner and wherein the identification label is comprised of from about 35 weight percent to about 90 weight percent syndiotactic 1,2-polybutadiene having a melting point which is within the range of about 70° C. to about 160° C. and from about 10 weight percent to about 65 weight percent of at least one polydiene rubber which is cocured with said syndiotactic 1,2-polybutadiene, and at least one pigment or colorant.
DETAILED DESCRIPTION OF THE INVENTION
In practicing this invention, standard uncured tires are built utilizing normal procedures. Such tires will typically be comprised of an outer circumferential tread, a supporting carcass therefor, two-spaced beads, two rubber sidewalls connecting said beads, and a rubber innerliner. Such tires can be standard black wall tires or decorative white wall tires. In any case, the uncured tire which is utilized is built employing standard procedures which are well known to persons skilled in the art of building tires.
In the practice of this invention, the identification label is affixed to the innerliner of the uncured tire before it is vulcanized (cured). The tire is then cured in a mold utilizing standard curing procedures. It is believed that the syndiotactic 1,2-polybutadiene (SPBD) and the diene rubbers in the identification label cocured with the rubber of the innerliner. In any case, the identification label becomes very strongly and permanently affixed to the tire innerliner. Because the identification label is affixed to the inside of the tire, abrasion of the identification label during normal tire operations is not a problem.
The syndiotactic 1,2-polybutadiene used in the practice of the subject invention normally has more than 65% of its monomeric units in a syndiotactic 1,2-configuration. SPBD can be prepared in an inert organic solvent utilizing the technique described in U.S. Pat. No. 3,901,868 or in an aqueous medium utilizing the process described in U.S. Pat. No. 4,506,031. U.S. Pat. No. 4,506,031 more specifically reveals a process for producing polybutadiene composed essentially of SPBD comprising the steps of:
(A) preparing a catalyst component solution by dissolving, in an inert organic solvent containing 1,3-butadiene (a) at least one cobalt compound selected from the group consisting of (i) β-diketone complexes of cobalt, (ii) β-keto acid ester complexes of cobalt, (iii) cobalt salts of organic carboxylic acids having 6 to 15 carbon atoms, and (iv) complexes of halogenated cobalt compounds of the formula CoX n , wherein X represents a halogen atom and n represents 2 or 3, with an organic compound selected from the group consisting of tertiary amine alcohols, tertiary phosphines, ketones, and N,N-dialkylamides, and (b) at least one organoaluminum compound of the formula AlR 3 , wherein R represents a hydrocarbon radical of 1 to 6 carbon atoms:
(B) preparing a reaction mixture by mixing said catalyst component solution with a 1,3-butadiene/water mixture containing desired amounts of said 1,3-butadiene:
(C) preparing a polymerization mixture by mixing carbon disulfide throughout said reaction mixture, and
(D) polymerizing said 1,3-butadiene in said polymerization mixture into polybutadiene while agitating said polymerization mixture. In the process described therein the crystallinity and melting point of the SPBD can be controlled by adding alcohols, ketones, nitriles, aldehydes or amides to the polymerization mixture.
The SPBD utilized in making the identification labels for tires has a melting point which is within the range of about 70° C. to 160° C. It is generally preferred for the SPBD utilized in making identification labels for passenger car or truck tires to have a melting point which is within the range of about 80° C. to about 150° C. with a melting point which is within the range of 90° C. to 125° C. being most preferred. The melting points referred to herein are the minimum endotherm values determined from DSC (differential scanning calorimetry) curves.
The compositions utilized in making the identification labels of this invention is a blend which is comprised of SPBD and at least one rubber which is cocurable with the SPBD. The rubber used in such blends can be virtually any type of elastomer which contains unsaturation that allows for sulfur curing. Typically, the elastomer will be one or more polydiene rubbers. Some representative examples of suitable polydiene rubbers include cis-1,4-polybutadiene, natural rubber, synthetic polyisoprene, styrene butadiene rubber, EPDM (ethylene-propylene-diene monomer) rubbers, isoprene-butadiene rubbers, and styrene-isoprene-butadiene rubbers. In many cases it will be desirable to utilize a combination of diene rubbers in the blend. For instance, the rubber portion of the blend can be a combination of chlorobutyl rubber, natural rubber, and EPDM rubber. It is particularly preferred to utilize a combination which contains from about 30 weight percent to about 80 weight percent chlorobutyl rubber, from about 15 weight percent to about 55 weight percent natural rubber, and from about 2 weight percent to about 10 weight percent EPDM rubber as the rubber component in such blends. A rubber composition which contains from about 55 weight percent to about 65 weight percent chlorobutyl rubber, from about 25 weight percent to about 45 weight percent natural rubber, and from about 3 weight percent to about 7 weight percent EPDM rubber is more highly preferred.
The blend utilized in preparing the identification labels will normally contain from about 35 weight percent to about 90 weight percent SPBD and from about 65 weight percent to about 10 weight percent elastomers which are cocurable with the SPBD. The inclusion of high levels of SPBD results in better adhesion, abrasion, and tear resistance for the cured material. High levels of SPBD also result in increased green strength and stiffness. Additionally, the use of high levels of SPBD reduces green tack which makes handling easier and allows for stacking without the use of a substrate. However, the incorporation of large amounts of SPBD into the blend also results in reduced flexibility and modulus. Accordingly, for the best balance of overall properties, the blend utilized will contain from about 50 weight percent to about 85 weight percent SPBD and from about 50 weight percent to about 15 weight percent cocurable rubbers. The blends which are most highly preferred will contain from about 65 weight percent to about 80 weight percent SPBD and from about 35 weight percent to about 20 weight percent of the elastomeric component.
The SPBD used in making the blends from which the identification labels are formed is generally incorporated into the blend in powder or pellet form. In other words, the SPBD is in the form of a powder or pellet at the time it is compounded with the rubber component utilized in making the blend of which the identification label is comprised.
The SPBD powder or pellets can be mixed into the rubber component utilizing standard mixing techniques. However, the mixing is normally carried out at a temperature which is at least as high as the melting point of the SPBD being utilized. During the mixing procedure, the SPBD is fluxed into the rubber with additional desired compounding ingredients. Such mixing is typically carried out in a Banbury mixer, a mill mixer or in some other suitable type of mixing device.
In an alternative embodiment of this invention, the blend utilized in preparing the identification label is prepared by inverse phase polymerization. For example, a blend of SPBD with cis-1,4-polybutadiene can be prepared in an organic solvent by inverse phase polymerization. In such a procedure, the cis-1,4-polybutadiene is first synthesized in an organic solvent under solution polymerization conditions. This polymerization can be catalyzed by using a variety of catalyst systems. For instance, a three component nickel catalyst system which is comprised of an organoaluminum compound, a soluble nickel containing compound and a fluorine containing compound can be utilized to catalyze the polymerization. Such a polymerization can also be catalyzed by utilizing rare earth catalyst systems, such as lanthanide systems, which are normally considered to be "pseudo-living". Such rare earth catalyst systems are normally comprised of three components which include (1) an organoaluminum compound, (2) an organometallic compound which contains a metal from Group III-B of the Periodic System, and (3) at least one compound which contains at least one labile halide ion. Metals from Group I and II of the Periodic System can also be utilized as catalysts for polymerizing 1,3-butadiene monomer into cis-1,4-polybutadiene. The metals which are most commonly utilized in such initiator systems include barium, lithium, magnesium, sodium and potassium with lithium and magnesium being the most commonly utilized. The cis-1,4-polybutadiene cement which is synthesized is then subsequently utilized as the polymerization medium for the synthesis of the SPBD. It will generally be desirable to add additional 1,3-butadiene monomer to the cis-1,4-polybutadiene cement for the synthesis of the SPBD. In some cases, it will also be desirable to add additional solvent. The amount of monomer added will be contingent upon the proportion of SPBD desired in the blend being prepared. It will, of course, also be necessary to add a catalyst system to the rubber cement which is capable of promoting a polymerization which results in the formation of SPBD. A detailed description of such catalyst systems is given in U.S. Pat. No. 3,778,424 which is herein incorporated by reference in its entirety.
The blend of SPBD and rubber will also contain other standard rubber chemicals. For instance, such blends will additionally contain sulfur, zinc oxide, and at least one desired colorant or pigment. They will also typically contain other rubber chemicals, such as antioxidants, accelerators, oils, and waxes in conventional amounts. For instance, the SPBD/rubber blend will normally contain from about 0.2 to about 8 phr of sulfur. It is generally preferred for the blend to contain from about 0.5 to 4 phr of sulfur with it being most preferred for such blends to contain from 1 to 2.5 phr of sulfur. A primary accelerator is generally also present at a concentration which is within the range of about 0.1 to about 2.5 phr. It is normally preferred for the primary accelerator to be present at a concentration which is within the range of about 0.2 to about 1.5 phr with it being most preferred for the primary accelerator to be at a concentration of 0.3 to 1 phr. Secondary accelerators will also commonly be utilized at a concentration which is within the range of about 0.02 to about 0.8 phr. Secondary accelerators are preferably utilized at a concentration of 0.05 to 0.5 phr with the utilization of 0.1 to 0.3 phr of a secondary accelerator being most preferred. Such SPBD/rubber blends will typically contain from about 1 to about 10 phr of various processing oils and it is generally preferred for such blends to contain from about 2.5 to about 7.5 phr of processing oils. The SPBD/rubber blend will generally contain from about 25 phr to about 100 phr of various fillers such as clay and/or titanium dioxide. It is normally preferred for such blends to contain from about 40 phr to about 80 phr fillers. It should be noted that titanium dioxide acts as both a filler and a white pigment. Some representative examples of colorants that can be utilized in the SPBD/rubber blend to impart desired colors to the identification labels include diarylid yellow 17, pththalocy blue 15, diarylid orange 13, and perm red 2B (red 48:1).
After the SPBD/rubber blend has been compounded as desired, it is processed into the desired identification label. A wide variety of techniques can be utilized in making the identification label. For instance, desired numbers or letters can be simply cut from a sheet of the SPBD/rubber blend. Such numbers and/or letters can then be affixed to the tire innerliner prior to curing the tire.
In a preferred embodiment of this invention, the identification labels are punched from a film of the SPBD/rubber blend. This can be accomplished by utilizing an electronically activated mechanical punching assembly in which dot matrices are punched from a film or tape of the SPBD/rubber blend and transferred to a strip of uncured innerliner. The uncured innerliner is typically comprised of the same rubber as is used in building the tire being labelled. The innerliner will typically be comprised of a halobutyl rubber, such as chlorobutyl rubber or a bromobutyl rubber. The tape or film from which the dot matrices are punched will typically be from about 5 mils to about 20 mils thick. It is generally preferred for the SPBD/rubber film or tape to have a thickness which is within the range of about 6 mils to about 14 mils with it being most preferred for the film or tape to have a thickness which is within the range of about 8 mils to about 12 mils. The innerliner strip to which the dot matrices are transferred are typically from about 25 mils to about 50 mils thick and are preferably from about 30 mils to about 40 mils thick.
The label strips are preferably affixed to the rubber innerliner of the uncured tire mechanically. However, the identification labels can be manually applied to the rubber innerliner in the inside of the uncured tire mechanically. This can be done by simply pushing the identification label against the innerliner and then subsequently curing the tire under conditions of heat and pressure utilizing normal curing procedures.
The present invention will be described in more detail in the following examples. These examples are merely for the purpose of illustrating the subject invention and are not to be regarded as limiting the scope of the subject invention or the manner in which it can be practiced. Unless specifically indicated otherwise, all parts and percentages are given by weight.
EXAMPLE 1
A SPBD/rubber blend containing 67 weight percent SPBD, 20 weight percent chlorobutyl rubber, 12 weight percent natural rubber and 1 weight percent EPDM rubber, based upon total polymers, was prepared using conventional Banbury mixing procedures for non-productive and productive batches. The SPBD/rubber blend also contained 2.50 phr of processing oils, 1.0 phr of antioxidants, 1.0 phr of stearic acid, 18.3 phr of clay, 35.0 phr of titanium dioxide, 0.067 phr of a blue pigment, 5.0 phr of zinc oxide, 1.2 phr of sulfur, and 1.54 phr of an accelerator. The SPBD utilized in this example had a melting point of 123° C. It should be noted that the SPBD utilized in accordance with this invention is a crosslinking thermoplastic resin. However, SPBD is considered to be a rubber in calculating phr (parts per hundred parts of rubber).
The SPBD/rubber blend was then calendared and slit into rolls of tape. The tape made had a width of about 1.25 inches and had a thickness which was within the range of about 8 mils to about 10 mils. The laboratory calendar was operated utilizing a mill temperature of 270° F., a top roll temperature 265° F., a middle roll temperature of 260° F., and a bottom roll temperature of 80° F. The rolls of tape made had a diameter of 11.5 to 12.0 inches and the tape could be let-off with minimum effort. The rolls of tape made contained approximately 1,000 feet of tape and weighed about 5.7 lbs. Each roll contained enough tape to make about 1,200 labels.
An electronically activated mechanical punching assembly was utilized to punch dot matrices from the SPBD/rubber tape. The dot matrices were transferred to uncured butyl rubber strips. The labels made contained 10 digit numeric codes. Each number was formed by 1/8 inch diameter white dots in a 5×4 array. The numbers were verified after application by a vision scanning/computer interface set-up. The resulting position of the label after the green tire is built is circumferentially inside the tire.
The dot matrix labels were applied to the innerliner of 12 different styles of tires each of which was built in 4 different sizes. These tires were cured utilizing standard factory procedures. The dot matrix codes in the tires were then read. The reader consisted of a line scan camera that was placed inside the center of the tires which were rotated 1.5 turns. The camera, which had an infinite focal length, captured the image of the dot matrices for computer processing. The computer detected the position of each dot in the matrix and decoded it into the corresponding numeral. The reader stations sensed the height and diameter of the tires which controlled the probe depth, centering and light intensities.
The dot matrices uniformly spaced upon tire shaping, cocured to the tire innerliner which provided excellent adhesion, and maintained excellent dot definition after curing. The dot matrix patterns in the tires exhibited good light reflectants for reading by the vision system. In fact, the tires built were read during these trials at an accuracy rate of 99.992 percent. Additionally, the quality and uniformity of the tires built utilizing this procedure was not sacrificed in any way. This example clearly shows that the technique of this invention is an effective and reliable means for permanently affixing identification labels to tires.
EXAMPLE 2
A SPBD/rubber blend containing 80 weight percent SPBD, 12 weight percent chlorobutyl rubber, 7 weight percent natural rubber and 1 weight percent EPDM rubber, based upon total polymers, was prepared using conventional Banbury mixing procedures for non-productive and productive batches. The SPBD/rubber blend also contained 1.50 phr of processing oils, 1.0 phr of antioxidants, 1.0 phr of stearic acid, 11.0 phr of clay, 3.0 phr of titanium dioxide, 0.04 phr of a blue pigment, 5.0 phr of zinc oxide, 1.2 phr of sulfur, and 1.54 phr of an accelerator. The SPBD utilized in this example had a melting point of 87° C. It should be noted that the SPBD utilized in accordance with this invention is a crosslinking thermoplastic resin. However, SPBD is considered to be a rubber in calculating phr (parts per hundred parts of rubber).
The SPBD/rubber blend was then calendared and slit into rolls of tape. The tape made had a width of about 1.25 inches and had a thickness which was within the range of about 8 mils to about 10 mils. The laboratory calendar was operated utilizing a mill temperature of 240° F., a top roll temperature 235° F., a middle roll temperature of 230° F., and a bottom roll temperature of 80° F. The rolls of tape made had a diameter of 11.5 to 12.0 inches and the tape could be let-off with minimum effort. The rolls of tape made contained approximately 1,000 feet of tape.
The method of preparing the labels and affixing to the tires are the same as discussed in Example 1.
SPBD imparts properties to green rubber that are desirable for improved handling characteristics for in mold applied white sidewall rings. The addition of SPBD having a melting point of 123° C. or 87° C. at any level results in reduced tack, increased stiffness, and increased static modulus for green stocks. In this series of experiments, various levels of SPBD were blended with a rubber blend containing 60% chlorobutyl rubber, 35% natural rubber and 5% EPDM rubber. The physical properties of the uncured SPBD/rubber films made are reported in Table I.
TABLE I______________________________________Example 1 2 3______________________________________SPBD Level 67 80 0SPBD MP 123° C. phr 67 -- --SPBD MP 87° C. phr -- 80 --Physical Properties for Green FilmTensile, psi 1400 1900 145Elongation, % 510 660 >90050% Modulus, psi 750 600 65Crescent Tear, ppi 260 295 --______________________________________
Example 3 was done as a control and did not include any SPBD. Tensile strength and elongation were determined by ASTM D-412. Crescent tear was determined by ASTM D-1004. As can be seen, the incorporation of SPBD into the rubber blend yields high green strength and stiffness without the need for precure.
While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without departing from the scope of the subject invention. | For a wide variety of reasons, it would be desirable to affix identification labels, such as serial numbers, to tires. Such labels should be capable of lasting the entire life of the tire which may include being retreaded on multiple occasions. From a commercial standpoint, it is also very important for the label and the means of affixing it to the tire to be inexpensive. This invention discloses such a technique for affixing identification labels to tires. This information specifically relates to a method of preparing a pneumatic rubber tire having an outer circumferential tread, a supporting carcass therefor, two-spaced beads, two rubber sidewalls connecting said beads, and a rubber innerliner having an identification label affixed thereto, the process including the steps of (a) applying the identification label to the rubber innerliner of an uncured tire, wherein the identification label contains about 35 to about 90 weight percent syndiotactic 1,2-polybutadiene having a melting point which is within the range of about 70° C. to about 160° C. and about 10 to about 65 weight percent of at least one polydiene rubber which is cocurable with the syndiotactic 1,2-polybutadiene, sulfur, zinc oxide and at least one pigment or colorant; and (b) curing the tire. Labels containing virtually any type of information can be affixed utilizing this technical. For instance, the identification labels can include conventional numbers and/or letters, computer readable dot matrix identification, or a bar code. | 1 |
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a method for forming wells in a high density semiconductor device, and more particularly to a method for effectively forming wells in a semiconductor device by eliminating a high-energy ion-implantation process.
[0002] Conventional methods for forming a well in a high integration semiconductor device can be greatly divided into two types as follows.
[0003] The first method is to form a well which has a doping profile of uniform density by diffusing ion implanted dopant to an appropriate depth at high temperatures for an extended period of time. This type of well is called a diffused well due to diffusion of impurities.
[0004] The improved process of a diffused well with respect to process simplification is disclosed in U.S. Pat. No. 4,889,825, entitled “High/Low Doping Profile for Twin Well Process” by Louis et al. This is a method for simplifying a photo mask process for a plurality of ion-implantation processes, for example, a well ion-implantation process, a field ion-implantation process, a channel ion-implantation process, and a counter doping ion-implantation process. However, this method also requires a diffusion process at high temperatures and for an extended period of time, and accordingly has various problems.
[0005] The second method is to simplify processes by eliminating a process of heat treatment from the aforesaid diffused well processes, wherein a retrograde well using a high-energy ion-implantation process is proposed. The retrograde well shows a peak value of impurities concentration at a particular depth inside a silicon substrate. When the retrograde well is adjacent to the surface of the substrate, impurities concentration falls.
[0006] Methods for forming the retrograde well are disclosed in U.S. Pat. No. 4,633,289, entitled “Latchup Immune, Multiple Retrograde Well High Density CMOS FET”, and in a paper written by Toshiyuki Nishihara et al in IEDM88, pp.100-103, 1988.
[0007] Referring to FIGS. 1A through 1C, a conventional method for forming a retrograde well can be described as follows.
[0008] First, field oxide film 12 is formed on a semiconductor substrate 10 through a conventional device isolation process as shown in FIG. 1A. Next, referring to FIG. 1B, a well of a first conductivity type 14 is formed by well implantation, a field implant region 16 is formed by field ion-implantation, and a channel implant region 18 is formed by channel ion-implantation, all of which are formed by using predetermined mask pattern 13 . Subsequently, referring to FIG. 1C, a well of a second conductivity type 24 , a field implant region 26 , and a channel implant region 28 are formed by using mask pattern 23 in the same manner as those in FIG. 1C, thereby forming a twin-well.
[0009] The graph in FIG. 2 is a doping profile showing the impurities concentration corresponding to the distance from the surface of a retrograde well formed through the aforesaid processes.
[0010] Referring to FIG. 2, a retrograde well of a P-well shows the impurities concentration at W where well ion-implantation of boron is performed at a high-energy level of approximately 700˜800 KeV, and at F where field ion-implantation of boron is performed at an approximately 130˜300 KeV. Point C indicates the impurities concentration at the depth where channel ion-implantation of boron fluoride (BF 2 ) is performed, for controlling the threshold voltage of a metal oxide silicon (MOS) transistor, at an energy level of approximately 40˜60 KeV. In the case of an N-well, after field ion-implantation, a process of high concentration ion-implantation is additionally performed so as to enhance the punchthrough characteristics of a PMOS transistor.
[0011] In the retrograde well processes, the well ion-implantation W restrains latchup and soft errors; and the field ion-implantation F not only determines device isolation characteristics but also has an effect on the active region in which transistors are formed, accordingly leading to a change in the electrical characteristics of transistors.
[0012] This retrograde well formed by high-energy ion-implantation serves to reduce process costs by eliminating the diffusion process at high temperatures and for an extended period of time, and further enhances the electrical characteristics of a device by restraining latchup and soft errors. However, these are poor advantages with respect to the increased production costs the process hours required in the manufacturing of a high-energy ion-implantation device.
[0013] The higher integration of the device leads to more manufacturing complications, thereby requiring more hours for the manufacturing process. A retrograde well process, which is derived from the conventional diffused well process, applied to a well formation process of 16M DRAM, accordingly shortens process hours. However, it takes about 62 days in the manufacturing of the 16M DRAM.
[0014] Therefore, the present invention proposes an advanced well process for shortening the process hours and enhancing production through process simplification, which facilitates in maintaining a balance in the characteristics and yield rate of a device by optimizing the retrograde well process of a 16M DRAM.
SUMMARY OF THE INVENTION
[0015] It is an object of the present invention to provide a method for forming a well in a semiconductor device which simplifies processes and enhances production without lowering the operational characteristics of a semiconductor device and the reliability thereof.
[0016] To accomplish the above object of the present invention, there is provided a method for forming a well in a high integrated semiconductor device without performing a high-energy well ion-implantation process wherein wells for forming transistors of a predetermined conductivity type are formed by a field ion-implantation process functioning as both a punchthrough stopper and a channel stopper.
[0017] Preferably, the method for forming wells of a second conductivity type, in which MOS transistors having a channel of a first conductivity type are to be formed, uses a field ion-implantation process performing both the functions of a punchthrough stopper and a channel stopper without a high-energy well ion-implantation process, and performs an ion-implantation process so that a well region formed by the field ion-implantation process has a depth if approximately 1.0 μm or less.
[0018] To accomplish the above object of the present invention, there is provided a method for forming a well in a complementary MOS (hereinafter called a CMOS) comprising the steps of: preparing a semiconductor substrate of a second conductivity type; forming a field oxide film for limiting the active region of the semiconductor substrate; forming a mask pattern on one side of the active region isolated by the field oxide film; forming a well of a first conductivity type wherein a field ion-implantation process is performed by ion-implantation at an energy level and dose selected for functioning as both a punchthrough stopper and a channel stopper, thereby forming transistors having the same type of channel as the substrate; and forming a well of a second conductivity type wherein a field ion-implantation process is performed using a mask having an opposite pattern to the mask used in the previous step and using a selected ion-implantation energy level, a selected dose, and a selected dopant without a high-energy ion-implantation process for retrograde well peak, thereby forming transistors having a channel of the conductivity type opposite to that of the substrate.
[0019] Preferably, the semiconductor substrate consists of silicon of orientation (100), impurities of the first conductivity type consists of phosphorus or arsenic, and impurities of the second conductivity type consists of boron. Here, it is preferable to form well regions of the first and second type within approximately 1.0 μm deep from the surface of the semiconductor substrate.
[0020] Further, to form the wells of the first conductivity type, it is preferable to have ranges of the selected-energy level between 350˜400 KeV and the selected dose between 7.0E12˜1.0E13 ions/cm 2 .
[0021] Meanwhile, to form the well of the second conductivity type, it is possible to use an energy level between 110˜160 KeV and a dose between 3.0E12˜5.0E12 ions/cm 2 .
[0022] According to conventional methods, a retrograde well had been formed by implementing a plurality of ion-implantation processes, for example: processes of well ion-implantation for deep well peak; field ion-implantation for enhancing a characteristic of device isolation; ion-implantation in forming a well for stopping punchthrough having a conductivity type opposite the substrate; and channel ion-implantation for controlling threshold voltage V th , particularly in which the ion-implantation process had used a high-energy level of more than 800 KeV. However, according to the present invention, wells which perform functions of both a punchthrough stopper and a channel stopper can be formed by implementing only a field ion-implantation process using an energy level of less than 400 KeV. Furthermore, in a test of a device produced by the improved well process according to the present invention, it was revealed that there was little difference in the reliability of this device and that of a “normal” device manufactured by the conventional method. Therefore, it is possible to simplify processes and to enhance production without lowering the operational characteristics of a device and the reliability thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] The above objects and advantages of the present invention will become more apparent by describing in detail a preferred embodiment thereof with reference to the attached drawings in which:
[0024] [0024]FIGS. 1A, 1B and 1 C are cross-sectional views of for illustrating the processes used in a method of forming a conventional retrograde well;
[0025] [0025]FIG. 2 is a doping profile showing impurities concentration corresponding to the distance from the surface of a conventional retrograde well;
[0026] [0026]FIGS. 3A through 3D are cross-sectional views illustrating the processes wherein an improved well process according to the present invention is applied to a CMOS device;
[0027] [0027]FIG. 4A is a doping profile showing impurities concentration corresponding to the distance from the surface of a well according to the present invention;
[0028] [0028]FIG. 5 is a graph comparing and analyzing a body effect of P-MOS transistors produced by the conventional method and the present invention.
[0029] [0029]FIG. 6 is a graph comparing and analyzing a body effect of N-MOS transistors produced by the conventional method and the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0030] An improved method for forming a well according to the present invention proposes to obtain the same characteristics as those of the retrograde well by simplifying the complicated manufacturing process, and can be particularly applied to the manufacturing of high density CMOS.
[0031] [0031]FIGS. 3A through 3D are cross-sectional views in turn illustrating the processes wherein the method for forming a well according to the present invention is applied to a CMOS having twin wells.
[0032] [0032]FIG. 3A shows a step of forming a field oxide film 32 for limitting the active region on a prepared semiconductor substrate 30 . Semiconductor substrate 30 uses P-type silicon doped with boron at a concentration of 1.5×10 15 cm −3 and a crystal orientation is (100). It is preferable to form field oxide film 32 to a thickness of approximately 4,500 Å using the conventional selective poly oxidation method (SEPOX). In order to eliminate a white ribbon phenomenon from being generated in forming field oxide film 32 , a secondary sacrificial oxide film of thickness 500 Å can be formed at the surface of substrate 30 by thinly oxidizing it through thermal oxidation, which is not shown in FIG. 3A. Further, field oxide film 30 can also be formed using the conventional local oxidation of silicon method (LOCOS).
[0033] [0033]FIG. 3B shows a step of forming N-well 34 wherein a P-field ion-implantation process is performed by using mask pattern 33 .
[0034] First, mask pattern 33 is formed on an active region of one side isolated by field oxide film 32 . For example, photoresist is coated on the whole surface of substrate 30 , and then exposed and developed, thereby forming first photoresist pattern 33 on a region of substrate 30 leaving the region expoaed where N-well 34 is to be formed.
[0035] Next, a P-field ion-implantation process is performed at a predetermined ion-implantation energy and dose, with first photoresist pattern 33 as a mask. Here, the ion-implantation energy and dose are selected so as to simultaneously perform functions of both a punchthrough stopper and a channel stopper without lower the latchup characteristic.
[0036] An improved N-well formation process according to the present invention makes it easier to control the depth (D) of the P-field ion-implantation region 34 of a well region within 1.0 μm, with an energy level in the range of approximately 350˜400 KeV with an impurity concentration and dose in the range of 7.0E12˜1.0E13 ions/cm 2 without lowering characteristics.
[0037] [0037]FIG. 4 is a vertical doping density profile of a well through one-dimensional simulation, after performing the P-field ion-implantation process. A conventional retrograde well has two peaks as shown in FIG. 2, but a well according to the present invention has one peak. The depth, d, of a conventional retrograde well 24 (FIG. 1C) is approxiamtely 2 μm, while the depth, D, of an improved well 34 (FIG. 3B) can be formed to a thinness of 1 μm or less. Therefore, a high-energy well ion-implantation process of approximately 800 KeV and an additional ion-implantation for punchthrough stop can be eliminated.
[0038] A channel ion-implantation process can for controlling the transistor voltage V th can be added to N-well 34 where a p-channel MOS transistor is to be formed. Each process condition is determined in accordance with the characteristics of the unit device.
[0039] [0039]FIG. 3C shows a step of forming P-well 44 where an n-channel MOS transistor is to be formed. A photoresist is coatded on the whole surface of substrate 30 , after eliminating first photoresist pattern 33 , and then exposed and developed, thereby forming a second photoresist pattern 43 on the substrate wherein the N-well is formed. Here, second photoresist pattern 43 is formed thick as to prevent penetration into N-well 34 in the ion-implantation for forming a P-well.
[0040] P-well 44 having a junction depth of less than 1.0 μm can be formed by performing an N-field ion-implantation with boron, for example, at an energy level of 140 KeV at a concentration of 3.5E12 ions/cm 2 using the mask mask of the second photoresist pattern 43 P-type impurities, going through a high-energy ion-implantation process for retrograde well peak. To control the threshold voltage of an N-MOS transistor, boron fluoride (BF 2 ) under the conditions of 40˜60 KeV and 1.0E12/cm 2 can be ion implanted.
[0041] [0041]FIG. 3D shows a step of respectively forming a p-channel MOS transistor and an n-channel MOS transistor on N-well 34 and P-well 44 , respectively. After eliminating second photoresist pattern 43 , gate oxide film 35 and gate polysilicon 37 are formed by using a photographic etching process Then p + source/drain region 39 of P-MOS and n + source/drain region 49 of N-MOS are formed, respectively. the succeeding processes are performed in the same manner as that performed in a conventional CMOS process.
[0042] The well ion-implantation process can be skipped in the above embodiment regardless of conductivity types, but can be used according to the various types of transistor to be made.
[0043] Accordingly, in forming N-well 34 having a conductivity type opposite substrate 30 , a retrograde N-well is formed by first high-energy ion-implantation of 800 KeV at a dosage of 1.0E13/cm 2 , subsequently by a second ion-implantation of 300 KeV and 5.0E12/cm 2 , The first ion-implantation is performed so as to control the peak concentration of the well and the second is performed so as to achieve the function of a channel stopper in an isolated region. In forming P-well 44 having the same conductivity type as that of substrate 30 , the electrical characteristics of the device can be obtained by optimizing the conditions of the N-field ion-implantation without going through a high-energy well ion-implantation process.
[0044] However, these processes can be performed by skipping only the N-well ion-implantation process. A person skilled in the art can understand that this can be applied to not only a CMOS but also to a unit device.
[0045] Tests concerning the reliability of the method for forming a well according to the present invention shows the following results.
[0046] First, optimization can be obtained by splitting the field ion-implantation process. With the elimination of the P-well ion-implantation process, optimization is achieved by selecting the N-field ion-implantation according to the threshold voltage of the N-MOS and results from comparing and analyzing the threshold voltage, device isolation, and punchthrough characteristics between a P-MOS produced by splitting the P-field ion-implantation process conditions due to the N-well skipping and a P-MOS produced by a method of a normal retrograde well formation.
[0047] The reliability of the electrical characteristics of devices with wells produced by a conventional method and the method according to the present invention, respectively, can be shown in FIGS. 5 and 6, which are graphs summarizing the measured body effect. The body effect is an indication of the change in the threshold voltage, V th , according to varying back bias voltages V BB supplied to the substrate, the change of the back bias voltage V BB simplifies control of the threshold voltage of the transistor and reduces contact capacitance, thereby monitoring the operation characteristics of a device. FIG. 5 shows an analysis of the body effect of splitting the P-MOS transistors according to back bias voltage V BB , in which the solid line indicates the characteristics of a transistor according to a conventional method and the dotted line according to the present invention. FIG. 6 shows the body effect on an N-MOS transistor.
[0048] As shown in FIGS. 5 and 6, the present invention shows almost the same result as that of a conventional method. Accordingly, it shows that the change of bulk concentration in skipping a high-energy well ion-implantation process has little effect on the characteristics of a unit device on the silicon surface.
[0049] In Table 1 the latchup characteristics are shown for different process conditions, wherein group A eliminates the P-well ion-implantation process, group B shows a conventional method of retrograde well formation and group C eliminates both ion-implantation processes of the N-well and the P-well.
TABLE 1 LATCHUP GROUP CHARACTERISTICS REMARKS A 9.13 V P-well skip B 9.07 V normal C 8.77 V N-, P-well skip
[0050] As shown in Table 1, the difference according to split is hardly noticeable and the latchup characteristics can be stabilized by optimizing the field ion implatation process condition according to the elimination of well ion-implantation.
[0051] Accordingly, proper control of the process condition for optimizing the electrical characteristics of a device ensures stabile reliability.
[0052] Therefore, the method for forming a well according to the present invention simplifies processes and enhances production without lowering the operational characteristics and reliability of a semiconductor device.
[0053] The present invention is not limited to the above examples and many other variations may be available to those skilled in this art. | A well ion-implantation process using an energy level equal to or lower than 400 KeV, instead of an energy level equal to or greater than 800 KeV, forms a well which functions as both a punchthrough stopper and a channel stopper and has few differences as compared to that of a device manufactured according to a conventional method, and, therefore, facilitates to simplify processes and enhance production without lowering the operational characteristics and reliability of a semiconductor device. | 7 |
FIELD OF THE INVENTION
[0001] The present invention relates to carbon based materials that are employed for hydrogen storage applications. The material may be described as the pyrolysis product of a molecular precursor such as a cyclic quinone compound. The pyrolysis product may then be combined with selected transition metal atoms which may be in nanoparticulate form, where the metals may be dispersed on the material surface. Such product may then provide for the reversible storage of hydrogen. The metallic nanoparticles may also be combined with a second metal or metal alloy to further improve hydrogen storage performance.
BACKGROUND OF THE INVENTION
[0002] The general requirements for improving hydrogen (H 2 ) storage within a solid medium include appropriate thermodynamics (favorable sorption-desorption enthalpies), relative fast kinetics (i.e. relative fast uptake and/or release), high storage capacity, effective heat transfer, high gravimetric and volumetric densities (e.g. relatively light in weight and conservative in space). Other desirable characteristics may include relatively long cycle lifetimes, adequate mechanical strength and durability. Solid storage (e.g. in metal hydrides) has shown some promise, but the demand for more efficient systems remains an on-going consideration. The U.S. Department of Energy has nonetheless established a multi-stage target for hydrogen storage capacity with respect to fuel cell applications. The targets for such hydrogen storage systems are about 4.5% by weight (wt.) by 2007, 6.0% (wt.) by 2009 and 9.0% (wt.) by 2015.
SUMMARY
[0003] In a first exemplary embodiment, the present disclosure relates to a method for forming a material for hydrogen storage by first supplying a cyclic quinone compound containing at least two ketone groups, wherein the quinone compound includes at least one metal alkoxide salt and optionally a halogen atom, wherein the quinone compound has a thermal degradation temperature. This may then be followed by pyrolyzing the cyclic quinone compound in air to a temperature that is within ±20° C. of the thermal degradation temperature to provide a pyrolysis product. This then may be followed by incorporating into the pyrolysis product metallic nanoparticles having a diameter of 1 nm to 100 nm wherein the metallic nanoparticles comprise one of Ti, V, Fe, Ni, Cu, Ru, Rh, Pd, Sn, Sb, W, Re, Pt, or Au. The pyrolysis product containing the metallic nanoparticles is capable of sorbing hydrogen at levels of 0.1 to 2.5 weight percent at temperatures of 20° C. to 30° C. at hydrogen pressures of 1-5 bars.
[0004] In a second exemplary embodiment, the present disclosure again relates to a method for forming a material for hydrogen storage by first supplying a cyclic quinone compound containing at least two ketone groups, wherein the quinone compound includes at least one metal alkoxide salt and optionally a halogen atom, wherein the quinone compound has a thermal degradation temperature. This may then be followed by pyrolyzing the cyclic quinone compound in air to a temperature that is within ±20° C. of the thermal degradation temperature to provide a pyrolysis product. This then may be followed by incorporating into the pyrolysis product metallic nanoparticles having a diameter of 1 nm to 100 nm wherein the metallic nanoparticles comprise one of Ti, V, Fe, Ni, Cu, Ru, Rh, Pd, Sn, Sb, W, Re, Pt, or Au in combination with a second metal or metals as an alloy selected from B, Al, V, Fe, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, or Bi. The pyrolysis product containing the metallic nanoparticles and the second metal is capable of sorbing hydrogen at levels of up to and including 10 percent by weight, at hydrogen pressures of 1-80 bars and temperatures of 20° C. to 30° C.
[0005] In a third exemplary embodiment, the present disclosure relates to a hydrogen storage material comprising a pyrolysis product of a cyclic quinone compound containing at least two ketone groups, wherein the quinone compound includes at least one metal alkoxide salt and optionally a halogen atom. Metallic nanoparticles are distributed in the pyrolysis product, the nanoparticles having a diameter of 1 nm to 100 nm wherein the metallic nanoparticles comprise one of Ti, V, Fe, Ni, Cu, Ru, Rh, Pd, Sn, Sb, W, Re, Pt, or Au. The pyrolysis product containing the metallic nanoparticles is capable of sorbing hydrogen at levels of 0.1 to 2.5 weight percent at temperatures of 20° C. to 30° C. at hydrogen pressures of 1-5 bars.
[0006] In a fourth exemplary embodiment, the present disclosure relates to a hydrogen storage material comprising a pyrolysis product of a cyclic quinone compound containing at least two ketone groups, wherein the quinone compound includes at least one metal alkoxide salt and optionally a halogen atom. The pyrolysis compound also includes metallic nanoparticles having a diameter of 1 nm to 100 nm wherein the metallic nanoparticles comprise one of Ti, V, Fe, Ni, Cu, Ru, Rh, Pd, Sn, Sb, W, Re, Pt, or Au, in combination with a second metal or metals as an alloy selected from B, Al, V, Fe, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, or Bi. The pyrolysis product containing the metallic nanoparticles is capable of sorbing hydrogen at levels of up to and including 10 percent by weight, at hydrogen pressures of 1-80 bars and temperatures of 20° C. to 30° C.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] Various features and advantages of the present disclosure may be better understood by reading the following detailed description, taken together with the drawings wherein:
[0008] FIG. 1 illustrates the air pyrolysis of sodium chloroanilate, otherwise known as 2,5-dichloro-3,6 dihydroxy-p-benzoquinone disodium salt, to provide a graphite oxide-like product which contains graphene layers.
[0009] FIG. 2 illustrates the general scheme for incorporating metallic nanoparticles, optionally with a second metal component, in the pyrolysis product of a cyclic quinone compound.
[0010] FIG. 3 provides X-ray diffraction data for the pyrolysis product of chloroanilate disodium salt, the pyrolysis product of chloroanilate disodium salt in combination with Pd nanoparticles (˜10 nm), and the pyrolysis product of chloroanilate disodium salt in combination with Pd nanoparticles (˜10 nm) in combination with Hg (Pd—Hg).
[0011] FIG. 4 provides infrared (IR) spectra of the pyrolysis product of chloroanilate disodium salt, the pyrolysis product of chloroanilate disodium salt in combination with Pd nanoparticles (˜10 nm), and the pyrolysis product of chloroanilate disodium salt in combination with Pd nanoparticles (˜10 nm) in combination with Hg (Pd—Hg).
[0012] FIG. 5A provides a high resolution transmission electron micrograph and the electron diffraction patterns (insert) of the pyrolysis product of a chloroanilate disodium salt.
[0013] FIG. 5B provides the high resolution transmission electron micrograph of the pyrolysis product of chloroanilate disodium salt in combination with Pd nanoparticles (˜10 nm).
[0014] FIG. 5C provides the high resolution electron micrograph of the pyrolysis product of chloroanilate disodium salt in combination with Pd nanoparticles (˜10 nm) in combination with Hg (Pd—Hg).
[0015] FIG. 6 illustrates the N 2 sorption/desorption isotherms at 77° K of: (a) Pd nanoparticles (˜10 nm); (b) the pyrolysis product of a choloroanilate disodium salt; (c) the pyrolysis product of chloroanilate disodium salt in combination with Pd nanoparticles (˜10 nm); (d) the pyrolysis product of chloroanilate disodium salt in combination with Pd nanoparticles (˜10 nm) in combination with Hg (Pd—Hg).
[0016] FIG. 7 provides the hydrogen sorption isothermal measurements at room temperature (298° K) for the pyrolysis product of a chloroanilate disodium salt and for such salt in combination with Pd nanoparticles (˜10 nm).
[0017] FIG. 8 indicates the sorption isothermal measurements at room temperature (298° K.) for the pyrolysis product of the chloroanilate disodium salt in combination with Pd—Hg, where the Pd is present at 80% by weight, Hg at 20% by weight, with respect to the pyrolysis product of the chloroanilate disodium salt.
DETAILED DESCRIPTION
[0018] The present disclosure is directed at the use of a graphite oxide-like derivative for hydrogen storage that may be derived from a graphite oxide-like precursor, which precursor may specifically amount to a metallic salt of a cyclic quinone ring compound. That is, one may utilize a cyclic ring compound, containing at least two ketone groups within the ring structure, which ring structure also includes one or more alkoxide metal salt functionalities. The cyclic quinone ring may optionally include one or more halogen atoms. For example, one may utilize the following compound
[0000]
[0000] wherein X may be a halogen (e.g. Cl or Br) and M + is reference to a metal cation, which may include, e.g., Na + , Li + or K + . As can be seen from the above, the cyclic quinone ring compound as illustrated contains two alkoxide salt functionalities (—C—O − M + ) on the indicated quinone ring structure
[0019] In addition, while a 6-membered ring is specifically illustrated above, it should be understood that the present disclosure applies to other types of quinone ring compounds, such as an 8-membered quinone ring. In addition, it is contemplated herein that one may also utilize fused ring quinones, e.g., quinones of the formula:
[0000]
[0000] Moreover, it should be noted that the number of fused quinone rings, while illustrated above at 3, may include fused ring quinone ring structures with ring numbers of 2 to 6. It may therefore now be noted that in a particular preferred embodiment, the cyclic quinone compound suitable for use as the graphite oxide-like precursor herein may have the following particular structure:
[0000]
[0000] which may also be recognized as the chloroanilate disodium salt of hydroquinione, with an empirical formula C 6 Cl 2 Na 2 O 4 .
[0020] It may then be noted that pyrolysis (heating) in air of the cyclic quinone salts, at temperatures that are at or within ±20° C. of the salt decomposition temperature, which in the case of the chloroanilate disodium salt, is about 290° C., will provide a graphite oxide-like material which then uniquely serves as the platform substrate for incorporation of various metals to provide for hydrogen storage capability. Accordingly, the decomposition temperature herein may be understood as that temperature where the cyclic quinone ring and/or the substituents covalently attached thereto undergo bond breaking and reformation. That is, upon pyrolysis, a graphite oxide-like product may be formed, which typically contains relatively small regions of graphene layers, thereby providing porosity, where a graphene layer may be understood as a single layer of graphite structure. A graphite structure herein is understood as multiple layers of hexagonally configured carbon atoms. In addition, functional groups such as —COOH, —C═O and —OH may be individually or collectively observed at the periphery of the layers.
[0021] FIG. 1 sets forth one general sequence for conversion of the preferred cyclic quinone compound, the chloroanilate disodium salt of hydroquinone, to the graphite oxide-like structure herein containing the illustrated bundles of graphene layers (which may also be understood as lamellae phase crystallites). Accordingly, in the case of the chloroanilate disodium salt of hydroquinone, pyrolysis may be carried out at a temperature of 300° C. in air for a period of about 2.0 hours and the obtained graphite oxide-like material may then be washed with water and an organic solvent (e.g. acetone) and dried for about 24 hours at 65° C.
[0022] Aside from the above, it is to be noted that the preferred technique to describe the pyrolysis products of cyclic quinone compound herein, is to do so with a consideration of the following characteristic parameters, as the assignment of a precise empirical compositional formula is currently considered to be relatively difficult and may fall short of properly describing the actual pyrolysis reaction product. Accordingly, the pyrolysis product of the cyclic quinone compound may be effectively characterized as one having a BET surface area in the range of 250 m 2 /g to 2500 m 2 /g, including all values and increments, at a variation of 1.0 m 2 /g. For example, the BET surface area may be about 400 m 2 /g to 600 m 2 /g. One particularly useful BET surface area was found to be about 510 m 2 /g. In addition, the pyrolysis product of the cyclic quinone compounds herein may be further defined as having a pore volume of 0.40 to 4.50 cm 3 /g, including all values and increments therein, at 0.1 cm 3 /g variation and a percent porosity of 30% to 99%. Furthermore, via electron paramagnetic resonance (EPR) analysis it was determined that the pyrolysis product of the cyclic quinone compounds herein had 90% or more of the EPR signal indicating the presence of unshared electrons (free radicals).
[0023] The pyrolysis product of the cyclic quinone compounds may then be combined with a first metal component, such as metallic nanoparticles. See FIG. 2 . In particular, the metallic nanoparticles may be configured such that they are dispersed on the surface of the pyrolysis product of the chloroanilate disodium salt. Suitable metallic nanoparticles may include Ti, V, Fe, Ni, Cu, Ru, Rh, Pd, Sn, Sb, W, Re, Pt, and/or Au. The nanoparticles may also be specifically incorporated into the exemplary chloroanilate disodium salt pyrolysis product in combination with a second metal or metals, as an alloy selected from B, Al, V, Fe, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, and/or Bi. The metallic nanoparticles (e.g. Pd or Pt) may therefore be initially present at a size of 1 nm to 100 nm, including all values and increments therein, in 1 nm variation. The level of metallic nanoparticles, either alone or in combination with a second metal or metals, which for incorporation into the chloroanilate disodium salt graphite oxide pyrolysis product, may be in the range of 5 percent by weight to 25 percent by weight, including all values and increments therein, at 1.0 percent by weight variation. Furthermore, the relative ratio of the metallic nanoparticles to the second metal or metals may be at a level of 10:1 to 1:10. For example, one may utilize 10 parts of Pd to 1 part of Hg, and vice versa.
[0024] It has been found that the use of the chloroanilate disodium salt pyrolysis product, in combination with, e.g. a nanoparticle of Pd, sorbs up to about 2.1 weight percent of hydrogen at room temperature and at hydrogen pressures of about 3 bar. In addition, such sorption of hydrogen may be readily released by desorption in which case the system provides a storage and release medium for delivery of hydrogen. Accordingly, in the broad context of the present disclosure, it may be appreciated that one may provide the pyrolysis product of a cyclic quinone ring compound, incorporate one or more of the metallic elements Ti, V, Fe, Ni, Cu, Ru, Rh, Pd, Sn, Sb, W, Re, Pt, and/or Au in nanoparticle form (1 nm to 100 nm), which then provides for the ability to releasably sorb hydrogen (H 2 ) at levels of 0.1-2.5 weight percent, at temperatures of 20° C. to 30° C., and at hydrogen pressures of 1-5 bars. In addition, upon desorption, the pyrolysis product containing the indicated metallic nanoparticles is in effect regenerated so that it may be repeatedly cycled for the corresponding release of hydrogen as may be contemplated for a particular “hydrogen-on-demand” application.
[0025] However, quite apart from the above hydrogen storage capability, it was next established that by alloying, e.g. Pd, with a second metal as noted above (e.g. Hg), followed again by combination with a pyrolysis product of a cyclic quinone ring compound, one provided what appears to be another entirely new metal-carbon system, indicating hydrogen storage values at levels of at least 8.0-10.0 percent by weight at room temperature and hydrogen pressures of up to and including 80 bars. Accordingly, in the broad context of the present disclosure, the pyrolysis products herein, combined with one or more metallic nanoparticles selected from the group consisting of Ti, V, Fe, Ni, Cu, Ru, Rh, Pd, Sn, Sb, W, Re, Pt, and/or Au, in combination with a second metal or metals as an alloy selected from the group consisting of B, Al, V, Fe, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, and/or Bi, can provide for the reversible sorption and desorption of hydrogen, at levels between 0.1 percent to 10 percent by weight, at hydrogen pressures of 1-80 bars, at temperatures of 20° C. to 30° C.
[0026] Reflecting back upon the earlier discussion regarding DOE targets, it should be immediately apparent that such metal-carbon system herein already exceeds the DOE target of providing a solid material storage composition of hydrogen of 6.0 weight percent by 2008, and is nearly close to the DOE target of 9.0 percent by weight for 2009. That being the case, it may be appreciated that the metal-carbon system herein may provide for a relatively low-cost solid state hydrogen uptake with hydrogen uptake values for a solid phase system that may now satisfy requirements for use within the transportation industry.
[0027] Attention is next directed to FIG. 3 , which provides the X-ray diffraction data for the pyrolysis product of chloroanilate disodium salt, the pyrolysis product of chloroanilate disodium salt in combination with Pd nanoparticles (˜10 nm), and the pyrolysis product of chloroanilate disodium salt in combination of Pd nanoparticles (˜10 nm) in combination with Hg (Pd—Hg). As can be seen, the pattern of the pyrolysis product of chloroanilate disodium salt in combination with Pd nanoparticles shows relatively sharp reflections apparently due to the presence of the Pd nanoparticles on the underlying graphite oxide-like substrate. The pyrolysis product of chloroanilate disodium salt in combination with Pd nanoparticles with Hg showed identical structure to the mineral potarite (Pd—Hg), which contains about 65.34 weight percent Hg and about 34.66 weight percent Pd. Reference herein to nanoparticles of ˜10 nm is reference to the feature that the nanoparticle size may vary ±2 nm for a given sample.
[0028] Attention is next directed to FIG. 4 , which provides infrared spectra (IR) of the pyrolysis product of the chloroanilate disodium salt, the pyrolysis product of the chloroanilate disodium salt including Pd nanoparticles (˜10 nm in diameter), and the pyrolysis product of chloroanilate disodium salt in combination of Pd nanoparticles (˜10 nm in diameter) in combination with Hg (Pd—Hg). As can be seen, the Pd and Pd—Hg samples retain the characteristics of the underlying pyrolysis product, exhibiting characteristic carbonyl absorption at 1710 cm −1 and also relatively broad absorptions at 1500-1100 cm −1 and 600 cm −1 , indicating the presence of hydroxyl (—OH) functionality. FIG. 5A provides a high resolution transmission electron micrograph image and the electron diffraction patterns (insert to FIG. 5A ) of the pyrolysis product of the chloroanilate salt. The image has been inverted for clarity (i.e. the carbon matrix is shown in white). FIG. 5B provides the high resolution transmission electron micrograph of the pyrolysis product of the chloroanilate salt which contains the Pd nanoparticles (˜10 nm in diameter), showing aggregates of Pd nanoparticles, as well as single Pd nanoparticles dispersed therein. FIG. 5C provides the high resolution transmission electron micrograph of the pyrolysis product of chloroanilate disodium salt in combination with Pd nanoparticles with Hg.
[0029] Attention is next directed to FIG. 6 , which illustrates the N 2 sorption/desorption isotherms at 77° K of Pd nanoparticles (˜10 nm in diameter), the pyrolysis product of the chloroanilate salt, the pyrolysis product of the chloroanilate disodium salt which contains the Pd nanoparticles (˜10 nm in diameter) and the pyrolysis product of chloroanilate disodium salt in combination with Pd—Hg nanoparticles. For all sorption/desorption plots herein ( FIGS. 6-8 ), it can be noted that the darkened symbols represent sorption and the hollow symbols represent desorption. The insert graph illustrates the sorption isotherms in log scale. In the normal scale the isotherms have been shifted for clarity by 200 cm 3 /g for the chloroanilate salt which contains the Pd nanoparticles (˜10 nm in diameter) and 400 cm 3 /g for the pyrolysis product of chloroanilate disodium salt in combination with Pd—Hg nanoparticles (˜10 nm in diameter). As can be seen, due to the porosity of the pyrolysis product, the N 2 isotherms (aside from that for Pd alone) are all relatively similar and indicative of a multi-scale pore system spanning from micropores (i.e. pores with sizes less than 2 nm) indicating a relatively steep increase in the amount sorbed at relatively low pressures, p/p 0 , to mesopores (i.e. pores of 2 nm to 50 nm) and indicating a hysteresis loop, to macropores (i.e. pores greater than 50 nm) and indicating an exponential increase of amount of N 2 sorbed where p/p 0 approaches the value of 1.0, and more specifically, is in the range of 0.90-1.0. Reference to “p” is the pressure of the applied nitrogen, and “p 0 ” is the pressure at saturation.
[0030] In such regard, it may therefore be appreciated herein that the addition of metallic nanoparticles, or the addition of the metallic nanoparticles in combination with a second metal (e.g. Hg) as disclosed herein, can be uniquely achieved without affecting the porosity of the pyrolysis products of the metallic salts of the cyclic quinone ring compound with respect to gas transport. That is, the porosity of the pyrolysis products remains undisturbed and the ability to efficiently interact with a gas due to diffusion and transport of the gas within the porous regions of the pyrolysis products is not compromised.
[0031] It is worth noting that the similarity of the isotherms (aside from that for Pd alone) appears to be the case for the entire pressure range (10 −5 to 1.0), indicating that the samples share the same pore system in all length scales. The BET surface areas for the samples in FIG. 6 were 510 m 2 /g for the pyrolysis product of the chloroanilate salt and 450-460 m 2 /g for the pyrolysis product treated either with Pd alone or with the Pd—Hg combination. With respect to the ˜10 nm diameter Pd nanoparticles on their own, such particles indicated a BET surface area of about 43 m 2 /g. It may therefore be appreciated that at a 10 percent by weight loading of the Pd nanoparticles and/or Pd—Hg nanoparticle combination, the value for the Pd nanoparticles on their own is consistent with the slight surface area decrease observed when the Pd nanoparticles and/or Pd—Hg nanoparticles combination is added to the pyrolysis products (0.90×510 m 2 /g)+(0.10×43 m 2 /g)=460 m 2 /g. This therefore suggests that no intercalcation or insertion of the nanoparticles into the matrix of the pyrolysis products had occurred.
[0032] It is therefore worth noting at this point that the pyrolysis products of a cyclic quinone ring compound allows for the incorporation and dispersion of either the above referenced metallic nanoparticles (Ti, V, Fe, Ni, Cu, Ru, Rh, Pd, Sn, Sb, W, Re, Pt, and/or Au) and/or the nanoparticles combined with a second metal or metals as an alloy (B, Al, V, Fe, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, and/or Bi) to provide an improved solid form hydrogen storage system. In addition, such hydrogen storage system is one wherein the various characteristics of the pyrolysis products, noted herein, remain relatively unchanged.
[0033] FIG. 7 shows the hydrogen sorption isothermal measurements at room temperature (298° K) for the pyrolysis product of the chloroanilate disodium salt and for such salt in combination with Pd. As can be seen, the amount of hydrogen sorbed on the pyrolysis product in the absence of the Pd (darkened symbols) is relatively small. However, as can be seen, addition of Pd to the pyrolysis product results in a marked improvement in the sorption of hydrogen. The amount sorbed in this particular example was about 2.1 percent by weight at the relatively low pressure of 3 bars (0.3 MPa) of hydrogen, at the temperature of 298° K. It therefore may be noted that the storage capacity of Pd is only about 0.72 percent by weight hydrogen, and in FIG. 7 , the amount of Pd in the pyrolysis product is about 10% by weight. That being the case, it can be appreciated that the relatively high capacity noted of about 2.1 percent by weight hydrogen storage in the pyrolysis product is due to some sort of synergistic effect of the Pd nanoparticles when incorporated into the pyrolysis product as noted herein.
[0034] Attention is next directed to FIG. 8 , which indicates the sorption isothermal measurements at room temperature (298° K) for the pyrolysis product of the chloroanilate disodium salt in combination with Pd—Hg, where the Pd was present at 80% (atoms) and the Hg was present at 20% (atoms). The isotherms indicate a practically linear shape revealing an uptake of around 8.0 percent by weight hydrogen at about 8 MPa (80 bars). In addition, a Langmuir fit of the equilibrium points (solid line) predicts an excess of more than 9.0% by weight hydrogen absorption at about 10 MPa hydrogen. As noted above, this complies with DOE targets for a solid state hydrogen sorption system for year 2010. Furthermore, as can be seen, the isotherms are reversible (solid symbols indicating sorption and open symbols indicating desorption).
[0035] Attention is next directed to the following non-limiting examples describing the specific formation of the pyrolysis product of the chloroanilate halogen salt, and the procedures for incorporation of metallic nanoparticles, optionally in combination with a second metallic component.
Pyrolysis of a Cyclic Quinone (Chloroanilate Disodium Salt) to a Graphite Oxide-Like Material
[0036] Chloranilic acid, disodium salt dihydrate was calcined at 300° C. in air for 2 hours. The obtained graphite oxide-like material was copiously washed with water and acetone prior drying at 65° C. for a day. 9
Pyrolysis Product of Chloroanilate Disodium Salt in Combination with Palladium
[0037] The pyrolysis product of choloroanilate disodium salt was combined with 10% w/w Pd and was derived as follows: 130 mg of the pyrolysis product of the chloroanilate disodium salt (hereinafter support) was suspended in 25 mL de-ionized water followed by the addition of 25 mg anhydrous PdCl 2 . The dissolution of the salt and subsequent coordination of the Pd(II) species to the surface exposed functional groups of the support was promoted by mild heating at 65° C. and by occasional sonication in an ultrasound bath. Then 50 mg NaBH 4 were added and the mixture was stirred for 1 h. The solid suspension was centrifuged, washed thoroughly with water and acetone and dried.
Pyrolysis Product of Chloroanilate Disodium Salt in Combination with Palladium/Mercury
[0038] The solid phase hydrogen storage material containing the Pd nanoparticles in combination with mercury (12 w/w %, Pd/Hg=4 atomic ratio, potarite phase) was prepared by suspending 140 mg of the pyrolysis product of the chloroanilate salt in 25 ml de-ionized water followed by the dissolution of 25 mg anhydrous PdCl 2 and 9.5 mg HgCl 2 . Salt dissolution was assisted by mild heating at 65° C. and sporadic sonication. Then 50 mg NaBH 4 were added and the mixture was stirred for 1 h. The solid suspension was centrifuged, washed thoroughly with water and acetone and dried.
[0039] The foregoing description of several methods and embodiments has been presented for purposes of illustration. It is not intended to be exhaustive or to limit the claims to the precise steps and/or forms disclosed, and obviously many modifications and variations are possible in light of the above teaching. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of “including,” “comprising,” or “having” and variations thereof herein is meant to encompass the items listed thereafter and equivalents thereof as well as additional items. It is intended that the scope of the invention be defined by the claims appended hereto. | The present invention relates to carbon based materials that are employed for hydrogen storage applications. The material may be described as the pyrolysis product of a molecular precursor such as a cyclic quinone compound. The pyrolysis product may then be combined with selected transition metal atoms which may be in nanoparticulate form, where the metals may be dispersed on the material surface. Such product may then provide for the reversible storage of hydrogen. The metallic nanoparticles may also be combined with a second metal as an alloy to further improve hydrogen storage performance. | 2 |
REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of application Ser. No. 912,425 filed June 5, 1979, now abandoned.
BACKGROUND OF THE INVENTION
This invention is related to name plates, and more particularly to a name plate in which a glass prism is mounted on a mirror having a mirrored surface spaced the thickness of the mirror from the bottom face of the prism. Several images of an exhibit on one face of the prism can be viewed through another prism face depending upon the direction of the user's line of sight and the prism.
SUMMARY OF THE INVENTION
The broad purpose of the present invention is to provide an improved name plate employing a glass prism mounted on a glass mirror to provide multiple images of an exhibit mounted on one face of the prism. One image is a reflection of the exhibit off the bottom face of the prism. As the viewer raises his line of sight, he views a second reflected image. Further raising of his line of sight will cause the first reflected image to fade out. If he raises his line of sight to a position generally perpendicular to the prism base, he will then view another, upside down, reflected image of the exhibit.
The second image is the result of the image being refracted through the thickness of the glass of the mirror while the first image is the result of the image being reflected off the bottom face of the prism. There is a transitory position of the viewer's line of sight when he views both images as one fades out and the other comes into view. This transitory state produces an apparent "ghost" image which provides an attention-getting feature of the name plate as a person passes the name plate.
Still further objects and advantages of the invention will become readily apparent to those skilled in the art to which the invention pertains upon reference to the following detailed description.
DESCRIPTION OF THE DRAWING
The description refers to the accompanying drawing in which like reference characters refer to like parts throughout the several views, and in which:
FIG. 1 is a perspective view of a name plate illustrating the preferred embodiment of the invention;
FIG. 2 is a sectional view of the name plate;
FIGS. 3, 4, and 5 are similar to FIG. 2. but showing different lines of sight of the viewer's eye; and
FIG. 6 is an exploded view of the preferred name plate.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawing, a preferred name plate, generally indicated at 10, comprises a base 12 and a prism 14. Base 12 has a rectangular configuration with a flat upper surface 16 and a recessed, rectangular midsection 18. A mirror 20 is seated in recess 18.
Referring to FIG. 2, mirror 20 is formed of a sheet of glass 22 having a reflective or mirrored coating 24. Mirrored coating 24 faces upwardly toward the prism and is on the bottom face of glass 20. The coating is spaced from prism 14 a distance corresponding to the thickness of glass 20.
Prism 14 is preferably of a prism glass and has a pair of end faces 26 and 28, a face 30 formed at a 90° angle with respect to face 32, and a 45° angle with respect to the bottom face 34.
Still referring to FIG. 2, an exhibit 36 comprises a series of letters etched into the surface of face 30. Faces 26, 28, and 30 are then coated with an opaque flat paint.
Exhibit 36 is observable through the prism by a line of sight 38 from the eye 40 of the viewer parallel to face 34.
Referring to FIG. 3, as the viewer changes his line of sight 38 toward the bottom face of the prism, he will then view a reflected, upside down image of exhibit 36.
Referring to FIG. 4, if the viewer then increases the angle between his line of sight and face 34, he will pass through a transistory state at which time he will view a double image caused by a portion of the exhibit's image being refracted through bottom face 34 of the prism into the mirror. This portion of the refracted image is reflected off mirrored surface 24. As he further increases the angle between his line of sight and bottom face 34 of the prism, he passes through a critical angle when the image reflected from the bottom face 34 of the prism fades out of sight and the refracted image, reflected off the mirror surface 24 of the mirror, comes into full view.
If the viewer continues to raise his line of sight to that illustrated in FIG. 5 to a position generally perpendicular to the bottom face 34 of the prism, he will view another image of the exhibit, upside down with respect to the first and second images.
Thus depending upon the angle of the user's line of sight and the prism, he can view either the exhibit itself or three reflected images of the exhibit. As a person moves past the prism, the appearance of the different images as they come into and fade out of view attract his attention.
Preferably the prism is seated in the recessed midsection 18 so that it will not slide off the base as the viewer tilts the base upwardly.
A felt pad 42 is attached to the bottom of the base to prevent the base from scratching the surface of a desk (not shown) on which the name plate is disposed. | A name plate comprising a right angle glass prism mounted on a mirror such that an exhibit mounted on one of the prism faces provides several images depending upon the user's line of sight of the prism. | 6 |
TECHNICAL FIELD
This invention relates generally to computer graphics systems and more particularly to a method and apparatus for approximating an exponential gradient.
BACKGROUND
An exponential gradient is a non-linear transition from one color or gray level to another in a graphic image. The rate of transition for the exponential gradient can be described by a function y which is equal to x e where e is greater than 1. The exponential gradient can be used to describe the color change from a first point in the graphic image to a second point in the graphic image where each of the points has an associated color (gray) value. The transition from the first color value at the first point to the second color value at the second point is characterized by the function y=x e .
When a computer graphics system (i.e., a raster image processor) processes an exponential gradient, the non-linear function (y=x e ) may be too difficult or time consuming to render. Exponential gradients can be approximated using a series of piece-wise linear segments. Part of the process includes determining a number of stops or stopping segment points for the approximation. Typically, the number of stops is pre-selected (a preset value for all exponential gradients that are processed for a given image) and results in an approximation that includes evenly divided segments. However, if there are too few linear stops, the approximation may be poor. If too many linear stops are created, both space and time will be wasted in the approximation process. Even if the proper number of stops is selected, the even distribution of the stops may likewise produce a poor approximation when a curvature of the original exponential gradient is significantly greater in one region than in another.
SUMMARY
In one aspect, the invention provides a method for a method for approximating a gradient, the gradient defining a nonlinear transition from one color or gray level to another in an image where the rate of transition is determined by the function y=x e where e>1. The method includes identifying an error tolerance, selecting a starting point and a set point on a curve defined by the function, defining a linear step from the start point to the set point and calculating a maximum error between the linear step and the curve. If the maximum error is less than or equal to the error tolerance, a portion of the gradient corresponding to the linear step is approximated with the linear step. If the maximum error is more than the error tolerance, a new set point on the curve closer to the starting point is selected and the calculating step and error checking steps are repeated.
Aspects of the invention can include one or more of the following features. The first set point selected can be an end point of the curve. The new set point selected can be half the distance between the set point and the starting point. The step of approximating the portion of the gradient can include determining if the set point is an end point for the curve. If the set point is not an end point for the curve, the set point can be set as a new starting point and the process can continue including selecting a new set point, else, the process ends and the gradient can be approximated using the defined linear steps. The new set point can be selected using the calculated maximum error. The new set point can be selected as being a point that corresponds to a linear step having a maximum error equal to the error tolerance. If the maximum error is less than the error tolerance, before approximating a portion of the gradient, the method can include continuing to select new set points on the curve beyond the first set point and repeating the calculating step until the maximum error associated with a new set point is equal to the error tolerance or the new set point is an ending point on the curve. Thereafter, a portion of the gradient corresponding to the linear step can be approximated with the linear step. The method can include checking to determine if the set point is an end point of the curve and, if not, approximating a second portion of the gradient including repeating the method with a previous set point as the starting point for a next approximation. The error tolerance can be a visual tolerance. The method can include using Newton's Method to select a set point on the curve to minimize the error between an approximation produced by the method and the curve.
In another aspect, the invention provides a method for approximating a gradient, the gradient defining a nonlinear transition from one color or gray level to another in an image where the rate of transition is determined by the function y=x e where e>1. The method includes identifying an error tolerance, selecting an optimal number of set points on a curve defined by the function including determining each set point by evaluating a maximum error between a line defined by a pair of set points and a corresponding portion of the curve using the error tolerance and approximating the curve by a series of linear portions connecting the set points.
In another aspect the invention can comprise a method for approximating a gradient, the gradient defining a nonlinear transition from one color or gray level to another in an image where the rate of transition is determined by the function y=x e where e>1. The method includes identifying an error tolerance, selecting an optimal number of linear stops on a curve defined by the function including using Newton's Method to recursively sub-divide the curve to find a next linear portion that approximates a corresponding portion of the curve within the error tolerance where each linear portion is defined by two linear stops, and locating subsequent linear stops until an end point of the curve is reached. The method includes approximating the curve by a series of linear portions connecting the linear stops.
In another aspect the invention provides a computer program stored on a tangible medium for approximating a gradient, the gradient defining a nonlinear transition from one color or gray level to another in an image where the rate of transition is determined by the function y=x e where e>1. The program includes instructions to identify an error tolerance, select a starting point and a set point on a curve defined by the function, define a linear step from the start point to the set point and calculate a maximum error between the linear step and the curve. If the maximum error is less than or equal to the error tolerance, a portion of the gradient corresponding to the linear step is approximated with the linear step. If the maximum error is more than the error tolerance, a new set point on the curve closer to the starting point is selected and the calculate and error checking instructions are repeated.
In another aspect the invention provides a computer program stored on a tangible medium for approximating a gradient, the gradient defining a nonlinear transition from one color or gray level to another in an image where the rate of transition is determined by the function y=x e where e>1. The program includes instructions to identify an error tolerance, select an optimal number of set points on a curve defined by the function including determine each set point by evaluating a maximum error between a line defined by a pair of set points and a corresponding portion of the curve using the error tolerance and approximate the curve by a series of linear portions connecting the set points.
I another aspect, the invention provides a computer program stored on a tangible medium for approximating a gradient, the gradient defining a nonlinear transition from one color or gray level to another in an image where the rate of transition is determined by the function y=x e where e>1. The program includes instructions to identify an error tolerance, select an optimal number of linear stops on a curve defined by the function including use Newton's Method to recursively sub-divide the curve to find a next linear portion that approximates a corresponding portion of the curve within the error tolerance where each linear portion is defined by two linear stops and locate subsequent linear stops until an end point of the curve is reached. The program includes instructions to approximate the curve by a series of linear portions connecting the linear stops.
Aspects of the invention can include one or more of the following advantages. The system can generate only as many optimally located linear stops as required to approximate an exponential gradient within a given visual tolerance. The system can incorporate a recursive sub-dividing process to define an exponential curve. Linear portions that approximate corresponding portions of the exponential curve within a given error tolerance can be identified. The process is repeated until the end of the curve is reached.
The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims.
DESCRIPTION OF DRAWINGS
FIG. 1 a shows an image that includes an object having a shading defined by an exponential gradient.
FIG. 1 b shows a graphical representation for the exponential gradient.
FIG. 2 is a flow diagram for a method for determining the optimal number of stops for a linear approximation for the exponential gradient of FIG. 1 b.
FIG. 3 is flow diagram for a method for selecting an optimal next segment point.
Like reference symbols in the various drawings indicate like elements.
DETAILED DESCRIPTION
Referring to FIG. 1 a , an image 100 includes an ellipse 102 having two end points 104 and 106 running along the major axis 108 of ellipse 102 . Each point includes color data, and more specifically a color value that describes the color of ellipse 102 at a respective point. A function can be used to describe the color transition for all other points in the ellipse. FIG. 1 b shows a graph of a function (f(x) ) for describing the color transition between points 104 and 106 . The function f(x) define by curve 110 is an exponential gradient. For any point in the ellipse, the color can be computed as a mix of some percentage (the weighting factor) of each of the respective colors associated with the two points 104 and 106 . The graph has been normalized in each access so that the distance and weights are scaled from 0 to 1 in each axis. To determine the color for a given point (a target point), the system can locate the intersection of the physical offset (for the target point in the x-axis from the reference point (either point 104 or 106 )) and the curve 110 to determine a weighting. The weighting determines the percentage of each color (the colors of points 104 and 106 ) used in producing the resultant color for the target point.
As described above, the y-axis of the graph represents the interpolation weight to be applied for a given point. The x-axis represents the physical offset location for points in the gradient. The graph of offset versus interpolation weight can be used to determine the color value for any point in the gradient. In this example, the graph defines a nonlinear transition from the color at a physical offset location 0 to the color at a physical offset of 1 or the end point of the gradient. The function f(x) can be approximated by a linear interpolation. Here, the function f(x), has been approximated by two segments: segment 111 that spans from point S 0 to S 1 and segment 112 that spans from point S 1 to point S 2 . Associated with approximation is an error tolerance T. The error tolerance T defines a visual tolerance that is acceptable for a point in the linear approximation. S i defines an end point of a segment. The end point can be both an end point of a previous approximation segment and a starting point of a next approximation segment.
FIG. 2 shows a method 200 for performing an approximation of the nonlinear gradient to produce the optimal number of stop points and as such an optimal number of approximation segments. The method begins by setting the start point S i for the current segment as the end point for the previous approximation segment (i.e., the last segment point recorded) ( 202 ). For the first segment, the start point is set to 0. The end point for the segment is set as the endpoint of the curve 110 ( 204 ). The slope of the approximation segment is calculated ( 206 ). The slope of the approximation can be calculated according to Equation 1.
m ( x,s )=( x e −s e )/( x−s )
Thereafter, a vertical measure of error for the approximation segment is calculated ( 208 ). The vertical measure of error N is defined as the greatest error for any chosen value of x along the length of the approximation segment. The vertical measure of error from the approximation to the exponential can be defined according to Equation 2.
N ( x , s ) = s e + ( e - 1 ) · ( m ( x , s ) e ) e e - 1 - s m ( x , s )
A check is made to determine if the vertical measure of error for the approximation segment is greater than the predetermined error tolerance T ( 210 ). If not, then the process continues at step 240 .
If the vertical measure of error exceeds the error tolerance T, then a next stop point between s and 1 is selected whose corresponding linear step has an error (vertical measure of error) at the tolerance limit ( 212 ). The next stop point is the stop point where the error calculated (in accordance with Equation 2) meets the error tolerance T. In order to determine the next stop point an iterative process can be applied. One implementation of an iterative process for determining the optimal next stop point is described in greater detail below in association with FIG. 3 . Thereafter, the next stop point is recorded as a segment point ( 214 ) and the process continues at step 202 .
In step 240 , the end point (1,1) is recorded as final segment point along with the start point (0, 0) and the process completes. The segment points can be used to create the gradient stops associated with linear segments to be used in the approximation for the non-linear gradient. The linear interpolated gradient will approximate the original exponentially interpolated gradient. A gradient stop can be assigned for each recorded segment point. The offset for each gradient stop is the first coordinate of the associated segment point. The color of each gradient stop is the linear interpolated color between colors of the endpoints (points 104 and 106 ) and can be calculated using the second coordinate of the segment point as a linear weighting factor. This color can be represented symbolically as (1−t)×a+t×b where a and b are the colors respectively of the end points for the gradient (e.g., points 104 and 106 of FIG. 1 a ).
Referring now to FIG. 3 , one implementation for selecting the next stop point (step 212 of FIG. 2 ) begins by picking a new stop point between S i and 1 ( 302 ). In one implementation, the new stop point can have an x value that is half way between S i and 1. Thereafter three values are computed. First a function needs to be introduced, referred to as the denominator, that is equal to the mathematical derivative of N (the vertical measure of error) with respect to x. The denominator defines the rate of change of the curve f(x). The derivative can be defined mathematically in accordance with Equation 3.
D ( x , s ) = ( ( m ( x , s ) e ) e e - 1 - s ) · ex e - 1 - m ( x , s ) x - s
The three values that are computed are, maximum vertical error for point x n ( 304 ), a speed factor a ( 306 ) and a next “x” value (x n+ 1) ( 308 ). The speed factor a is equal to the error that was calculated for a given iteration minus the tolerance T divided by the derivative d where:
N ( x n , s ) - T D ( x n , s )
The next x value x n+1 is equal to the current x value (x n ) minus the speed factor a where:
x n + 1 = x n N ( x n , s ) - T D ( x n , s )
Thereafter, a check is made to determine if the absolute value of the speed factor a is greater than a fixed value ( 310 ). In one implementation, the fixed value is a small non-negative number, such as 0.0001. If the absolute value is greater, then a next x is selected (n is increased by 1 where x n +1, is selected closer to S i ) ( 312 ) and the process returns to step 304 . Otherwise, the point (x n+ 1, x n+1 e ) is recorded as the next segment point ( 314 ) and S i (the prior segment point) is set as x n+1 . In one implementation, the next “x” (x n+1 ) is selected in accordance with Equation 5. Alternatively, the next x can be selected by again selecting a point that is half way between the last x (x n ) and the most recent x processed in the direction determined by the sign of the adjustment value a. This alternative process will not however move as quickly to the optimal next segment point. The process then continues as described above computing the greatest error associated with the next approximation segment. The iterative process described moves very quickly to the optimal next x (segment point) that has maximum error value that is exactly at the tolerance value. This is true because of how the error calculated is used to determine the next x point.
A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims. | A method and computer program for approximating a gradient, the gradient defining a nonlinear transition from one color or gray level to another in an image where the rate of transition is determined by the function y=x e where e>1. The method includes identifying an error tolerance, selecting an optimal number of set points on a curve defined by the function including determining each set point by evaluating a maximum error between a line defined by a pair of set points and a corresponding portion of the curve using the error tolerance and approximating the curve by a series of linear portions connecting the set points. | 6 |
FIELD OF THE INVENTION
[0001] The present application relates to the mechanical field, specifically to the valve actuation technology for vehicle engines, particularly to a combined rocker arm device for an auxiliary engine valve event.
BACKGROUND OF THE INVENTION
[0002] In the prior art, the method of conventional valve actuation for a vehicle engine is well known and its application has more than one hundred years of history. However, due to the additional requirements on engine emission and engine braking, more and more engines need to produce an auxiliary engine valve event, such as an exhaust gas recirculation event or an engine braking event, in addition to the normal engine valve event. The engine brake has gradually become the must-have device for the heavy-duty commercial vehicle engines.
[0003] The engine braking technology is also well known. The engine is temporarily converted to a compressor, and in the conversion process the fuel is cut off, the exhaust valve is opened near the end of the compression stroke of the engine piston, thereby allowing the compressed gases (being air during braking) to be released. The energy absorbed by the compressed gas during the compression stroke cannot be returned to the engine piston at the subsequent expansion stroke, but is dissipated by the engine exhaust and cooling systems, which results in an effective engine braking and the slow-down of the vehicle.
[0004] There are different types of engine brakes. Typically, an engine braking operation is achieved by adding an auxiliary valve event for engine braking event into the normal engine valve event. Depending on how the auxiliary valve event is generated, an engine brake can be defined as:
1. Type I engine brake: the auxiliary valve event is introduced from a neighboring existing cam in the engine, which generates the so called Jake Brake; 2. Type II engine brake: the auxiliary valve event generates a lost motion type engine brake by altering existing cam profile; 3. Type III engine brake: the auxiliary valve event is produced from a dedicated cam for engine braking, which generates a dedicated brake valve event via a dedicated brake rocker arm; 4. Type IV engine brake: the auxiliary valve event is produced by modifying the existing valve lift of the engine, which normally generates a bleeder type engine brake; and 5. Type V engine brake: the auxiliary valve event is produced by using a dedicated valve train to generate a dedicated valve (the fifth valve) engine brake.
[0010] An example of engine brake devices in the prior art is disclosed by Cummins in U.S. Pat. No. 3,220,392. The engine brake system based on the patent has enjoyed a great commercial success. However, this engine brake system is a bolt-on accessory that fits above the engine. In order to mount the brake system, a spacer needs to be positioned between the cylinder and the valve cover. This arrangement may additionally increase height, weight, and cost to the engine.
[0011] Among these above five types of engine brakes, the third one, i.e. the dedicated cam or the dedicated rocker arm brake, has the best engine brake power. However, the existing dedicated rocker arm brake device cannot be applied to the engines with the valve bridge being parallel or almost parallel to the rocker arm.
SUMMARY OF THE INVENTION
[0012] An object of the present application is to provide a combined rocker arm device for producing an auxiliary engine valve event, so as to solve the technical problem in the prior art that the dedicated rocker arm brake system cannot be applied to the engines with the valve bridge being parallel to the rocker arm and to address the technical problems of increased engine height, weight and cost of a conventional engine brake device.
[0013] The combined rocker arm device for producing an auxiliary engine valve event of the present application is used to generate an auxiliary valve event of an engine, and the engine including a conventional valve actuator, the conventional valve actuator including a cam, a rocker arm shaft, a conventional rocker arm and a valve, wherein the combined rocker arm device includes an auxiliary actuator and a transition rocker arm, the auxiliary actuator acts on the transition rocker arm, and the transition rocker arm acts on the valve.
[0014] Further, the auxiliary engine valve event generated by the combined rocker arm device includes a valve event for engine braking.
[0015] Further, the auxiliary actuator of the combined rocker arm device includes an auxiliary rocker arm and an auxiliary cam, the auxiliary rocker arm and the conventional rocker arm are mounted on the rocker arm shaft side by side, one end of the auxiliary rocker arm is connected to the auxiliary cam, and the other end of the auxiliary rocker arm is placed adjacent to the transition rocker arm; the auxiliary rocker arm includes an actuation mechanism being provided with an actuation piston, the actuation mechanism includes an non-operating position and an operating position; in the non-operating position, the actuation piston of the actuation mechanism retracts, and the auxiliary rocker arm is separated from the transition rocker arm; and in the operating position, the actuation piston of the actuation mechanism extends, and the auxiliary rocker arm is connected to the transition rocker arm.
[0016] Further, a rocking axis of the transition rocker arm maintains relatively static during the auxiliary engine valve event.
[0017] Further, in the combined rocker arm device, the auxiliary rocker arm is a brake rocker arm, the auxiliary cam is a brake cam, the brake rocker arm includes a brake actuation mechanism being provided with a brake piston, the brake actuation mechanism includes an non-operating position and an operating position; in the non-operating position, the brake piston of the brake actuation mechanism retracts, and the brake rocker arm is separated from the transition rocker arm; and in the operating position, the brake piston of the brake actuation mechanism extends, and the brake rocker arm is connected to the transition rocker arm.
[0018] Further, in the combined rocker arm device, the transition rocker arm is rotationally mounted on the conventional rocker arm of the engine, and the transition rocker arm has a rocking shaft parallel to a rocker arm shaft of the conventional rocker arm.
[0019] Further, in the combined rocker arm device, the transition rocker arm shares the rocker arm shaft with the conventional rocker arm.
[0020] Further, the combined rocker arm device also includes an auxiliary spring located between the auxiliary rocker arm and the transition rocker arm.
[0021] Further, the transition rocker arm of the combined rocker arm device includes a rocking limiter.
[0022] The working principle of the present application is as follows, when the auxiliary engine valve event is needed, i.e. when the engine needs to be converted from the normal engine operation state to the engine braking state, the engine braking controller is turned on. The brake actuation mechanism in the brake rocker arm is converted from the non-operating position to the operating position, and the brake rocker arm is connected to the transition rocker arm. The motion from the auxiliary cam. i.e. the brake cam, is transmitted to the exhaust valve through the brake rocker arm and the transition rocker arm, thereby producing the auxiliary valve event for engine braking. When engine braking is not needed, the engine braking controller is turned off. The brake actuation mechanism retracts from the operating position to the non-operating position, and the brake rocker arm is separated from the transition rocker arm. The motion from the brake cam cannot be transmitted to the exhaust valve, and the engine is disengaged from the braking operation, and back to the normal operation state.
[0023] The present application has positive and obvious effects over the prior art. In the present application, less or no height, size and weight of the engine need to be increased, the application scope of the dedicated cam or the dedicated rocker arm brake device is enlarged, the engine braking performance is improved, and the affect of the engine braking operation on the engine ignition operation is reduced.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] FIG. 1 is a schematic diagram illustrating the positional relationship among a transition rocker arm, a conventional rocker arm and a valve actuator of a combined rocker arm device according to an embodiment of the present application;
[0025] FIG. 2 is a side view of the transition rocker arm of the combined rocker arm device for an auxiliary engine valve event according to an embodiment of the present application;
[0026] FIG. 3 is a top view of the transition rocker arm of the combined rocker arm device for an auxiliary engine valve event according to an embodiment of the present application;
[0027] FIG. 4 is a schematic diagram illustrating the positional relationship between a brake rocker arm and the conventional rocker arm of the combined rocker arm device for an auxiliary engine valve event according to an embodiment of the present application;
[0028] FIG. 5 is a schematic diagram illustrating the brake rocker arm and its relative position with the combined rocker arm device for an auxiliary engine valve event according to an embodiment of the present application; and
[0029] FIG. 6 is a schematic diagram illustrating the conventional valve lift profile and the auxiliary valve lift profile (engine brake valve lift) for the combined rocker arm device for an auxiliary engine valve event according to an embodiment of the present application.
DETAILED DESCRIPTION OF THE EMBODIMENTS
Embodiment
[0030] FIG. 1 is a schematic diagram illustrating the positional relationship among a transition rocker arm 2103 , a conventional rocker arm 210 and a valve actuator 200 of a combined rocker arm device for an auxiliary engine valve event according to an embodiment of the present application. The auxiliary valve event generated by the combined rocker arm device of the present embodiment is an exhaust valve event for engine braking. The conventional engine exhaust valve event is generated by the engine exhaust valve actuator 200 . The auxiliary exhaust valve event for engine braking is generated by an auxiliary actuator. The auxiliary actuator includes an auxiliary rocker arm (shown as a brake rocker arm) 2102 and an auxiliary cam (shown as a brake cam 2302 shown in FIG. 5 ). It should be noted that the embodiment should not be regarded as limitation on the scope of the claims, but rather as exemplification of the present application.
[0031] 100311 The exhaust valve actuator 200 has many parts, including a cam 230 , a cam follower 235 , a conventional rocker arm 210 , a valve bridge 400 and exhaust valves 300 ( 3001 and 3002 ). The exhaust valves 300 are biased on valve seats 320 in an engine cylinder block 500 by engine valve springs 310 ( 3101 and 3102 ) to prevent gases flowing between the engine cylinder and an exhaust manifold 600 . The conventional rocker arm 210 is rotationally mounted on a rocker arm shaft 205 and transmits the motion from the cam 230 to the exhaust valves 300 for cyclic opening and closing of the exhaust valves 300 . The exhaust valve actuator 200 also includes a valve lash adjusting screw 110 and an elephant foot pad 114 . The valve lash adjusting screw 110 is fixed on the rocker arm 210 by a nut 105 . On an inner base circle 225 , the cam 230 has a conventional cam lobe 220 to generate the conventional valve lift profile (see 2202 in FIG. 6 ) for the conventional engine (ignition) operation.
[0032] As shown in FIGS. 1 , 2 and 3 , the transition rocker arm 2103 is rotationally mounted on the conventional rocker arm 210 . A cutting groove 270 is provided at a lower portion of the conventional rocker arm 210 , two ears 272 and 274 are respectively formed at two sides of the cutting groove 270 , and a shaft hole 276 is formed in the two ears 272 and 274 . A transition rocker arm shaft 2052 is disposed in a shaft hole 278 of the transition rocker arm 2103 (see FIG. 2 and FIG. 3 ), and then is installed in the shaft hole 276 . The transition rocker arm shaft 2052 and the rocker arm shaft 205 are parallel to each other. Therefore, the transition rocker arm 2103 can rock with respect to the conventional rocker arm 210 with the rocking range controlled by a rocking limiter. The rocking limiter includes a limiting end 217 of the transition rocker arm 2103 . The rocking range of the transition rocker arm 2103 is controlled by controlling a distance between the limiting end 217 and the conventional rocker arm 210 . The rocking range of the transition rocker arm 2103 is determined by a rocking range of the auxiliary rocker arm (i.e. the brake rocker arm) 2102 (the brake rocker arm 2102 is described more specifically in FIG. 4 and FIG. 5 ) due to the reason that the transition rocker arm 2103 is located under the brake rocker arm 2102 and is actuated by the brake rocker arm 2102 . The transition rocker arm 2103 is also located above a brake pushrod 116 (the exhaust valve 3001 ). The transition rocker arm 2103 may not need the brake pushrod 116 , but directly act on the valve bridge 400 or the exhaust valve 3001 . The auxiliary spring or brake spring 198 in FIG. 1 is used to prevent the transition rocker arm 2103 and the brake rocker arm 2102 from not-following or colliding.
[0033] FIGS. 2 and 3 are the side view and top view of the transition rocker arm 2103 respectively, which are used to further describe the positional relationship among the transition rocker arm 2103 , the brake rocker arm 2102 and the brake pushrod 116 (or the exhaust valve 3001 ). The brake rocker arm 2102 acts on an upper surface 2181 on an end 218 , near the exhaust valve, of the transition rocker arm 2103 , while a lower surface 2182 of the transition rocker arm 2103 acts on the brake push rod 116 (or the exhaust valve 3001 ). A distance between the two acting points is shown by the reference numeral 279 (see FIG. 3 ).
[0034] FIG. 4 is a schematic diagram illustrating the positional relationship between the auxiliary rocker arm (i.e. the brake rocker arm) 2102 and the conventional rocker arm 210 of the combined rocker device according to the embodiment of the present application, wherein the brake rocker arm 2102 and the conventional rocker arm 210 are installed on the rocker arm shaft 205 side by side.
[0035] FIG. 5 is a schematic diagram illustrating the brake rocker arm 2102 and its relative position with the combined rocker arm device according to the embodiment of the present application. The brake rocker arm 2102 includes a brake actuation mechanism 100 . The brake actuation mechanism 100 includes an actuation piston (a brake piston) 160 which is moveable between a non-operating position and an operating position. When in the non-operating position as shown in FIG. 5 , i.e. when engine braking is not needed, the brake piston 160 of the brake actuation mechanism 100 retracts, and the brake rocker arm 2102 is separated from the transition rocker arm 2103 thereby forming a gap 132 between the brake rocker arm 2102 and the transition rocker arm 2103 . The gap 132 is adjustable by an adjusting screw 1102 of a brake valve lash adjusting mechanism, such that the motion generated by the auxiliary cam lobes (the brake cam lobes) 232 and 233 on the inner base circle 2252 of the brake cam 2302 cannot be transmitted to the exhaust valve 3001 .
[0036] When the auxiliary valve event, i.e. the engine braking, is needed, the engine brake controller (not shown) is turned on to supply engine oil, and the engine oil acts on the brake actuation mechanism 100 , such that the brake piston 160 is extended from the retracted non-operating position (as shown in FIG. 5 ) to the operating position, thereby eliminating the gap 132 between the brake rocker arm 2102 and the transition rocker arm 2103 , that is the brake rocker arm 2102 is connected to the transition rocker arm 2103 . Through the cam follower 2352 , the brake rocker arm 2102 and the brake actuation mechanism 100 thereof, the transition rocker arm 2103 and the brake pushrod 116 , the motion generated by the auxiliary cam lobes (the brake cam lobes) 232 and 233 on the inner base circle 2252 of the brake cam 2302 is transmitted to the exhaust valve 3001 , thereby generating the auxiliary engine valve event for engine braking.
[0037] The auxiliary spring or the brake spring 198 in FIG. 1 is shown again in FIG. 5 . The auxiliary spring 198 is located between the brake rocker arm 2102 and the transition rocker arm 2103 to separate the above two components. An upward force of the spring 198 biases the brake rocker arm 2102 on the brake cam 2302 . A downward force of the spring 198 biases the transition rocker arm 2103 on the brake pushrod 116 . When the brake push rod 116 is pushed downward along with the valve bridge 400 and the exhaust valve 300 by the exhaust valve actuator 200 (see FIG. 1 ), the downward force of the spring 198 biases the transition rocker arm 2103 on the conventional rocker arm 210 (see FIG. 1 ). If the deformation of the spring 198 is large enough, the transition rocker arm 2103 does not need to have the rocking limiter, that is, the limiting end 217 is not needed. In this way, the transition rocker arm 2103 becomes a “semi-rocker arm” and is always in contact with the brake pushrod 116 (or the exhaust valve 3001 ). It should be noted that the force of the auxiliary spring or the brake spring 198 is much smaller than the preload force of the engine valve spring 3101 .
[0038] FIG. 6 is a schematic diagram illustrating the conventional valve lift profile 2202 and the auxiliary valve lift profiles (the engine brake valve lift) 2322 and 2332 for the combined rocker arm device according to the embodiment of the present application. The conventional valve lift profile 2202 generated by the valve actuator 200 corresponds to the conventional cam lobe 220 on the inner base circle 225 of cam 230 as shown in FIG. 1 . The auxiliary valve lift (the engine brake valve lift) profiles 2322 and 2332 generated by the brake rocker arm 2102 and the transition rocker arm 2103 correspond to the auxiliary cam lobes (the brake cam lobes) 232 and 233 on the inner base circle 2252 of the brake cam 2302 as in FIG. 5 .
[0039] In FIG. 6 , the conventional valve lift profile 2202 is separated from the auxiliary valve lift profiles 2322 and 2332 , thus the actuation timing of the conventional rocker arm 210 is staggered from that of the brake rocker arm 2102 . When the brake rocker arm 2102 actuates the transition rocker arm 2103 , the conventional rocker arm 210 is stationary. Therefore, the rocking shaft 2052 (as shown in FIG. 1 ) of the transition rocker arm 2103 mounted on the conventional rocker arm 210 is also stationary. In other words, when the auxiliary cam lobes 232 and 233 of the cam 2302 (as shown in FIG. 5 ) actuates the brake rocker arm 2102 , the transition rocker arm 2103 and the valve 3001 to produce the auxiliary valve lift profiles 2322 and 2332 , a rocking axis of the transition rocker arm 2103 is stationary.
[0040] Therefore, the rocking shaft 2052 of the transition rocker arm 2103 can also be installed on other portions of the engine, for example, sharing the rocker shaft 205 with the conventional rocker arm 210 , as long as the rocking axis of the transition rocker arm 2103 can remain relatively static when the auxiliary rocker arm produces the auxiliary valve event. In addition, the actuation mechanism on the auxiliary rocker arm 2102 can also be transferred onto the transition rocker arm 2103 .
[0041] While the above description contains many specific embodiments, these embodiments should not be regarded as limitations on the scope of the present application, but rather as specific exemplifications of the present application. Many other variations are likely to be derived from the specific embodiments. For example, the combined rocker arm device described herein can be used to produce the auxiliary engine valve event not only for engine braking, but also for exhaust gas recirculation and other auxiliary engine valve events.
[0042] In addition, the combined rocker arm device described herein can be used not only for overhead cam engines, but also for push rod/tubular engines, and can be used not only for exhaust valve actuation, but also for intake valve actuation.
[0043] Also, the auxiliary actuator described herein can include not only the brake rocker arm and the brake cam, but also other actuation mechanisms, including mechanical, hydraulic, electromagnetic, or a combined mechanism. Therefore, the scope of the present application should not be defined by the above-mentioned specific examples, but by the appended claims and their legal equivalents. | A combined rocker arm apparatus for actuating auxiliary valve of engine, comprises an auxiliary actuator, a main rocker arm and a secondary rocker arm. The auxiliary actuator comprises an auxiliary rocker arm and an auxiliary cam. The auxiliary rocker arm and the main rocker arm are mounted on the rocker arm shaft in parallel. The auxiliary rocker arm is connected to the auxiliary cam at one end and adjacent to the secondary rocker arm at the other end. The auxiliary rocker arm includes a drive mechanism which provided with a piston. In the non-operation mode of the drive mechanism, the piston is drawn back, then the auxiliary rocker arm is disconnected with the secondary rocker arm; in the operation mode of the drive mechanism, the piston is pushed out, then the auxiliary rocker arm is connected with the secondary rocker arm. | 5 |
BACKGROUND OF THE INVENTION
[0001] The invention is concerned with wastewater treatment and especially efficient removal of refractory biodegradable compounds including so called microconstituents from wastewater in a membrane bioreactor (MBR) process.
[0002] A great deal of research has been undertaken to characterize the ability of conventional activated sludge and membrane bioreactor (MBR) technologies to remove microconstituents. Microconstituents are dissolved pollutants that are usually measured on the parts per billion (ppb) or parts per trillion (ppt) level. They include personal care products, pharmaceutical materials and hydrocarbons. Microconstituents are often refractory, long-chain organic compounds that are difficult to degrade biologically given typical solids residence times (less than 30 days).
[0003] In conventional activated sludge processes using sedimentation or membrane filtration for removal of suspended solids, post-disinfection is used to inactivate or kill pathogenic organisms. In addition to disinfection, post treatment including high pressure filtration (e.g. reverse osmosis) is sometimes employed to remove microconstituents.
[0004] Submerged MBR (sMBR) technology has a unique advantage over CAS systems using sedimentation for the separation of solids for biologically treated wastewater in that activated sludge concentrations can be more than three times higher allowing for a longer SRT given the same volume. Research suggests that running at longer SRT can lead to better removal of some refractory compounds and specifically some microconstituents. However, results are mixed and studies have not shown a sufficient correlation between treatment efficiency and SRT; therefore, the efficacy of MBR as compared to CAS Systems remains unquantifiable.
[0005] Prior art, whether CAS or MBR, often involves the use of high-pressure filtration such as reverse osmosis (RO) followed by post-oxidation (or post disinfection) of permeate using one or more oxidative compounds. The list includes ozone, chlorine and ultraviolet (UV) radiation. High-pressure permeate filtration, in some cases followed by oxidative post-disinfection, has been successful in destroying some microconstituents but is expensive and in many cases impractical. Moreover, the use of chlorine can lead to the formation of undesirable disinfection byproducts, some of them known carcinogens.
SUMMARY OF THE INVENTION
[0006] In a system and process of the invention, pretreated (screened, degritted) wastewater is saturated with ozone or contacted with a second stream of ozonated permeate for partial treatment or conditioning of refractory biodegradable compounds including microconstituents. The degraded ozone forms oxygen which is then used to offset biological process requirements.
[0007] The byproducts of wastewater ozonation are smaller, more readily biodegradable compounds and oxygen. The oxygen produced during ozonation is used to meet a portion of the total biological demand for aerobic processes in the system and in some cases may evolve as bubbles, partially offsetting the need for air scouring of submerged membrane separators.
[0008] Ozonating wastewater breaks down non- or less-biodegradable compounds including microconstituents into more readily biodegradable compounds that can be subsequently treated in an activated sludge MBR process at a shorter SRT. Given a target mixed liquor suspended solids (MLSS) concentration a shorter SRT translates into a reduced tank volume, allowing for what is called process intensification (reducing plan area and tank volume requirements to achieve a given treatment objective). For example, ozone can break down benzene rings into smaller carbon molecules readily consumed by microorganisms reducing the SRT required for treatment from 30 days to less than 5 days.
[0009] In one embodiment of the invention, pretreated (fine screened, degritted, etc.) wastewater (influent) is essentially saturated with ozone to concentrations ranging between 25 mg/l and 100 mg/l before being fed directly into an MBR. Given the dilute concentrations of carbon substrate in municipal wastewater, it is possible to safely aerosolize influent and contact with ozone for saturation but the range is limited to protect against auto-ignition (typically less than 80 psig depending on loading). In another embodiment, treated permeate with virtually non-detectable amount of carbon materials is essentially saturated and the ozonated stream contacted with pressurized influent. This method of contacting influent with ozone requires water to be filtered twice but allows for higher concentrations of ozone to be safely achieved, increasing viability of the invention.
[0010] As explained above, the ozonated wastewater will contain a greater portion of more readily biodegradable oxygen demand (rBOD) and be oxygen-rich, making it more treatable and improving process efficiency in three ways by reducing: (1) the volume of the tank by more than 20%; (2) the supplemental oxygen requirement by 20%-40% and; (3) the amount of air required for scouring membrane separators by 5%-10% depending on the residual oxygen concentration (above 10 mg/l gas evolution will occur). The total amount of oxygen required for any biological process is a function of the pollutant loading and other site conditions. The invention uses the oxygen byproduct of ozonation to meet some or all of the demand set by the process. Additional oxygen will ordinarily be necessary to meet the total biological demand, but not in all cases.
[0011] It is among the objects of the invention to improve the space efficiency and process efficiency of MBRs in removing microconstituents by contacting wastewater with ozone as a form of partial treatment or conditioning, thus breaking down refractory compounds into readily biodegradable materials, utilizing the oxygen byproduct of ozonation to supplement process oxygen, and in many cases offsetting membrane air scouring through gas evolution. These and other objects, advantages and features of the invention will be apparent from the following description of a preferred embodiment, considered along with the accompanying drawings.
DESCRIPTION OF THE DRAWINGS
[0012] FIGS. 1 and 2 are flow charts showing prior art liquid side wastewater treatment, with sedimentation or membrane filtration and with conventional post-treatment oxidation.
[0013] FIG. 3 is a flow chart indicating one embodiment of the invention where ozonated influent is fed directly into an MBR for full biological treatment and solids separation (filtration).
[0014] FIG. 4 is a flow chart indicating a second embodiment of the invention wherein ozonated influent is allowed to fully react before being fed into an MBR for full biological treatment and solids separation (filtration).
[0015] FIG. 5 is a flow chart indicating a third embodiment of the invention wherein a ozonated, reacted influent is saturated with oxygen to meet all or most of the process oxygen requirements.
[0016] FIG. 6 is a flow chart indicating a fourth embodiment of the invention wherein a slip stream of permeate is ozonated and then contacted with influent.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0017] FIGS. 1 and 2 show systems used in the prior art. In the system of FIG. 1 influent 10 enters the denitrification zone 12 , from which it passes to an aerobic zone 14 . Recycle back to the denitrification zone is shown at 15 , via a pump 16 . Process air is shown introduced to the aerobic zone by a blower 18 . As indicated, mixed liquor exiting the aerobic zone at 20 is introduced to a sedimentation tank 22 , from which settled sludge is withdrawn at 24 and delivered via a pump 26 to be recycled into the aerobic zone 14 , as shown at 28 .
[0018] In the conventional system of FIG. 1 , supernatant 30 from the sedimentation tank 22 goes to a membrane filtration zone 32 , where further solids are removed, and the permeate liquid may then be put through high pressure filtration in a reverse osmosis (RO) treatment 34 . The resulting liquid may be put through an oxidative post-disinfection treatment, indicated at 36 (this treatment could involve chlorination or other disinfectant or oxidative treatments). The membrane separation 32 can be for removing total suspended solids (TSS), turbidity, and pathogens. The RO treatment 34 can be for further removal of solids measured as silt density index (SDI), microconstituents, ionic species and pathogens. Post disinfection at 36 is generally for sterilizing or killing remaining pathogens (e.g. viruses) but can also be used to destroy microconstituents. These processes are expensive.
[0019] FIG. 2 shows a prior art system very similar to that of FIG. 1 , with the exception that a membrane filtration zone 38 replaces the sedimentation tank 22 . Air scour is shown introduced to the membrane zone 38 by a blower 40 , for cleaning the membranes and also to supply process air in the zone 38 . This zone 38 also replaces the membrane filtration shown at 32 in FIG. 1 , and again, the permeate from membrane filtration can be put through reverse osmosis or high pressure filtration at 34 , and a post-disinfection treatment at 36 , the zones 34 and 36 being for the purpose of removal or destruction of pathogens, microconstituents and other components as noted above that have been present in the influent.
[0020] FIG. 3 shows one embodiment of the invention. Here, influent 10 , which has been fine-screened or degritted in a pretreatment step, is shown as put under pressure by a pump 42 , so that it is delivered under pressure into the ozone saturation zone 44 . Pressure can be, for example, about 25 to 80 psig, or somewhat higher. The influent is aerosolized in the presence of gaseous ozone and saturated according to Henry's Law, to achieve saturation concentrations greater than 25 mg/l. However, the solids in the wastewater are combustible, so that aerosol pressure must be controlled to keep the aerosol at a safe level to prevent auto-ignition.
[0021] In the system of FIG. 3 the ozonated, saturated or essentially saturated influent passes into a membrane biological reactor or MBR, shown at 46 . From the point of saturation 44 , dissolved ozone rapidly reacts with carbonaceous materials including refractory organic compounds such as microconstituents. Depending on the hydraulic residence time (HRT) between saturation and discharge into the membrane biological reactor 46 , some or all of the ozone may be converted into oxygen. A blower 40 is shown introducing air for air scour in the MBR 46 . The ozonated, ozone rich influent entering the MBR is depressurized; the MBR zone is not under pressure. As a result, a small envelope or area around the point of discharge is temporarily supersaturated and conversion of remaining ozone to oxygen is rapid in the presence of mixed liquor (ML). Some of the oxygen byproduct may evolve as bubbles in the MBR or all of the oxygen can diffuse into the bulk solution. This helps supply process oxygen to the ML in the MBR. In addition, the ozone introduced in the zone 44 breaks down microconstituents or refractory materials as explained above, resulting in smaller, more readily biodegradable compounds as well as the released oxygen. The oxygen bubbles evolving in the MBR 46 can contribute to air scouring of the membrane separators, and the point of introduction of the ozonated influent in the MBR tank 46 can be arranged so that the evolving bubbles add to the air scour bubbles from the blower 40 for scouring membranes.
[0022] As indicated in FIG. 3 , permeate at 48 can be directed to an optional denitrification zone 50 , where a final denitrification step includes running the permeate through filters or other equipment for removal of nitrates. Denitrified permeate effluent from the zone 50 is shown at 52 .
[0023] By use of the ozonation, particularly at saturation or near-saturation and under pressure, this produces a greater proportion of more readily biodegradable oxygen demand and results in reduction of tank volume, reduction of supplemental oxygen requirements and usually reduction in scour air requirements, depending on the residual oxygen concentration and the evolution of bubbles in the zone 46 . With enough process oxygen supplied to the MBR and with sufficient inventory of biological solids in the MBR, a separate aerobic zone is not necessary. By not putting the influent directly into an anoxic zone, as conventionally done, the system of the invention can take advantage of the oxygen created by ozonation. Although the system theoretically gives up the efficiency of using nitrates of a recycle stream (e.g. the stream 15 in FIG. 1 ) to meet oxygen demand in an initial anoxic zone, the ozonation makes up for this through breakdown of refractories and reduction of supplemental oxygen requirements.
[0024] FIG. 4 shows a variation of the system of FIG. 3 . In this modified embodiment the ozonated influent is allowed to fully react before being fed into an MBR 46 for full biological treatment and solids separation by filtration. The treatment of influent 10 is similar to the system of FIG. 3 , except that on leaving the ozonation zone 44 the ozonated influent is allowed to more fully react in a pressurized ozone reaction zone 54 . This permits the ozone to be kept in solution, preferably at near saturation under the pressurized conditions, for a longer period of time so that breakdown of microconstituents can be more thorough. The remaining steps and zones are similar to those of the FIG. 3 system.
[0025] FIG. 5 shows a third embodiment of the invention, a variation of the FIG. 4 system. This system adds to FIG. 4 an oxygen post-saturation zone 56 downstream of the ozone reaction zone 54 . The ozonated, reactive influent from the zones 44 and 54 is then saturated or essentially saturated with oxygen, preferably still under pressure, to provide sufficient oxygen to meet essentially all of the process oxygen requirements. Pressure may be in a range of about 80 to 110 psig, to produce an oxygen concentration of at least about 250 mg/l, and preferably about 300 mg/l. Again, the biological reactions occur in the MBR 46 , in which the influent is depressurized. Oxygen may evolve as useful scouring bubbles, reducing blower 40 requirements and providing process oxygen; soluble oxygen may also diffuse from a zone of supersaturation around the point of discharge and into the bulk solution at less than or equal to standard conditions from both the reacted ozone remaining in solution and the oxygen introduced in the zone 56 .
[0026] FIG. 6 is another flow chart showing a further modification of the systems described above. In this form of system, influent at 10 is again pressurized via a pump shown at 42 and enters an ozone reaction zone 58 followed by an oxygen saturation zone 60 , both under pressure. The ozone in the stream comes from a pressurized permeate stream, a recycle stream 61 with ozonation, as described below. The influent stream, blended with permeate, is saturated or essentially saturated with oxygen at the pressure in the zone, which may be in the range of about 80 to 200 psig, and the influent at this point has ozone. The influent with dissolved oxygen is then delivered to an MBR 62 , where the liquid is depressurized and oxygen diffuses into the bulk solution, offgases forming scouring bubbles, or both, depending on conditions. Again, any bubbles formed can be used to supplement air scour via a blower 40 , lowering air scour requirements in most cases. Oxygen concentration can be maintained greater than about 8 mg/l to increase aerobic respiration rates and reduce necessary residence times. The permeate 64 from the MBR is then primarily directed to an optional denitrification zone 50 , if included in the system, and denitrified permeate effluent exits the system at 52 (or discharged as effluent without denitrification). Alternatively, the MBR zone 62 (as with the MBR zones in FIGS. 3-5 ) can be maintained at a low residual oxygen concentration, less than about 2 mg/l, to induce simultaneous nitrification and denitrification, removing nitrates and ordinarily avoiding the need for zone 50 .
[0027] However, a portion of the permeate 64 from the MBR is directed, as shown at 66 , through a pressurizing pump 68 and to an ozone saturation zone 69 , under pressure, as the permeate stream 61 described above. Thus the permeate at 61 , which may comprise about 25 percent or more of the permeate at 64 , is saturated or essentially saturated with ozone at the pressure under which it is maintained (range of approximately 20 psi to 100 psi). This pressurized, ozonated stream enters the influent stream downstream of the influent pump 42 , producing at 72 an ozone-laden influent mix which has combined the essentially ozone-saturated permeate at 61 with the raw and pressurized influent. This is the pressurized influent to the ozone reaction zone 58 and then to the oxygen saturation zone 60 , producing a heavily oxygen and ozone-laden influent on depressurized entry into the MBR 62 . Oxygen bubbles evolve in the MBR from both the oxygen and ozone contained in the influent, providing for essentially all process oxygen requirements in the zone 62 and potentially reducing air scour requirements by the blower 40 . As discussed above, this system safely ozonates the permeate water, which can be by high-pressure aerosol methods, rather than directly ozonating the influent as in the systems of FIGS. 3 and 4 .
[0028] In a variation of the system as described, oxygen alone can be saturated into the incoming wastewater. Such a system could be as in FIG. 3 or 4 , but with oxygen saturation and reaction zones rather than ozone saturation and reaction zones. Oxygen pressures can be higher, such as a range of about 110 to 300 psig, and can produce an oxygen concentration greater than about 300 mg/l.
[0029] All references to pressure in p.s.i. refer to gauge pressure (psig, above atmospheric). References to supersaturation are relative to saturation levels at standard temperature and pressure.
[0030] The above described preferred embodiments are intended to illustrate the principles of the invention, but not to limit its scope. Other embodiments and variations to these preferred embodiments will be apparent to those skilled in the art and may be made without departing from the spirit and scope of the invention as defined in the following claims. | In a sewage treatment system, microconstituents, including personal care products and pharmaceutical materials, often difficult to degrade biologically, are removed by supersaturating the untreated wastewater feed with ozone. This breaks down refractory microconstituents into more readily biodegradable materials, subsequently treated preferably in an activated sludge membrane bioreactor process. The oxygen biproduct of ozonation is utilized by feeding the oxygen into an aerobic part of the plant to meet a portion of the biological demand, thereby increasing efficiency of ozone use in the process. | 2 |
This is a continuation of application Ser. No. 699,992, filed June 25, 1976, now abandoned.
The invention relates to a take-up head for a bulk material conveyor installation, the head having a take-up aperture for upward conveyance of bulk material and a rotary feeder around the take-up aperture to feed the material inwardly towards that aperture. Such take-up heads are used particularly (though not exclusively) in ship unloading installations employing a pneumatic conveying pipe or a chain conveyor for lifing bulk material out of a ship's hold.
It is known that the action of moisture and pressure makes many bulk materials lose their easy flow properties when they spend a relatively long period of time in the hold of a ship, and they form such a compact mass that strong mechanical forces are required to loosen them for offloading.
Ships and the bulk materials in them are at times subjected to considerable movements because of the motion of the water. This leads to substantial technical difficulty during offloading if the offloading installation is fixed on shore and the take-up head has to carry out specific movements and apply mechanical force for loosening, conveying and taking up the bulk material independently of relative movements between ship and offloading installation.
One known solution utilizing a rotary feeder around the take-up aperture does not allow systematic unloading. With greatly compressed material there is a tendency to drill holes in the bed of bulk material in honeycomb fashion so that thin "walls" of bulk material are left standing several meters in height. These walls have to be broken up in order to allow the bulk material to be brought to the take-up head. It would be possible to force the take-up head to carry out desired movements with a rope system, but in many cases this is very cumbersome.
The invention has aimed at developing an apparatus which in at least some of its forms can be introduced through small openings such as the hatches on a ship, and can loosen mechanically and take up the bulk material without the use of rope systems and the like.
Bulk materials such as wheat flow freely to the suction nozzle of a pneumatic conveyor where they are taken up and transported away, and the method of operation is straightforward. However, bulk materials with poor flow properties must initially be loosened and fed to the suction nozzle so that the desired conveying output can be maintained.
The same applies to ship unloading installations using chain conveyors.
In material transfer work with high delivery rates (for example, 100 tons per hour and above per conveying unit), dragline crawler apparatus and other means known in the construction industry are used in order to bring the bulk material to the take-up head of the unloading installation.
In recent times, the same object has been achieved by providing a special scraper conveyor which is moved and controlled in conjunction with the unloading installation. Thus, in a very economical manner large quantities can be transferred in a very short time without dust nuisance and without risk of accident to the operators. Relative movements between ship and shore is taken up by special construction of the entire unloading installation. But in many cases it has not been possible to utilize these measures in small installations while keeping within economical limits.
It has been found disadvantageous on many occasions that ship unloading installations in the medium and relatively small conveying capacity range of possibly up to a few hundred tons per hour, and particularly with products which have difficult flow properties or are tightly compacted, could only be used at the intended capacity rate with the use of feed scoops and other aids. Therefore, part of the objective has been to develop an apparatus which in at least some of its forms is suitable for relatively small and medium unloading installations wherein an optimum material removal technique would be possible in accordance with particular conditions such as the size of the ship, the type and condition of the product, etc.; so that, for example, one horizontal layer of bulk material after the other can be taken away without requiring expensive force-transmitting and anti-overloading systems.
Accordingly in one of its aspects the invention provides a take-up head for a bulk material conveyor installation, the head having a take-up aperture for upward conveyance of bulk material, a standing part, a rotary feeder at the take-up aperture and a drive for rotating the feeder relative to the standing part for inward feed of material to the take-up aperture, at least one anchorage member of which at least part can be raised and lowered and which extends outwardly with respect to the take-up aperture, and a downwardly projecting hold member coaxial with the rotary feeder, the arrangement being such that in use of the head the hold member can engage in the underlying bulk material thereby to help hold the head against lateral movement and the anchorage member can engage in the bulk material remote from the rotary member thereby to help anchor the standing part against rotation. Preferably the rotary feeder includes spiral vanes extending spirally outward as seen in plan of the feeder and arranged for inward feed of material to the take-up aperture. The or each anchorage member preferably extends radially with respect to the standing part, and is preferably pivotally secured to the standing part so that it can be raised and lowered with respect thereto.
In one preferred form of the invention, a plurality of anchorage members are provided each being a radially extending pivotable arm pivotally attached to the standing part and preferably having a blade at its remote end region to facilitate anchorage in the bulk material.
In an alternative preferred form the anchorage member is itself an auxiliary conveyor extending radially from the standing part. In the course of conveying loosened material to the take-up aperture the auxiliary conveyor can work its way into the bulk material and hence provide anchorage therein.
In forms of the invention in which the take-up aperture leads into a pneumatic conveyor pipe, the hold member may be fast with the rotary feeder so as to rotate therewith.
On the other hand, in forms of the invention cooperating with a chain conveyor, the take-up head may include a reversal station for the chain conveyor, the reversal station having at least one lateral take-up aperture and being open underneath whereby cross bars of the conveyor chain while extending underneath constitute the hold member.
For ship unloading installations and pneumatic conveying pipe preferably comprises per se known telescopically mobile intermediate elements and the ship chain conveyor comprises special joints so that in both cases movements of ships can be absorbed and are not transmitted to structural parts of the ship unloading installation connected to dry land.
According to another of its aspects the invention provides a method of taking up bulk material into a conveyor which includes the steps of lowering onto the bulk material a take-up head having a take-up aperture, rotating a feeder around the take-up aperture for inward feed of material to that aperture, causing a downwardly projecting hold member co-axial with the feed member to engage in the underlying bulk material to help hold the head against lateral movement and causing an anchorage member extending outwardly with respect to the take-up aperture to engage in the bulk material remote from the rotary member to help anchor against rotation a standing part from which the rotary feeder is rotated. For unloading bulk material from the hold of a ship the method preferably includes the step of moving the take-up head laterally from time to time by appropriate movement of a land based jib from which the take-up head is suspended thereby to take up increasing parts of a layer of bulk material from the hold, and preferably also the step of lowering the take-up head further by appropriate movement with respect to a land based jib after the take-up head has taken up a layer of material and then causing it to take up a subjacent layer.
According to yet another of its aspects the invention provides a take-up head for a bulk material conveyor installation, the head having a take-up aperture for upward conveyance of bulk material, a standing part, a feeder at the take-up aperture for inward feed of material to the take-up aperture and an auxiliary conveyor which extends outwardly with respect to the take-up aperture and which can be raised and lowered and be rotated with respect to the take-up aperture, and which has a raised transfer end proximate the take-up aperture for delivery of material into the feeder from above the drive means for rotation of the auxiliary conveyor relative to the standing part. This form of take-up head may of course be used in conjunction with the features described in relation to other aspects of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
For a better understanding of the invention three embodiments thereof will now be described with reference to the accompanying drawings in which:
FIG. 1 shows partly in elevation and in section the take-up head of a pneumatic conveying pipe of a first embodiment;
FIG. 2 is a section taken along line II--II of FIG. 1;
FIG. 3 illustrates the arrangement of the feed spiral, the loosening and centering tip and the pivotable arms of the embodiment of FIGS. 1 and 2;
FIG. 4 shows in elevation and partly in section the take-up head with a chain conveyor of a second embodiment;
FIG. 5 is a section taken along the line V--V of FIG. 4;
FIG. 6 illustrates diagrammatically a complete unloading installation that includes the embodiment of FIGS. 4 and 5;
FIG. 7 shows a third embodiment with an auxiliary conveyor; and
FIG. 8 is a section taken along the line VIII--VIII of FIG. 7.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows the first embodiment of the invention with a pneumatic conveying pipe 1. A lower telescopic pipe 1' can be slid into the conveying pipe 1. The conveying pipe 1 also comprises an elastic or flexible intermediate element 1" which allows for substantial horizontal swivelling movement of the take-up head 2. The telescopic pipe 1' ends in the lower region of the take-up head 2 with a take-up aperture 3. By means of a flange 4 a standing or stationary part in the form of a frame 5 is connected rigidly to the telescopic pipe 1' to act as a protective frame or guard. In and below the protective frame 5 is mounted a rotary feeder in the form of a rotary plate 7 provided with feed spirals 6. The rotary plate 7 is mounted by means of a lower axial bearing 8 and an upper radial bearing 9 so as to be capable of rotational movement on the telescopic pipe 1'. The rotary plate 7 also has a toothed driving wheel 10 in the upper region which can be rotated by a chain 11 engaging a toothed wheel 12 driven by a drive motor 13. The protective frame 5 also comprises a covering ring 14 which together with a second protective ring 15 situated on the rotary plate 7 prevents product from readily gaining access to the region of the drive. The entire take-up head can be lifted and lowered by ropes 16 which are secured on a strap 17 of the telescopic pipe 1'. The lifing and lowering apparatus (not shown) can be adapted to suit the particular requirements in each case. Anchorage members in the form of pivotable arms 20 are connected pivotably to the protective frame 5 in each case by a pivot pin 21 extending horizontally. Each pivotable arm 20 consists of an extension bar 22 and a blade 23. Supports 24 for the pivotable arms 20 are secured to the protective frame 5, each having an upper abutment 25 and a lower abutment 26.
The pivotable arm 20 is shown in an upper working position at the right-hand side of the illustration. The blade 23 has sunk into the product. At the left-hand side the pivotable arm 20' is shown in the lowest end position and the pivotable arm 20" shown in dot-dash lines is shown in the uppermost end position. In this constructional form the pivotable arm 20 can move freely within an angle to about 90°.
As shown by FIGS. 2 and 3 the feed spiral 6 is an assembly of three separate spiral vanes. Three or more spirals have the advantage of more uniform and steadier running than two spirals or even only one spiral. Four pivotable arms 20 are provided outside the working region of the feed spiral assembly 6 on the protective frame 5.
FIG. 3 also shows diagrammatically a hold member in the form of a tip 30 here consisting of a three-pronged tip which (as shown in FIG. 1) projects beyond the feed spiral into the bulk material. The tip 30 is made from simple flat sections and connected directly to the feed spiral 6.
The pivotable arms 20 prevent rotation of the stationary protective frame 5 and therefore of the telescopic tube 1' since at least one of the pivotable arms 20 is in contact with the bulk material. The conveying pipe 1 together with the protective frame 5 and the pivotable arms 20 are intended normally to carry out only an upwardly or downwardly directed movement. However, the tip 30 preferably carries out a rotary movement with the rotary plate 7. The resistance presented by the bulk material to the rotary movement of the feed spiral, or in other words the reaction forces, are transmitted directly by way of the driving wheel 10, the chain 11, the toothed wheel 12 and drive motor 13 to the protective frame 5, and then taken by the pivotable arms 20 in the bulk material itself. The tip 30 is formed of three upright flat sections 31 which are brought together and connected to the feed spiral 6.
The embodiment shown in FIGS. 1 to 3 operates as follows.
The conveying pipe 1 and therefore the entire take-up head 2 with the telescopic pipe 1' is suspended on a support structure constructed somewhat as shown in FIG. 6, and can be brought to any desired point in the predetermined working range and lowered onto the bulk material. It is not important whether the tip 30, the feed spiral 6 or the pivotable arms 20 happen to contact the bulk material first, since small heaps of bulk material present only small resistance. But it is very important that at least one of the pivotable arms 20 and the tip 30 come into contact with the bulk material before the actual loosening and feeding work is carried out by the feed spiral 6. The large reaction moments usually occur only once the feed spiral 6 begins to feed the product over a large area to the aperture 3 of the telescopic pipe 1'. The tip 30 immediately works its way into the bulk material. Since it is not formed of a horizontally extending flat disc but is formed of upright flat section members, it has a loosening and centering action at the same time. The centering action can be imagined as similar to that of wood drills. The deeper the rotary plate 7 works into the bulk material, the greater does the resistance opposed to the rotary movement become. But the pivotable arms 20, or the blades 23 to be more precise, continually descend further into the bulk material and thus can take up very considerable reaction forces in the peripheral direction of the rotary plate 7. If, as shown by FIG. 1, the take-up head is applied against a sloping face of a pile of material and if it did not embody the present invention, the entire head would be driven or knocked away from the slope at the first substantial resistance encountered by the feed spirals. This is now effectively prevented by the tip 30. Before the take-up head encounters the bulk material the pneumatic suction fans (not shown here) are of course already switched on for producing a strong flow of conveying air into the pneumatic conveying pipe. The suction air provided for conveying purposes can, as is known, draw in the product only over a very restricted aspiration region.
It has been found that the cooperation of the feed spiral and the tip 30 keeps loosened-up bulk material ready in an easily flowing condition directly at the foresaid aspiration region. The feed spiral and the tip 30 thus assist the drawing of the bulk material into the pneumatic conveying pipe 1 in a very advantageous manner. The bulk material can be taken up uniformly with very high conveying throughflow rates and conveyed away so that the energy provided for the individual conveyors can be utilized in a more satisfactory manner than hitherto.
The take-up head can be lowered to any desired depth, for example to the bottom of bulk carrier barge. In order to prevent damaging the bottom of the barge it is possible to provide foot elements on the protective frame 5 which project beyond the tip 30 and on which the entire take-up head can rest. When the take-up head reaches the bottom of the boat, it can be drawn upwards with the telescopic pipe 1' and the pneumatic conveying pipe, and the operation can be repeated after moving the entire conveying unit laterally. The feed spiral need not lie on the bulk material over its entire area, since at least one, two or three pivotable arms 20 and the tip 30 can always be made to operate.
FIGS. 4 and 5 show an embodiment of the invention with a take-up head 35 including a chain conveyor 38. The rotary plate 36 itself is identical in construction to that of FIG. 1 and some of its reference numerals have been adopted. In this embodiment, the entire rotary plate 36 is constructed so that it can be lifted and lowered with respect to the chain conveyor 38. The chain conveyor 38 comprises a take-up aperture 41 at each of the two sides of the lower portion of the take-up head 37. The chain conveyor 38 comprises two duct portions, a return duct 39 and the actual product conveying duct 40. The two duct portions are closed off from the outside. Below a reversal station 42 the take-up head 35 is open so that the individual cross-bars 44 of the conveying chain 45 project beyond the closed wall portions to the take-up head. The take-up head 37 has supports 46 at each corner which project a slight distance beyond the outermost points of the cross-bars 44, so that the bottoms of ships cannot be damaged by the cross-bars 44.
The rotary plate 36 can be lifted and lowered by two hydraulic cylinders 50. The control of the hydraulic cylinders 50 is not shown, but is effected in the usual way from a control desk or panel for the chain conveyor installation. Both hydraulic cylinders 50 are shown in their full length in FIG. 6. The entire rotary plate 36 together with the protective frame can be lifted or lowered by approximately half the height of the take-up head 37. The usual working position will correspond approximately to the full-line position. For further unloading of the residue or remnant of bulk material the rotary plate 7 can then be brought into the position shown in dot-dash lines. Depending on the characteristics of the product and the specific application concerned, the rotary plate 36 can be adjusted into any working position between the two extreme end positions.
FIG. 6 shows in a diagrammatic manner a complete ship unloading installation incorporating the take-up head of FIGS. 4 and 5. The terrace-like contours shown for the material being unloaded from the ship are intended to indicate that the bulk material is no longer in a flowable condition, so that it is necessary to loosen and break down the bedded material to be able to unload economically. The take-up head 35 is in direct contact with the bulk material and anchored therein as already explained. The movements of the ship are transmitted directly to the take-up head 35 and the chain conveyor 38. Between a conveyor 59 and the chain conveyor 38 a transfer joint 51 and a telescopic pipe 52 are arranged which can take up these movements. The chain conveyor 38 is held by means of a rope 53 which in its turn is held on a jib 54 of an unloading tower 55. The bulk material can be fed to land vehicles or the like or into storage means by way of a down pipe 56. The unloading tower 55 can travel at right angles to the plane of the drawing and the jib 54 can be lifted or lowered about a pivoting joint 56 as indicated in dot-dash lines. The movements of the ship disturb neither the construction of the unloading installation nor the working of the take-up head 37.
Operation is as follows.
The take-up head 37 is lowered by the jib 54 and the rope 53 onto the bulk material. In this first phase the rotary plate 36 is in its uppermost position relatively to the take-up head 37. The chain conveyor 38 is the first to contact the product and it digs into the product by means of its downwardly projecting cross-bars 44 constituting the hold member or tip in this case. The cross-bars 44 also dig into the consolidated bulk material as scraper elements. If the bulk material is tightly compacted, and fails to flow or slide to follow the digging action, then after the take-up head 37 has worked its way in approximately as far as the middle height of the take-up aperture 41, the rotary plate 36 is lowered onto the bulk material. The take-up head 37 is secured against swinging out of position laterally by the lowest part of the take-up head 37 which has already worked itself into the product. Since the pivotable arms 20 contact the product before the feed spiral, they can immediately prevent rotational movement of the take-up head 37. The rotary plate 36 is left in the position once selected for it relatively to the take-up aperture 41. The unit comprising chain conveyor 38 and rotary plate 36 is lowered into the product in accordance with the progressive digging-away of the bulk material. Only when the supports 46 strike against the bottom, for example of a barge, the rotary plate 36 is also lowered almost as far as the bottom. It is quite possible to arrange that the downwardly projecting cross-bars 44 of the chain conveyor 38 may be protected laterally and downwardly where appropriate by guard means to prevent direct contact with persons working in the hold, thus preventing accidents.
The arrangement and operation of the pivotable arms 20 is in accordance with the construction of FIG. 1. The main difference in the construction of FIGS. 4 and 5 is primarily the special construction of the tip 30, and also the possibility of displacing the entire rotary plate 7 together with the protective frame 5 relatively to the chain conveyor 38 and its take-up aperture 41.
In the constructional form shown in FIG. 1, it would be quite possible to displace the rotary plate relatively to the conveying pipe or the take-up aperture 3. But since the vertical displacement of the feed spiral 6 relatively to the take-up aperture 3 would mainly be for residual or remnant unloading rather than the main unloading operation, there would mostly be no point in providing for the rotary plate 7 to be displaced relatively to the pneumatic conveying pipe 1. In the chain conveyor 38, on the other hand, the displacement of the rotary plate 36 relatively to the aperture 41 follows from the general construction of the conveyor, more particularly the construction of the take-up head.
The drive of the rotary plate can be effected in various ways. It is possible to construct the drive motor 13 as an electric motor or as a hydraulic drive.
The third embodiment shown in FIGS. 7 and 8 comprises the following main groups. A pneumatic conveying pipe 100, a common frame 101, a rotary plate 102 with tip 103, an anchorage member in the form of an auxiliary conveyor 104, an upper main rotary bearing 105 and a lower main rotary bearing 106.
The arrangement for suspending the entire take-up head can be similar to those of the first and second embodiments, so that here again the entire unit is anchored in the bulk material.
The pneumatic conveying pipe 100 comprises in the uppermost portion reinforcing ribs 110 and also two flange connections 111 and 112. A race ring 113 of the upper main rotary bearing 105 and a race ring 114 of the lower main rotary bearing 106 are connected securely to the pneumatic conveying pipe 100.
The pneumatic conveying pipe 100 terminates below in a take-up suction aperture 115. The common frame 101 can be turned about the pneumatic conveying pipe 100 by means of the two main rotary bearings 105 and 106, so that the auxiliary conveyor which is pivotably connected to the common frame 101 can be swung through perhaps 360° about the vertical axis 116 of the pneumatic conveying pipe 100, as indicated in FIG. 8. The swinging movement is carried out by a drive motor 117 by way of a toothed wheel 118, a chain 119 and a toothed wheel 120.
The auxiliary conveyor is secured to be capable of being lifted and lowered by means of a horizontal pivotable joint 120 on the common frame 101. The lifting and lowering movements are carried out by a hydraulic cylinder 121 which is also arranged on the common frame 101, and is connected by control lines to a control desk.
The auxiliary conveyor 104 preferably comprises a conveying chain 122 with scraper blades 123 so that the bulk material can be loosened and conveyed. The conveying chain is driven by a motor 124 and drive chains 125. In addition to the necessary elements such as clamping devices 126, etc., the auxiliary conveyor 104 is formed with an angled structure as a special feature of it. In the horizontal working position, which is shown in full lines, the inner transfer end 130 is directed obliquely upwards in the region of the rotary blade 102. These arrangements result in a particularly advantageous method of operation since the bulk material is moved without unnecessary pressure, transverse displacements etc. directly into the working range of the feed spiral of the rotary plate 102. With good constructional arrangement of the entrainment elements of the rotary plate, for example in the form of logarithmic spirals, the bulk material can be conveyed from the place from where it is moved into the working region of the rotary plate over the shortest distance to the tip 103 and engaged there by conveying force while in the moved state, and transported away.
Mechanical loosening, conveying, acceleration and pneumatic transport can in this way supplement one another in the optimum manner.
It is not important at which region in the peripheral direction of the rotary plate 102 the auxiliary conveyor 104 delivers the bulk material, the conditions always being the same.
The feature of arranging the horizontal pivoting joint 120 or rather the inner transfer end 130 above the rotary plate 102 so that the bulk material is not pressed laterally against the rotary plate but lifted over, and conveyed from above into the working region of the rotary plate 102, has been found to be particularly advantageous.
It will be readily appreciated that on the one hand the rotary plate 102 with the tip 103 gives the auxiliary conveyor 104 the necessary hold against horizontal slipping away of the entire head, and on the other hand the auxiliary conveyor 104 gives the rotary plate 102 the necessary anchorage for preventing turning movement of the entire unit about the vertical axis 116.
The rotary plate can be constructed substantially in accordance with FIG. 1. In the illustrated construction a drive motor 131 is mounted on the common frame.
There is arranged about the feed spiral of the rotary plate 102 a holding ring 132 which takes up the constant large thrusting forces of the auxiliary conveyor in the lateral direction, and prevents rotary plate 102 working its way laterally. As can be seen from FIG. 7, the holding ring 132 does not extend along the entire height of the feed spiral, and need not necessarily be formed of a complete closed ring.
Since these are apparatus of great size and it is often necessary for the working operations to be controlled and supervised by a person, a control chain 140 can be secured on the common frame 101.
The constructions described above allow a very wide range of use, both in pneumatic conveying pipes and also chain conveyors, which can achieve reliable loosening and conveying away of bulk materials at a considerable delivery rate, by optimum cooperation of rotary plate and conveying element even in very difficult conditions with tightly compressed bulk materials and when working on sloping faces of material beds.
The advantageous method of operation is obtained as a result of the cooperation of the securing element with the preferably mechanically moved tip. The securing element prevents more particularly turning movements of the take-up head. The tip gives the take-up head guidance in the direction of the axis of rotation of the feed spiral, so that the conveying unit in general is prevented from swinging out laterally even under extreme conditions, and the bulk material can be loosened and fed to the suction nozzle in all cases.
The force required for loosening and taking up the bulk material can be completely received and absorbed by bulk material and take-up head cooperating with one another, the consolidated state of the bulk material being usefully employed, and the take-up head being anchored in the said material.
If the frame is constructed as an accident protection frame for the feed spiral, it normally does not carry out any rotary movement.
If upper and lower abutments for the pivotable arms are provided, then in the condition of rest the pivotable arms because of their own dead weight remain in the lower end position and contact the product when the take-up head is lowered before the feed spiral. The pivotable arms could also be held in the lowest position by spring force. It is expedient if the lower and upper positions of the pivotable arms are situated approximately symmetrically relatively to a horizontal straight line drawn through the pivoting point. When the take-up head is lowered, as a result, there is a slightly outwardly directed movement of the pivotable arms which therefore penetrate to an increased extent into the bulk material. On downward movement in the bulk material the pivoting arms move upwards relatively to the feed spiral. In the uppermost end position of the pivotable arms the outermost tips are again at a relatively small diameter relatively to the central position. The take-up head can penetrate downwards into the bulk material to an extent depending on the type of material removing technique selected. When the take-up head is taken out of the product the pivotable arms can be swung into the lowest end position and drawn upwards.
It is also very advantageous to construct the pivotable arms as blades at their outer ends. Thus they present very little resistance to the lifting and lowering of the take-up head, whereas they present the maximum possible effective surface against movement in the peripheral direction.
The outermost tips of the pivotable arms are to project in the outermost working position to the extent of at least 10-20% of the rotor diameter beyond the rotor.
When the mechanically moved tip is formed of upright elements, for example a projecting three-pronged tip, it works its way into the bulk material by a rotary movement and at the same time keeps ready in a loosened-up state the material introduced by the feed spiral.
Similarly when the mechanically moved tip is formed of chain elements guided about the reversal station they rapidly dig into the bulk material. The operation can be compared to the wheel of a motor car which is digging itself very quickly into snow and in the extreme case results in the unpleasant effect that the entire car is prevented from further horizontal movement.
Since the chain in chain conveyors is turned round through a relatively tight bend about the reversal station, there are only brief duration small horizontal forces which can be balanced already by the inertia of the take-up head.
After the feed signal encounters the bulk material, the speed at which the entire unit is lowered is determined substantially by the rotary plate, since it has a much larger bearing contact surface than the chain conveyor. The moved chain elements must ensure further conveyance of the bulk material and the penetration of the take-up head into the bulk material.
Therefore in the case of a chain conveyor the tip gives the take-up head a very strong centering or directing force preventing any swinging-out movements to the side.
In the construction that includes an auxiliary conveyor the individual conveying elements are balanced to a particularly good extent relatively to one another, which is very important more particularly in the case of a pneumatic conveying pipe.
A pneumatic conveying pipe is only capable of drawing in freely flowing bulk materials.
The auxiliary conveyor loosens the bulk material and guides it continuously to a region of an annular working area of the feed spiral, which conveys it, loosened up, directly to the reception aperture of the pneumatic conveying pipe. The auxiliary conveyor gives the feed spiral the necessary "grip" to prevent the unit from "turning in a circle". The thrust forces of the auxiliary conveyor are taken up by the feed spiral.
In this construction it has been found very advantageous to arrange about the feed spiral the preferably nonrotating lateral holding ring which is secured on the common frame. The holding ring laterally shields at least partly the said feed spiral so that a proportion of the considerable lateral thrust forces of the auxiliary conveyor are taken over by the holding ring. In this way, it is possible to prevent the feed spiral from working its way out of position towards the side. The continuously rotating feed spiral forms a circular hole when there is downward movement into the bulk material and without a downward movement the feed spiral takes bulk material from an annular area. This fact is utilized by arranging for the auxiliary conveyor to slightly lift the bulk material and feed it from above into the circular area operated on by the feed spiral. The auxiliary conveyor can in principle be turned through 360° in order to remove bulk material over a large circular area, and can transfer the bulk material to the feed spiral at any part of the circular ring area worked, without any change in the transfer conditions. A continuous flow of bulk material can be maintained from the auxiliary conveyor by way of the feed spiral into the pneumatic conveying pipe, so that the latter can be operated without interruption at a constant maximum output, the result of this being that high rates of delivery are possible while using small amounts of energy per unit conveyed. This solution also allows optimum suction conditions, the bulk material being accelerated mechanically directly into the take-up aperture of the pneumatic conveying pipe, and this again helps to keep the energy consumption of the entire unloading installation at an advantageous low level. Thus it becomes possible to use pneumatic unloading installations with little constructional outlay and, relative to purely mechanical unloading installations, with relatively low consumption of energy per unit with conveying rates of up to several 100 tons per hour. Here again the relative movements between ship and unloading installation can be taken up by simple telescopic parts or known joints. In this way no expensive control or antioverloading arrangements are required, such as are necessary with large mechanical installations. | The disclosure is directed to a take-up head for a conveyor installation that removes bulk material from the hold of a ship. The take-up head includes a vertical conveying tube carried by a frame, the lower end of the tube defining a take-up aperture. A rotary feeder having a plurality of radially extending spiral veins is rotatably driven to drive material inwardly to the take-up aperture. A holding device, which takes various forms in the several embodiments, projects downward in coaxial relation relative to the feeder to engage the bulk material and resist lateral movement of the take-up head. Anchoring apparatus, which takes the form of a plurality of laterally extending pivotal arms or a laterally extending auxiliary conveyor, is constructed for lowering into engagement with the material to resist rotation of the frame as the feeder rotates. The take-up head is suspended from an on-shore jib that moves the head to various positions within the ship's hold to remove all bulk material. | 1 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. provisional application Serial No. 60/345,137, filed on Oct. 19, 2001.
FIELD OF THE INVENTION
The present invention relates to anti-pathogenic air filtration media and to air handling systems and personal devices that use air filters.
BACKGROUND OF THE INVENTION
Modern heating, ventilating and air conditioning (“HVAC”) systems recycle a large proportion of conditioned air, resulting in improved energy efficiency. Unfortunately, recycling of the air concentrates pathogens in enclosed areas where people congregate, like homes, office buildings and hospitals. This increases the burden on the immune systems of humans who live and work in such enclosed spaces and increases the risk of contracting an airborne infection.
Air handling equipment is also a refuge for microbes. Air ducts are dark and shielded from ambient UV light that inhibits the growth of many types of bacteria in outdoor environments. Condensation that occurs while the system is in cooling operation provides moisture to support growth of microorganisms. Dust particles deposited on the surfaces of ducts and air filters provide nutrients to microorganisms. Such nutrition is especially plentiful on air filters, which process thousands of cubic feet of dust laden air daily. It is now recognized that particulate filters for HVAC systems are propagators of airborne bacteria and are at least partly responsible for transmission of tuberculosis, Legionnaires disease and narcosomal infections in health care facilities. The development of High Efficiency Particulate Air (“HEPA”) air filters has not obviated the problem. HEPA filters are able to trap smaller particles than conventional filters, like some airborne microorganisms, and to hold them but they do not capture all airborne microorganisms and are not equipped to kill the microorganisms that they capture. Effort has been expended to develop HVAC systems with a reduced tendency to propagate microorganisms, with considerable emphasis being placed on the development of effective, long-lasting antimicrobial air filters.
U.S. Pat. No. 3,017,329, which issued in 1962, describes a germicidal and fungicidal filter that is said to decrease the likelihood that objectionable odors or viable germs and spores caused by bacteria or fungi colonies will be thrown off the filter. The filter contains a conventional non-woven filter medium with a coating of germicidal and fungicidal active agent applied either by spraying or bathing. The active agent is selected from organo silver compounds and organo tin compounds, which arc pH neutral and highly toxic to mammals. The active agent can be applied to the non-woven fiber during the conventional manufacturing process of a filter wherein the non-woven fiber is immersed in an aqueous bath containing a binder and optionally a fire retardant. Heating of the treated fabric drives off water, cures the binder and, according to the '329 patent, fixes the germicide onto the filter medium.
U.S. Pat. No. 3,116,969 describes a filter having an alkyl aryl quaternary ammonium chloride antiseptic compound that is held onto the filter fibers by a tacky composition that includes a hygroscopic agent, a thickening agent and a film forming agent.
U.S. Pat. No. 3,820,308 describes a sterilizing air filter having a wet oleaginous coating containing a quaternary ammonium salt as the sterilizing agent.
Dever, M. et al, Tappi Journal 1997, 80(3), 157, reports the results of a study of the antimicrobial efficacy achieved by incorporating an antimicrobial agent into the fibers of melt blown polypropylene air filters. Three unidentified antimicrobial agents were tested individually. Each agent was blended with polypropylene, which was then melt-blown to form the antimicrobial filter medium. Only two of the antimicrobial agents were detectable in the filter medium by FTIR after processing. The blended filter media were tested against common strains of gram positive and gram negative bacteria. Filter media containing the two detectable agents had antimicrobial properties, but the agents also affected the physical properties of the polypropylene by functioning as nucleating agents. Consequently, the polypropylene blends yielded filters with reduced collection efficiencies and thicker fibers than filters made from unblended polypropylene.
Foard, K. K. & Hanley, J. T., ASHRAE Trans. 2001, 107, 156, reports the results of field tests of the antimicrobial efficacy of filters treated with one of three unidentified antimicrobial agents. In field tests where microbial growth was seen on an untreated dust-loaded filter medium, growth also was seen on the treated counterpart. Known antimicrobial filter treatments produced little effect under the conditions in which they arc used.
Kanazawa, A. et al. J. Applied Polymer Sci. 1994, 54, 1305 describes an antimicrobial filter medium prepared by covalently immobilizing antimicrobial phosphonium chloride moieties onto a cellulose substrate. The filter was made by reacting a trialkyl-(3-trimethoxysilylpropyl) phosphonium chloride with the hydroxy groups of the cellulose. The investigators found that the chain length of the alkyl groups on phosphorous affected the potency of the filter but not the packing density. According to their measurements, the density of phosphonium chloride in the resulting filter was in excess of that which would be expected for a monolayer, thus indicating that the phosphonium salts were stacked. More lipophilic phosphonium salts, ie. those with longer alkyl chains, tended to have a higher capacity for capturing bacteria.
Okamoto, M. Proceedings of the Institute of Environmental Sciences and Technology, 1998, 122, discusses the use of silver zeolite as an antimicrobial agent in an air handling filter. According to the investigators, the silver zeolite was attached by a special binder to one side of the filter.
U.S. Patent Publication No. 2001/0045398 describes a process for the preparation of a non-woven porous material having particles immobilized in the interstices thereof by contacting the material with a suspension of particles of predetermined size and urging the suspension through the material so as to entrain the particles in the interstices of the material. The treated material is said to be useful as an antimicrobial barrier.
According to its English language abstract, International Publication No. WO 00/64264 discloses a bactericidal organic polymeric material for filters which is made of a polymer base comprising a backbone and bonded thereto a polymeric pendant group comprising units derived from an N-alkyl-N-vinylalkylamide and triiodide ions fixed to the polymeric material.
International Publication No. WO 02/058812 describes a filter medium containing timed release microcapsules of an antimicrobial agent. The microcapsules contain the agent suspended in a viscous solvent, which slowly diffuses out of the porous shell of the microcapsule. The microcapsules may be held to the fibrous substrate with an adhesive base such as gum arabic.
Other methods of removing infectious airborne microorganisms have been developed. One method uses a device that draws contaminated air into an enclosed chamber where it is percolated through a liquid so that the microorganisms become encapsulated in the liquid. This device suffers from drawbacks. Intimate mixing of the contaminated air with the liquid must be effected in order for the pathogens to be captured and eliminated. This design is not well suited for the high flow rates of a HVAC system and would be awkward and unwieldy to install and service.
Another method uses electrostatic precipitation to disinfect an airstream containing microorganisms, wherein electrostatic precipitation is combined with photocatalytic oxidation as discussed in U.S. Pat. No. 5,993,738. A system of this type uses electricity to charge the particulate matter in the air stream and an opposing grounded collector plate for collecting the charged particulates, wherein a photocatalyst and UV light destroy pathogens accumulating on the collector plates. The most widely available antimicrobial filter system for commercial or residential use, however, employs an ultraviolet light in combination with a filter. For instance, in U.S. Pat. No. 5,523,075 a filter chamber was described as having a series of UV lamps producing a specific wavelength of UV light to destroy airborne bacteria. One drawback of these filtering systems is that it is energy intensive to power the LW lamp and thus very expensive. Commercial HVACs in e.g., hospitals, use this filtration technology as do some home air purifiers (e.g., Ionic Breeze from Sharper Image).
There remains a need for further improvement in anti-microbial air filters. It is one goal of the present invention to provide an anti-pathogenic air filtration medium for air handling systems like HVACs commonly found in commercial and residential enclosed spaces like homes, hospitals, factories, office buildings and the like. Of course, the filter media of the present invention also find use against microorganisms deliberately introduced into the environment by combatants or terrorists. Gas masks typically offer protection against chemical agents, but not against biological pathogens like anthrax, small pox and the like. The filter media of the present invention are able to provide such protection when incorporated into a replaceable filter cartridge of a gas mask. U.S. Pat. No. 6,435,184, which is hereby incorporated by reference, provides a description of a conventional gas mask structure.
SUMMARY OF THE INVENTION
In one aspect, the present invention provides an anti-pathogenic air filtration medium comprising: a fibrous substrate comprising a plurality of intermingled fibers and surrounding each of a substantial proportion of the plurality of fibers, an anti-pathogenic coating comprising a polymer network. The polymer network may be a randomly cross-linked polymer, a covalently cross-linked linear polymer, a cast mixture of linear polymers cross-linked by ionic or hydrogen bonding interactions, a cross-linked polysiloxane polymer or a hybrid inorganic-organic sol gel material.
The polymer network may be anti-pathogenic in that it contains pendent functional groups or functional groups in the polymer backbone that are disruptive of the biological activity of microorganisms. Such groups include acidic groups, like sulfonic acid groups; quaternary ammonium groups, like alkyl pyridinium groups; and oxidizing functionality, like pyrrolidone-iodine complexes.
In an alternative embodiment, the polymer network is not necessarily anti-pathogenic but, under conditions of use, is capable of forming a gel with a liquid comprising an active agent in at least one non-volatile liquid diluent. Such liquids include solutions of acids, bases and oxidizing agents, metal colloid suspension, surfactant-laden oils and solutions of antimicrobial drugs.
In further aspects, the invention provides processes for fabricating the air filtration media of the invention as well as air filters and cartridges for air filters containing the air filtration media of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides an anti-pathogenic air filtration medium. A “pathogen” as that term is used in this disclosure refers to any disease-producing microorganism, including viruses, bacteria, algae, fungi, yeasts, and molds. The anti-pathogenic air filtration medium of this invention disrupts the biological activity of pathogens that become entrained in the filtration medium. The disruption in biological activity may kill the organism or inhibit its propagation.
The air filtration medium of the present invention comprises a fibrous substrate and an anti-pathogenic coating surrounding a substantial proportion of the substrate's fibers. Preferably, the anti-pathogenic coating surrounds not less than 80% of the fibers.
The anti-pathogenic coating comprises a polymer network. The air filtration medium acquires its stable antimicrobial characteristics from the coating and, in some embodiments, from the polymer network of the coating. The anti-pathogenic coating exploits the sensitivity of pathogens to harsh chemical environments, such as conditions of extreme pH and oxidizing conditions. In the past, it has been difficult to impart such properties to the fibrous media used in air filters. Liquid acids and bases, like aqueous solutions of hydrochloric acid, sulfuric acid, and liquid organic amines, are difficult to immobilize on a fibrous substrate. The same is true for strong liquid oxidizers and strongly solublizing substances like surfactant laden oils. As previously discussed, apparatuses that bubble air through liquids are unwieldy to incorporate and maintain in high volume air handling systems. Solid bases and oxidants like alkali metal and alkaline earth metal hydroxides are difficult to adhere to a fibrous substrate.
The polymer network does not significantly affect the physical properties of the substrate fibers, like tensile strength, elasticity and resistance to deformation.
The fibrous substrate is any porous natural or synthetic material made of intermingled fibers. The fibrous substrate can be woven or non-woven. Exemplary natural materials suitable for use as a fibrous substrate include cotton, wool and cellulose. Exemplary synthetic materials suitable for use as the fibrous substrate include spun polylakylenes such as polypropylene, polyethylene and the like; glass (i.e. fiberglass), polyester, cellulose acetate, polystyrene, vinyl, nylon, rayon, acrylic, acrylonitrile and high performance engineering plastics that can be spun into fibers. Especially preferred synthetic materials for forming the fibrous substrate are commercially available products: Teflon® and Teflaire® (PTFE), SoloFlo® (HDPE), Sontara® and Dacron® (polyester) and Xavan®, all of which are products of DuPont Chemical Co., as well as Airex® (fiberglass and polyester). The preferred fibrous substrates have large surface areas for air contact while causing little air resistance, resulting in a low pressure drop during operation. Techniques for weaving and forming non-woven fibrous mats from natural and synthetic materials arc well known in the art. Fibers of non-woven material may be held together with a binder.
The network polymer can be essentially any polymer that can withstand acidic, basic, oxidizing or strongly solubilizing substances without decomposing. Generally, the network polymer will be either (1) a randomly cross-linked polymer such as is formed by co-polymerization of a monomer with a bi- or multi-functional cross-linking agent, (2) a covalently cross-linked linear polymer, (3) a network formed of a mixture of linear polymers cross-linked by ionic or hydrogen bonding interactions, (4) a cross-linked polysiloxane polymer or (5) a hybrid inorganic-organic sol gel material. Exemplary random cross-linked polymers include cross-linked poly(styrene sulfonic acid) (free acid or salt), cross-linked polyacrylic acid (free acid or salt), poly(vinyl pyridine) quaternary ammonium salts, cross-linked polyethylenimine quaternary ammonium salts and cross-linked poly(hydroxyethylmethacrylate) (“polyHEMA”). Exemplary covalently cross-linked linear polymers include cross-linked carboxymethylcellulose and other cross-linked cellulose ethers (free acid or salt). Exemplary mixtures of linear polymers cross-linked by ionic or hydrogen bonding interactions include mixtures of poly(vinylpyrrolidone) and poly(sodium styrene sulfonate) and mixtures of poly(ethylene glycol) and poly(vinylpyrrolidone) and mixtures of carboxymethyl cellulose and hydroxyethyl cellulose and innately gel-forming polymers such as guar gum, xanthan gum and sodium alginate. Exemplary polysiloxanes include poly(dimethylsiloxane). Exemplary hybrid inorganic-organic materials include networks formed via the sol gel process from mixtures of tetrethoxysilane (TEOS) and bis(triethoxylsilyl)alkanes, such as bis(triethoxysilyl)methane.
Air filtration media of the present invention are provided in two embodiments. The embodiments are differentiated by the way that anti-pathogenic characteristics are imparted to the coating.
In one embodiment, the network polymer is anti-pathogenic. Cross-linked poly(styrenesulfonic acid) (free acid or salt), cross-linked poly(acrylic acid) (free acid or salt), cross-linked poly(methacrylic acid), cross-linked poly(vinyl pyridine) quaternary ammonium salts and cross-linked polyethylenimine quaternary ammonium salts are examples of anti-pathogenic network polymers.
In another embodiment, the network polymer is a gel-forming polymer that under conditions of use is gelled with an anti-pathogenic liquid. Cross-linked polyHEMA, cross-linked carboxymethylcellulose and other cross-linked cellulose ethers (free acid or salt), cast mixtures of poly(vinylpyrrolidone) and poly(sodium styrene sulfonate), cast mixtures of poly(ethylene glycol) and poly(vinylpyrrolidone), cast mixtures of carboxymethyl cellulose and hydroxyethyl cellulose, guar gum, xanthan gum, sodium alginate, and poly(dimethylsiloxane) are examples of gel-forming polymers.
The air filtration medium is fabricated by curing a pre-polymer in the presence of the fibrous substrate. The term “curing” means polymerizing a mixture of a monomer and a cross-linking agent, covalently cross-linking a linear polymer or oligomer and partially desolvating a mixture of linear polymers that form stable ionic or hydrogen bonding interactions between polymer chains. As used herein, the term “pre-polymer” refers to: a mixture of “monomers,” small molecules of the same structure that undergo repeated addition to form a polymer and a cross-linking agent; to linear polymers that can be covalently cross-linked; to mixtures of linear polymers that cross-link by ionic or hydrogen bonding interactions; and to oligomers, which may be non-identical that can react to form a cross-linked polymer, like poly(dimethylsiloxane) pre-polymer.
Depending upon the curing conditions and the substrate, the polymer network may be covalently bound to the fibrous substrate, for instance, if the substrate has sites of unsaturation and the network polymer is formed around the fibers by addition polymerization. However, while not intending to be bound by any particular theory, it is believed that the polymer network adheres to a substrate fiber by forming a substantially continuous sheath around the fiber that cannot be separated without cleavage of covalent, ionic or hydrogen bonding interactions within the network.
In the novel process for producing the inventive air filtration media, the fibrous substrate is contacted with and preferably saturated with a solution of pre-polymer in a pre-polymer solvent. Contacting may be practiced by immersing the substrate in the solution, by spraying the solution on the substrate or other means that wets the fibers of the fibrous substrate.
Preferably, the fibrous substrate is immersed in the pre-polymer solution. After immersion, the fibrous substrate is removed from the pre-polymer solution. Excess pre-polymer solution is allowed to drain from the substrate for a period of minutes to hours after wetting, or the fibrous substrate is blotted with an absorbent material to remove excess pre-polymer solution. The remaining pre-polymer on the surface of the fibers is then cured under appropriate conditions for the particular polymer sought to be produced.
When curing involves heating, the curing temperature should not be so high as to decompose the reactants. The time required for curing will depend on the curing temperature or, if cured by irradiation, then on the intensity of the irradiation. Therefore, the curing time can vary greatly.
Generally, the solvent for the pre-polymer solution may be water or any organic solvent. Preferred solvents arc water, glycerol, poly(ethylene glycol) and silicone oil, with mixtures of water and glycerol being especially preferred.
In addition to pre-polymer, the pre-polymer solution will contain a cross-linking agent, unless the pre-polymer is bi- or multi-functional so that it can cross-link without a separate agent. Those skilled in the art of polymer chemistry recognize that many crosslinking agents exist and that their selection depends upon the functional groups or reactive intermediates on the polymer with which they are intended to react. Examples of cross-linking agents are provided below in descriptions of preferred processes for forming the network polymer.
The pre-polymer solution also may contain viscosity modifiers. A viscosity modifier may be used to control the amount of solution that remains on the substrate after draining or blotting which, in turn, affects the thickness of the coating. An especially preferred solvent system is about two parts water and one part glycerol, whose viscosity is such that it may be used advantageously without a separate viscosity modifier. The selection and use of viscosity modifiers is well known in the art.
In addition to the above-described components of the solution, the solution may further contain any additives that do not inhibit the curing, such as surfactants and other substances added to improve the solubility of the other components in the solvent.
This description turns now to the means whereby antimicrobial properties are imparted to the air filtration medium. In embodiments that possess an anti-pathogenic polymer network, chemical functionality on the polymer network establishes chemical conditions that are destructive to pathogens that come in contact with the air filtration medium. Such functionality may be acidic, basic, oxidizing or have detergent properties that disrupt the cell membrane of pathogens.
Non-limiting examples of coating polymers that have anti-pathogenic chemical functionality are poly(4-styrenesulfonic acid), poly(acrylic acid), poly(methacrylic acid), poly(4-vinyl pyridine) quaternary ammonium salts and polyethylenimine quaternary ammonium salts and poly(vinylpyrrolidone) iodine complexes, all of which can be formed on the substrate fibers as a randomly cross-linked polymer.
Randomly cross-linked polymers can be formed by polymerizing mixtures of a monomer and a bi- or multi-functional cross-linking agent. Exemplary cross-linking agents include divinylbenzene (DVB), which is preferred for use with poly(styrenesulfonic acid) monomer and its salts. Additional exemplary cross-linking agents that are preferred for use with acrylic acid and methacrylic acid monomer are 1,4-butane diol diacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, tris(methacryloyloxymethyl) propane, allyl methacrylate, tartaric acid dimethacrylate, N,N′-methylene-bisacrylamide, hexamethylene bis(methacryloyloxyethylene) carbamate, 2-hydroxytrimethylene dimethacrylate and 2,3-dihydroxytetramethylene dimethacrylate, 1,3-butanediol diacrylate, di(trimethylolpropane) tetraacralate, poly(ethylene glycol) diacrylate, trimethylolpropane ethoxylate, poly(propylene glycol) dimethacrylate, bisphenol A dimethacrylate and 1,4-butandiol acrylate, with 1,4-butanediol acrylate being especially preferred. Additional exemplary cross-linking agents that are preferred for use with amine functionalized monomers are diepoxides, blocked isocyanates and epichlorhydrin.
The formation of a anti-pathogenic polymer network of a randomly cross-linked polymer is further illustrated with poly(styrene sulfonic acid). A anti-pathogenic coating of cross-linked poly(4-styrenesulfonic acid) may be applied by free radical addition polymerization of 4-styrenesulfonic acid monomer and a cross-linking agent. The polymerization may be initiated with UV irradiation (with or without a chemical initiator) or with thermal initiation with a chemical initiator. Conventional chemical initiators may be employed, such as azo compounds, like 2,2′-azoisobutynitrile (“AIBN”), 1,1′-azobis(cyclohexanecarbonitrile), and 4,4′-azobis(4-cyanovaleric acid); peroxides, like di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, isobutyl peroxy octoate, t-butyl peroctoate, n-butyl-4-4′-bis(t-butylperoxy) valerate, Percadox® and the like; and inorganic peroxides such as ammonium persulfate, potassium persulfate, sodium persulfate, and hydroxymethanesulfinic acid, with potassium persulfate being especially preferred.
The concentration of 4-styrenesulfonic acid in the solution is preferably from about 1 wt. % to about 25 wt. %, more preferably about 5 wt. %. The divinylbenzene is preferably present in an amount of from about 0.05 mole % to about 15 mole % with respect to 4-styrenesulfonic acid, more preferably from about 1 mole % to about 5 mole %. A preferred solvent is a mixture of water and glycerol, preferably in a ratio of about 2 to 1. This solvent mixture appears to have an optimal viscosity for producing a 4-styrenesulfonic acid coating. The pH of a pre-polymer solution of 4-styrenesulfonic acid should be below 3, preferably to below 2, and most preferably to below 1. An emulsifying agent, like sodium dodecyl sulfate, also may be added in an amount to dissolve the cross-linking agent. The solution need not be highly concentrated, however. As shown in Example 1, solutions of about 5 wt % 4-styrenesulfonic acid yield a sufficient density of acid functionality to impart an anti-pathogenic property to the air filtration medium.
The fibrous substrate is wetted with the pre-polymer solution and optionally partially dried. Thereafter, the substrate is heated and/or irradiated with a UV lamp to initiate polymerization. When thermal initiation at 85° C. with AIBN is used, the air filtration medium is sufficiently cured in a few hours.
As an alternative to the foregoing procedure for forming a polymer network of 4-styrene sulfonic acid over the substrate fibers, the polymer network can be formed by polymerizing styrene and divinylbenzene to form a polymer network of cross-linked polystyrene and then the polymer network can be sulfonated, for example, by treating the coated fibrous substrate with sulfur trioxide.
An anti-pathogenic air filtration medium having other anti-pathogenic functional groups on the network polymer can be fabricated using a similar procedure. For instance, and as further illustrated in Example 3, 4-vinyl pyridine is polymerized with a bis(vinylic) cross-linking agent according to the above-described procedure. The resulting cross-linked poly(vinyl pyridine) is then converted to a poly(vinyl pyridine) quaternary ammonium salt. The poly(vinyl pyridine) quaternary ammonium salt can be formed by immersing the coated fibrous substrate in a solution of an alkyl bromide, preferably a C 4 -C 24 alkyl bromide, more preferably a C 6 -C 12 alkyl bromide like lauryl bromide, which is especially preferred. The alkyl bromide converts the pyridine groups into pyridinium bromide salts that are toxic to microorganisms.
An alternative process for forming a poly(4-vinyl pyridine) quaternary ammonium salt polymer network is polymerization of a 4-vinyl pyridine quaternary ammonium salt, which avoids contacting the coated fibrous substrate with a solution of alkyl bromide.
A polymer network of polyethylenimine can be produced from commercially available oligomeric pre-polymer. BASF markets low molecular weight branched polyethylenimine suitable for use as pre-polymer under the brand names Lupasol® and Lugalvan®. If necessary, the pH of the pre-polymer solution should be adjusted to above 10, preferably to above 11, and most preferably to above 12, by adding a suitable strong base such as sodium hydroxide to either solution before the substrate is contacted with the basic layer. When starting with an ethylenimine oligomer, preferred cross-linking agents are epichlorohydrin, diepoxides such as bisphenol A diglycidyl ether. Other preferred crosslinking agents are epoxy resins, especially solid epoxy resins having an epoxy equivalent weight of between 400 and 3000, preferably from 600 to 2000, and most preferably from 500 to 1000. Yet other preferred cross-linking agents are anhydrides such as 4,4′-oxydiphthalic anhydride.
In an alternative embodiment of the air filtration medium of the invention, the network polymer is a gel-forming polymer that under conditions of use is gelled with an anti-pathogenic liquid. Suitable gel-forming polymers include starch, cellulose, guar gum, xanthan gum, alginic acid and other polysaccharides and gums and derivatives thereof such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl-2-hydroxyethyl cellulose, hydroxypropylmethyl cellulose (“HPMC”) and carboxymethyl cellulose, poly(vinylpyrrolidone), poly(hydroxyethyl methacrylate) and polyethylene glycol methacrylates having anywhere from two to about twelve ethoxy repeat units and mixtures of poly(vinylpyrrolidone) and poly(sodium styrene sulfonate), mixtures of poly(ethylene glycol) and poly(vinylpyrrolidone), and mixtures of carboxymethyl cellulose and hydroxyethyl cellulose.
Coatings of poly(vinylpyrrolidone) and hydrophilic methacrylate polymers can be applied by free radical addition polymerization in the presence of a difunctional or multi-functional cross-linking agent such as those previously described with reference to polymerization of 4-styrenesulfonic acid. Especially preferred cross-linking agents are bis-methacrylates and bis-methacrylamides such as triethanolamine dimethacrylate, triethanolamine trimethacrylate, tris(methacryloyloxymethyl) propane, tartaric acid dimethacrylate, N,N′-methylene-bisacrylamide, hexamethylene, bis(methacryloyloxyethylene) carbamate, 2-hydroxytrimethylene dimethacrylate and 2,3-dihydroxytetramethylene dimethacrylate.
Coatings of some gel-forming polymers may be applied by casting a solution or dispersion of the polymer onto the fibrous substrate. Pre-polymers that can be cast to form a polymer network around the fibers include starch, cellulose, guar gum, xanthan gum alginic acid and other polysaccharides and gums and derivatives thereof such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl-2-hydroxyethyl cellulose, hydroxypropylmethyl cellulose (“HPMC”) and carboxymethyl cellulose, mixtures of poly(vinylpyrrolidone) and poly(sodium styrene sulfonate), mixtures of poly(ethylene glycol) and poly(vinylpyrrolidone).
A gel-forming polymer network can be cast from these pre-polymers by dissolving the pre-polymer in a mixture of a volatile solvent, like water or lower alcohol, and a non-volatile solvent, like glycerol, poly(dimethylsiloxane), polyethylene glycol and polypropylene glycol. The fibrous substrate is immersed in the solution to coat the fibers and then dried to remove the volatile solvent. The polymer coat remains on the fibers and the non-volatile solvent component plasticizes the polymer.
Coatings of gel-forming polymers also can be applied by cross-linking linear polysaccharide polymers in the presence of the fibrous substrate. For example, HPMC can be cross-linked to form a polymer network around the substrate fibers a follows. Linear HPMC pre-polymer, available from under the trade name Methocel® from DuPont, is dissolved in water along with a blocked isocyanate. The fibrous substrate is wetted with the solution, e.g. by immersing and removing from the solution and blotting to remove excess solution, then heated at 85° C. for two hours to dry and cross-link the polymer. Then, the fibrous substrate is immersed in a solution of sodium hydroxide in water to provide a basic anti-pathogenic environment. Another process for cross-linking a linear polysaccharide polymer, carboxymethyl cellulose, is described below.
Polydimethylsiloxane (PDMS) pre-polymer mixtures containing dimethylsiloxane oligomers derivatized for cross-linking and a catalyst are commercially available from Dow Corning Co. under the tradename Dow Corning Resins®, Silastic® and Sylgard®. A silicone polymer coating can be formed on a fibrous substrate by modifying well known procedures in the art for curing silicone pre-polymer into silicone polymer gel. The fibrous substrate is wetted with the pre-polymer mixture and then cured by exposing the wetted substrate to conditions known in the art for curing silicone polymers.
The anti-pathogenic liquid can be either a solution, colloidal suspension or dispersion of any anti-pathogenic substance. Examples of anti-pathogenic liquids that may be retained in the gel-forming polymer network are solutions of acids, bases and oxidizing agents; metal colloidal suspensions, surfactant laden oils and solutions of antimicrobial drugs.
A volatile component of the anti-pathogenic liquid, such as water, will evaporate when the gel coating is exposed to a steady stream of air in a HVAC system. By using a much less volatile diluent, such as glycerol, the gel-forming polymer will remain swollen. Glycerol is a preferred diluent. It is hygroscopic as well as non-volatile, and, as such, will tend to pick up moisture from the air helping to retain the gel-forming polymer in swollen condition. Other non-volatile diluents suitable for this purpose are oils, poly(dimethylsiloxane), polyethylene glycol and polypropylene glycol.
Acids, bases and oxidants (like bleach or organic peroxides) can be immobilized on the air filtration medium by contacting the fibrous substrate coated with a gel-forming polymer network with a solution of the active agent and a non-volatile diluent.
For an acidic environment, the active solution can be prepared with strong mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, or phosphoric acid.
For a basic environment, the active solution can be prepared with strong bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or calcium hydroxide, preferably sodium hydroxide.
The active solution also can be prepared with oxidants such as sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, iodine, PVP-iodine potassium permanganate, trichlorocyanuric acid and sodium dichlorocyanuric acid, hydrogen peroxide and organic peroxides, such as di-t-butyl peroxide. A preferred oxidant is calcium hypochlorite.
The active solution also can be a surfactant-laden oil. When pathogens contact the surface of the substrate, they strongly adhere to the surface and the surfactant molecules encapsulate and eliminate the adsorbed pathogen. Preferred polymers for use in conjunction with surfactant-laden oils are poly(methyl methacrylate) and cross-linked cellulose ethers. Suitable surfactants include non-ionic surfactants, for example Triton® and Tween®. Suitable oils include vegetable oils such as soy bean oil, corn oil and sunflower oil.
A coating of poly(methyl methacrylate) can be formed around the substrate fibers by free radical addition polymerization of methyl methacrylate in the presence of a cross-linking agent such as those previously described as being preferred for polymerization of acrylic acid.
A fibrous substrate having a coating of cross-linked cellulose ether may be fabricated as follows. A pre-polymer solution is prepared from hydroxymethyl cellulose, which is commercially available under the trade name Natrosol® from Hercules Chemical Co., and a cross-linking agent. Preferred cross-linking agents are melamine formaldehyde resins, urea formaldehyde resins, such as Kymene® available from Hercules Chemical Co. and dimethylolurea. An especially preferred cross-linking agent is Kymene® 917 in combination with an ammonium chloride catalyst (10 wt. % with respect to Kymene®). The fibrous substrate is immersed in and removed from, or sprayed with, the pre-polymer solution. The fibrous substrate is then dried and cured at 80° C. for two hours. The resulting fibrous substrate having a coating of gel-forming polymer may subsequently be contacted with a surfactant laden oil to produce an anti-pathogenic air filtration medium. Alternatively, the oil and surfactant can be added to the pre-polymer solution.
The anti-pathogenic filter with a coating of gel-forming polymer is further illustrated with a metal colloid suspension. Certain metal colloidal suspensions, specifically silver and copper and more particularly silver, have demonstrated anti-pathogenic activity against a broad spectrum of bacterial species. Metal colloids with anti-pathogenic activity, preferably silver and copper, most preferably silver, can be incorporated into the filter in one step by including them in the pre-polymer solution before contacting with the fibrous substrate and curing. Alternatively, a coating of gel forming polymer can be formed prior to contacting the air filtration medium with the metal colloid. In this two-step process, the coating preferably is desolvated such as by heating before contacting with the metal colloid. Then the fibrous substrate with a desolvated coating will take up the colloid upon contact.
The metal colloids may be incorporated into the pre-polymer solution by a variety of methods. In one method, the metal colloids are prepared and then added to the pre-polymer solution. The metal colloids may be prepared by reduction of metal salts via chemical, electrochemical or irradiative processes, which are known to those of skill in the art. For example, silver salts may be reduced to metallic silver with sodium borohydride (chemical), an electric potential (electrochemical) or with visible light (irradiative). Metal colloids are typically made up of particles with a mean diameter between 10 and 500 nanometers. Passivating agents may be added to the reducing medium to control particle size and coat the particle surface to minimize particle aggregation. Common passivating agents include bovine serum albumin, casein, and bovine milk proteins (e.g. powdered milk). Preferably, the passivating agents contain functional groups that react with the components of the pre-polymer solution. More preferably, the passivating agents are physically entrained within the colloidal particle to facilitate entrapment of the colloidal particle within the coating.
The general procedure previously described by which a coating of gel-forming polymer can be formed on a fibrous substrate can be used to concurrently coat the substrate with the gel-forming polymer and entrain a metal colloid suspension in the coating. A pre-polymer solution of carboxymethyl cellulose and polyacrylic acid is prepared, optionally with a wetting agent, like WetAid NRW®. A preferred pre-polymer solution contains from about 2 to about 6 wt. %, more preferably about 4 wt. % carboxymethyl cellulose; from about 2 to about 10 wt. %, more preferably about 5 wt. % poly(acrylic acid) having a molecular weight of from about 100,000-125,000 a.u.; and from about 0.05 to about 0.5 wt. % wetting agent in an approximately 2:1 mixture of water and glycerol. In addition, from about 3 to about 10 wt. %, more preferably about 6 wt. % of metal colloid is added to the pre-polymer solution. Optionally a passivating agent like Kathon CG-ICP® can be added preliminarily to the metal colloid to help disperse the metal particles. After thorough mixing and a uniform dispersion is obtained, the fibrous substrate is immersed in the dispersion. After removal, the treated substrate is dried and cured according to the general procedure.
The metal colloids also may be prepared directly within the pre-polymer solution. A soluble metal salt of silver or copper is mixed with between one and all components of the pre-polymer solution and then exposed to reductive conditions that induce colloid formation. This approach offers a potential advantage in that a viscous solution of between one and all components of the pre-polymer solution can prevent aggregation of the nascent colloidal particles. Furthermore, one or more of the components of the pre-polymer solution may function as a passivating agent for the colloid particles.
The gel-coated embodiments of this invention possess the advantage that fibrous substrates, which are less efficient and costly than HEPA substrates can attain collection efficiencies comparable to those of HEPA filters through pore size reduction, reduction of particle bounce and increase in particle impingement. When contaminated air moves through the pores of the air filtration medium, pathogens encounter the surfaces of the substrates supporting the active layer via collision or diffusion. The proportion of pathogens impinging on the air filter that are retained is expressed as the filter's collection efficiency. A filter's collection efficiency depends on the pore size and thickness of the air filtration medium and the size of the pathogen. Anti-pathogenic filters having a gel-forming polymer network coating will tend to increase the collection efficiency of the fibrous substrate to which it is adhered by two distinct mechanisms. First, a gel coating will increase the thickness of the fibers and concomitantly reduce the pore size. The extent of pore size reduction is controlled by the amount of polymer, degree of cross-linking and choice of solvent in the pre-polymer solution. Second, the gel coatings are generally more adherent to small particles than the surfaces of fibrous substrates conventionally used to make air filters. The effect of coatings of anti-pathogenic polymer networks on a substrate's collection efficiency will vary depending upon the choice of pre-polymer and the pre-polymer solution solvent system. The pre-polymer solvent system affects the collection efficiency of the filter because its viscosity affects the amount of pre-polymer that adheres to the filter after removal of the fibrous substrate from the pre-polymer solution or spraying.
The anti-pathogenic effectiveness of an air filter relates to the death rate of pathogens that become entrained on the air filter. The anti-pathogenic effectiveness of a filter depends on the susceptibility of a particular pathogen to the anti-pathogenic component of the coating and the loading level. One of the benefits of this invention is that the active agent is uniformly dispersed on the filter.
The anti-pathogenic agent may inhibit propagation of the pathogen without killing it a low loading levels. Although, the invention contemplates air filtration media, air filters and filter cartridges that are effective at inhibiting the propagation of pathogenic microorganisms, air filters and filter cartridges made in accordance with this invention preferably cause the death of 75% or more of the pathogens to which it is directed, e.g. those sensitive to acidic, basic or oxidizing conditions, after 24 hours of capture on the filter.
Protection from a broad spectrum of airborne pathogens is afforded by using a combination of filter media each having a different anti-pathogenic environment. Mechanisms for multiple microorganism capture and elimination can be implemented simultaneously in a compact assembly. A plurality of air filtration media made in accordance with this invention, each exploiting a different anti-pathogenic mechanism, can be stacked in a single device such as a filter for an HVAC system or replaceable cartridge for a gas mask. In addition, anti-pathogenic air filters of this invention can be used in tandem with conventional air filters. Air filters of this invention can be positioned either upstream so as to function as a pre-filter for the conventional filter or they can be downstream of the conventional filter, which then would serve as a pre-filter for the anti-pathogenic filter. Accordingly, the present invention also provides devices comprising one or more layers of air filtration media in stacked arrangement.
The application of a gel-forming polymer layer to the fibers of an air filter offers the opportunity to retain auxiliary substances that do not physi- or chemi-sorb on the filtration medium such as flame-retardant chemicals, odor-absorbing compounds and chemical neutralizers. In this way, the gel-forming polymer coating acts as a binder for these substances.
In addition to its anti-pathogenic activity, the coatings of some embodiments will neutralize certain toxic gases without having to add separate chemical neutralizers. Basic, acid and oxidizing coatings made in accordance with the invention deactivate some chemical agents. For instance, a gel-forming polymer network treated with a solution of base will neutralize acid gases like cyanide, hydrogen chloride, phosgene and hydrogen sulfide. Further, chemical absorbents, like activated carbon, can be incorporated into the coating to augment the coating with activity against chemical agents as further illustrated in Example 6. The reactivity of other active agents in gel coatings and of anti-pathogenic polymers toward other toxic gases will be readily apparent to those skilled in the art of handling and disposing of toxic chemicals.
Although this invention has been described with respect to certain specific embodiments, it will be appreciated by those skilled in the art that various modifications may be made without departing from the spirit and scope of the invention. The present invention is further illustrated by the following examples.
EXAMPLES
Example 1
Coating of a Fibrous Substrate with an Acidic Polymer
An aqueous solution is made of the following: 30 wt. % glycerol, 5 wt. % styrene sulfonic acid, 0.1 wt. % divinylbenzene, 0.13 wt. % 2,2′-azobisisobutyronitrile, 0.02 wt. % potassium persulfate, and 0.5 wt. % sodium dodecyl sulfate. A fiberglass pad is dipped in the above solution, padded dry, and then cured at 85° C. for 2 h.
Example 2
Coating a Fibrous Substrate with a Surfactant Laden Emulsion
An aqueous solution is made of the following: 30 wt. % glycerol, 5 wt. % methyl methacrylate, 0.1 wt. % 1,4-butanediol diacrylate, 0.13 wt. % 2,2′-azobisisobutyronitrile, 0.02 wt. % potassium persulfate, and 1 wt. % Triton X-100, and 10 wt. % soy bean oil. A non-woven polyethylene pad is dipped in the above solution, padded dry, and then cured at 85° C. for 2 h.
Example 3
Coating of Fibrous Substrate with a Basic Polymer and Derivatization to Form an Anti-pathogenic Quaternized Amine Gel Coating
An aqueous solution is made of the following: 30 wt. % glycerol, 5 wt. % vinyl pyridine, 0.25 wt. % divinylbenzene, 0.13 wt. % 2,2′-azobisisobutyronitrile, 0.02 wt. % potassium persulfate, and 0.5 wt. % sodium dodecyl sulfate. A polyester pad was dipped in the above solution, padded dry, and then cured at 85° C. for 2 h. The pad is then dipped in an aqueous solution of lauryl bromide.
Example 4
Coating a Fibrous Substrate with a Basic Gel Layer
An aqueous solution containing 30 wt. % glycerol, 5 wt. % polyethylenimine and 0.25 wt. % glycerol propoxylate triglycidyl ether. A polyester pad is immersed in the solution, blotted dry and cured at 100° C. for 6 hours. The polyester pad is then immersed in an aqueous sodium hydroxide solution of pH 12 or greater containing 30 wt. % glycerol, removed from the solution, blotted dry and dried at 50° C. for two hours.
Example 5
Concurrent Formation of a Gel-Forming Polymer Coating over the Fibrous Substrate and Entrainment of Metal Colloid in the Coating
An aqueous solution is prepared using 4 wt. % carboxymethyl cellulose (Aqualon 7L2; Aqualon, subsidiary of Hercules Chemical Co.), 5 wt. % poly(acrylic acid) (MW=100,000-125,000; Polacryl), 0.1 wt. % WetAid NRW wetting agent (BFGoodrich, Charlotte, N.C.), 0.05 wt. % Kathon CG-ICP preservative (Rohm and Haas, La Porte, Tex.), and 6 wt. % colloidal silver particles. A polyester pad is immersed in solution, blotted and dried at 195° F. for 5 minutes and cured at 335° F. for thirty seconds.
Example 6
Concurrent Formation of a Gel-Forming Polymer Coating over the Fibrous Substrate and Entrainment of Activated Carbon in the Coating
A formulation similar to Example 5 is prepared, substituting activated carbon powder (8% by weight) in place of the metal colloid. The carbon, having a particle size of approximately 40 μm, is available from Fluka Chemical (Milwaukee, Wis.). A polyester pad is dipped into each solution, padded and dried at 195° F. for 5 minutes and cured at 335° F. for thirty seconds.
Example 7
Formation of an Oxidizing Gel Coating
An aqueous solution is made of the following: 20 wt. % tetraethoxysilane, 20 wt. % bis(triethoxysilyl)methane, 10 wt. % glycerol, and 0.05 wt. % citric acid. A fiber glass pad is dipped in the above solution, blotted, and then cured by steam heating for 6 h. The pad is then dipped in an aqueous solution of 2% sodium hypochlorite and 0.5% cyanuric acid. | The present invention provides an anti-pathogenic air filtration medium comprising a fibrous substrate whose fibers are coated with coating comprising a polymer. The coating provides an environment that is destructive to airborne pathogens. In particular, the filter medium can be used in a building air handling system that both filters the air and eliminates pathogens. The filter medium also can be used to create a new bio-protective gas mask that not only offers protection against chemical warfare agents, but also provides protection against biological pathogens. | 3 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to motor-driven compressors used in vehicle air conditioning systems to compress refrigerant, and more particularly, to motor-driven compressors having a motor driven by a power supply, such as a battery.
2. Description of Related Art
Motor-driven compressors are known in the art. For example, Japanese Unexamined Patent Publication No. 2000-291557 describes a motor-driven compressor formed with a housing containing a compression portion and a motor for driving the compression portion to compress refrigerant. In this known motor-driven compressor, a drive circuit for controlling the operation of the motor is disposed adjacent to a suction port for refrigerant gas. In the drive circuit, a capacitor is included as one of the components of an inverter. The capacitor is provided to smooth, i.e., to reduce or eliminate, the alternating current component or ripple current of current supplied from a direct-current (DC) power supply to the motor. According to this known motor-driven compressor, a cooling device, such as a radiator, fan, water cooling radiator or water circulating pipes, is no longer necessary for cooling the drive circuit.
In the known motor-driven compressor, however, a high-frequency, ripple current flows through the capacitor, thereby increasing the heat generated in the capacitor. Moreover, the increase in heat generated in the capacitor by the ripple current may require an increase in the size of a capacitor used to handle the increased heat generated by such high-frequency, ripple current. The increased size of the capacitor may increase the cost of the capacitor. In addition, because the drive circuit may be manufactured separately and attached to the motor-driven compressor, the capacitor may extend from a housing of the motor-driven compressor. As a result, the size of the known motor-driven compressor with a built-in inverter may increase due to any increase in the size of the capacitor.
SUMMARY OF THE INVENTION
A need has arisen in motor-driven compressors that use capacitors for smoothing current supplied to the motor, to reduce the overall size of the motors. Further needs have arisen to reduce the manufacturing cost of such motor-driven compressors and to facilitate heat transfer from the capacitors.
In an embodiment of this invention, a motor-driven compressor comprises a housing containing a compression portion and a motor for driving the compression portion to compress refrigerant. The compressor housing further comprises a suction housing for introducing the refrigerant. A capacitor is provided for smoothing current supplied from a power source to the motor. The capacitor is disposed in contact with the suction housing. In further embodiments of this invention, the capacitor may be disposed on various portions of the suction housing and in one of a plurality of orientations relative to an axial direction of the motor-driven compressor. The selected orientations facilitate heat transfer and reduce the overall dimensions of the motor-driven compressor.
Other objects, features, and advantages of embodiments of this invention will be apparent to, and understood by, persons of ordinary skill in the art from the following detailed description of the invention and the accompanying drawings.
BRIEF DESCRIPTION OF DRAWINGS
The present invention may be more readily understood with reference to the following drawings.
FIG. 1 is a vertical, cross-sectional view of a motor-driven compressor, according to a first embodiment of the present invention.
FIG. 2 is a vertical, cross-sectional view of a motor-driven compressor, according to a second embodiment of the present invention.
FIG. 3 is a vertical, cross-sectional view of a motor-driven compressor, according to a third embodiment of the present invention.
FIG. 4 is a circuit diagram of a drive circuit for use in the motor-driven compressors depicted in FIGS. 1-3.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Referring to FIG. 1, a motor-driven compressor according to a first embodiment of the present invention is shown. A motor-driven compressor 10 has a discharge housing 11 , an intermediate housing 12 , and a suction housing 13 . Housings 11 , 12 , and 13 may be made from a metal or a metal alloy, including aluminum or an aluminum alloy. Intermediate housing 12 and discharge housing 11 are connected by a plurality of fasteners, such as bolts 14 a. Suction housing 13 and intermediate housing 12 are connected by a plurality of fasteners, such as bolts 14 b. Thus, a common housing 15 comprises discharge housing 11 , intermediate housing 12 , and suction housing 13 . Discharge housing 11 has a discharge port 16 formed through an axial end surface. The compression portion comprises a fixed scroll member 17 and an orbiting scroll member 18 . Fixed scroll member 17 and orbiting scroll member 18 are provided in discharge housing 11 , so that both scroll members 17 and 18 interfit to form a refrigerant compression area 19 .
Fixed scroll member 17 includes an end plate 21 , a spiral element 22 provided on one surface of end plate 21 , and a securing portion 23 formed on another surface of end plate 21 . Securing portion 23 is fixed to an inner surface of a side wall of discharge housing 11 by a plurality of bolts 24 . Orbiting scroll member 18 includes an end plate 26 , a spiral element 27 provided on one surface of end plate 26 , and a cylindrical boss portion 28 projecting from another surface of end plate 26 . A rotation prevention mechanism 29 comprises a plurality of balls, each of which travels in a pair of rolling ball grooves formed in opposing ring-shaped races and is provided between a surface of end plate 26 and an axial end surface of intermediate housing 12 . Rotation prevention mechanism 29 prevents the rotation of orbiting scroll member 18 , but allows an orbital motion of orbiting scroll member 18 at a predetermined orbital radius with respect to a center of fixed scroll member 17 . Alternatively, an Oldham coupling may be used as the rotation prevention mechanism.
As shown in FIG. 1, a drive shaft 31 is disposed within intermediate housing 12 and suction housing 13 . One end portion of drive shaft 31 has a first portion 31 a with a diameter that is less than a diameter of a central portion of drive shaft 31 . Another end portion of drive shaft 31 has a second portion 31 b with a diameter that is greater than the diameter of the central portion of drive shaft 31 . Suction housing 13 has a partition wall 32 at its axial middle portion. Partition wall 32 extends across a width of suction housing 13 . A cylindrical projecting portion 33 is provided on one surface of partition wall 32 to extend toward the compression area 19 . Reduced diameter first portion 31 a is rotatably supported by projecting portion 33 via a bearing 34 . Increased diameter second portion 31 b is rotatably supported by intermediate housing 12 via a bearing 39 . An eccentric pin 31 c projects from an end surface of increased diameter second portion 31 b in a direction along an axis of drive shaft 31 . Eccentric pin 31 c is inserted into an eccentric bushing 42 , which is rotatably supported by boss portion 28 of orbiting scroll member 18 via a bearing 41 .
A motor 35 is disposed within intermediate housing 12 and suction housing 13 . Motor 35 comprises a stator 36 , a coil 37 , and a rotor 38 . Stator 36 is fixed on an inner surface of intermediate housing 12 and suction housing 13 . Coil 37 is provided around stator 36 . Rotor 38 is fixed on drive shaft 31 .
In motor-driven compressor 10 , a plurality of sealed terminals 43 are provided on an upper or left portion of partition wall 32 in suction housing 13 , as depicted in FIG. 1. A refrigerant suction port 44 is provided through an outer surface of a side wall of suction housing 13 . Suction housing 13 also includes an opening, which is located at an end of suction housing 13 away from intermediate housing 12 . The opening of suction housing 13 is covered by a lid 45 . Lid 45 is fixed to an axial end of suction housing 13 via a plurality of fasteners, such as bolts 49 . Lid 45 may be formed from a metal or a metal alloy, including aluminum or an aluminum alloy, as is used to form suction housing 13 . In addition, lid 45 may be formed from materials such as iron or magnetic materials. Preferably, lid 45 is made from a material capable of providing shielding against electromagnetic radiation. In addition, lid 45 protects electrical circuits provided within motor-driven compressor 10 from damage due to water and foreign materials.
A drive circuit 46 includes a control circuit 47 and an inverter 48 . Drive circuit 46 is provided on, and fixed to, a surface of partition wall 32 within suction housing 13 . Inverter 48 is connected to output terminals 43 . A capacitor chamber 50 for receiving a capacitor 51 is provided on an upper exterior wall of suction housing 13 . Capacitor 51 , which smoothes current sent or supplied to motor 35 , is inserted into capacitor chamber 50 . Thus, capacitor 51 is in contact, e.g., direct contact, with suction housing 13 . Capacitor 51 is connected to an external power source (not shown), such as a battery mounted on the vehicle, via a connector 52 , which is provided on an upper wall of suction housing 13 . Electric power is supplied to drive circuit 46 and other electrical components, via connector 52 . In this embodiment of motor-driven compressor 10 , because capacitor 51 is in contact with suction housing 13 , heat transfer from capacitor 51 to suction housing 13 may effectively be facilitated.
Referring to FIG. 2, a motor-driven compressor according to a second embodiment of the present invention is shown. In this embodiment, parts that are the same or substantially similar to those disclosed in the first embodiment of the motor compressor are designated by like numerals, and explanations thereof are omitted hereinafter. In this embodiment of motor-driven compressor 10 , a capacitor chamber 53 for receiving a capacitor 51 is formed at a lower portion of suction housing 13 , as depicted in FIG. 2, and opens along an axial direction of motor-driven compressor 10 . Capacitor 51 is inserted into capacitor chamber 53 along an axial direction of motor-driven compressor 10 . Thus, capacitor 51 is in contact, e.g., direct contact, with suction housing 13 . As a result, because capacitor 51 is in contact with suction housing 13 , heat transfer from capacitor 51 to suction housing 13 may effectively be facilitated. Moreover, because capacitor 51 is inserted into capacitor chamber 53 formed in an interior portion of suction housing 13 , a reduction of the dimensions of motor-driven compressor 10 may be achieved. Consequently, the manufacturing cost of motor-driven compressor 10 may be reduced, as well.
Referring to FIG. 3, a motor-driven compressor according to a third embodiment of the present invention is shown. In this embodiment of the present invention, parts that are the same or substantially similar as those disclosed in the first embodiment of the motor-driven compressor are designated by like numerals and explanations thereof are omitted hereinafter. In this embodiment of motor-driven compressor 10 , a capacitor chamber 54 for receiving a capacitor 51 is formed at a lower portion of suction housing 13 , as depicted in FIG. 3, and opens in a direction substantially transverse to an axial direction of motor-driven compressor 10 . Capacitor 51 is inserted into capacitor chamber 54 . Thus, capacitor 51 is in contact, e.g., direct contact, with suction housing 13 . As a result, because capacitor 51 is in contact with suction housing 13 , heat transfer from capacitor 51 to suction housing 13 may effectively be facilitated. Moreover, because capacitor 51 is inserted into capacitor chamber 54 formed in suction housing 13 , a reduction of the dimensions of motor-driven compressor 10 may be achieved. Consequently, the manufacturing cost of motor-driven compressor 10 may be reduced, as well.
FIG. 4 depicts the circuit structure of drive circuit 46 of motor-driven compressor 10 . Drive circuit 46 has a circuit structure similar to that disclosed in Japanese Unexamined Patent Publication No. H9-163791. Motor 35 may be a three-phase current motor and may comprise three coils 64 a, 64 b, and 64 c coupled to one another. Motor 35 may be, for example, a brushless motor. Motor 35 also may include a rotor 38 comprised of a permanent magnet and a stator 36 having coils 64 a, 64 b, and 64 c. In inverter 48 , a plurality of transistors 61 a, 61 b, 61 c , 63 a, 63 b, and 63 c are provided. Transistors 61 a, 61 b, 61 c, 63 a, 63 b, and 63 c are coupled to control circuit 47 . Control circuit 47 controls a switching operation of transistors 61 a, 61 b, 61 c , 63 a, 63 b, and 63 c.
In inverter 48 , transistors 61 a , 61 b , 61 c , 63 a , 63 b , and 63 c are divided into positive-side transistors 61 a , 61 b , and 61 c , and negative-side transistors 63 a , 63 b , and 63 c . Positive-side transistors 61 a , 61 b , and 61 c form upper arms, while negative-side transistors 63 a , 63 b , and 63 c form lower arms in inverter 48 . Both positive-side transistors 61 a , 61 b , and 61 c and negative-side transistors 63 a , 63 b , and 63 c are coupled to an external DC power source 65 , which may comprise a battery, via a capacitor 51 .
Further, diodes 66 a , 66 b , 66 c , 67 a , 67 b , and 67 c are coupled between the emitters and the collectors of transistors 61 a , 61 b , 61 c , 63 a , 63 b , and 63 c , respectively. Diodes 66 a , 66 b , 66 c , 67 a , 67 b , and 67 c return a counter-current generated by three-phase motor 35 to DC power source 65 . Specifically, when the operation of motor 35 is stopped, or when the chopping (i.e., cutting a peak or a bottom of a wave, or both) of the pulse code modulation is deactivated, diodes 66 a , 66 b , 66 c , 67 a , 67 b , and 67 c cause a counter-electromotive force, generated from coils 64 a , 64 b , and 64 c of motor 35 , to be applied to DC power source 65 . Usually, the internal capacitance of each of diodes 66 a , 66 b , 66 c , 67 a , 67 b , and 67 c is set at the same internal capacitance as each of corresponding transistors 61 a , 61 b , 61 c , 63 a , 63 b , and 63 c. Moreover, diodes 66 a , 66 b , 66 c , 67 a , 67 b , and 67 c protect transistors 61 a , 61 b , 61 c , 63 a , 63 b , and 63 c from damage due to counter-electromotive forces.
Moreover, each of the base sides of transistors 61 a , 61 b , 61 c , 63 a , 63 b , and 63 c is coupled to control circuit 47 . The collector sides of upper arms (i.e., transistors 61 a , 61 b , and 61 c ) and the emitter sides of lower arms (i.e., transistors 63 a , 63 b , and 63 c ) are coupled to DC power source 65 for supplying power to the transistors. Capacitor 51 is coupled between the poles of DC power source 65 for smoothing the current supplied to motor 35 .
In operation, control circuit 47 sends control signals to transistors 61 a , 61 b , 61 c , 63 a , 63 b , and 63 c. When motor-driven compressor 10 is to be stopped, the switching operations of transistors 61 a , 61 b , 61 c , 63 a , 63 b , and 63 c first are briefly deactivated. After that, while the upper arms (i.e., transistors 61 a , 61 b , and 61 c ) are maintained in a deactivated condition, the lower arms (i.e., transistors 63 a , 63 b , and 63 c ) are activated for a time period that is not less than a predetermined period. By this procedure, operation of motor-driven compressor 10 is stopped completely and smoothly.
In inverter 48 , when motor-driven compressor 10 is operated under normal operating conditions, the transistors 61 a , 61 b , 61 c , 63 a , 63 b , and 63 c receive control signals from control circuit 47 , and inverter 48 converts the DC current supplied by DC power source 65 into a three-phase current at a suitable phase differentiation for operating motor 35 . The three-phase current is supplied to motor 35 .
As described above, in a motor-driven compressor according to various embodiments of the present invention, because a capacitor is in contact with a suction housing, heat transfer from the capacitor may effectively be facilitated. Moreover, the overall dimensions of the motor-driven compressor may be reduced. In addition, the manufacturing cost of the motor-driven compressor may be reduced.
Although the present invention has been described in connection with preferred embodiments, the invention is not limited thereto. It will be understood by those skilled in the art that other embodiments, variations, and modifications of the invention will be apparent to those skilled in the art from a consideration of this specification or practice of the invention disclosed herein, and may be made within the scope and spirit of this invention, as defined by the following claims. | A motor-driven compressor according to the present invention is formed with a housing that contains a compression portion and a motor for compressing refrigerant. The compressor housing further is provided with a suction housing for introducing the refrigerant. A capacitor is provided for smoothing a current that is supplied from a power source to the motor. The capacitor is in contact with the suction housing. In such motor-driven compressors, because the capacitor is in contact with the suction housing, heat transfer from the capacitor to the housing may effectively be facilitated. In further embodiments of the present invention, the capacitors may be disposed on various portions of the suction housing and in various orientations relative to an axial direction of the motor-driven compressor. These selected orientations reduce the dimensions of the motor-driven compressor. | 5 |
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
[0001] The invention relates to a semiconductor module containing an addressing circuit for addressing memory cells of a memory array. An amplifier circuit is provided for amplifying a signal read from a memory cell and an input/output circuit is provided for reading data in or from the memory cells. A voltage supply circuit supplies an internal voltage to the components. A first evaluation circuit is connected to a switching signal and is suitable for outputting a switch-off signal for switching off the voltage supply circuit via an output if the switching signal represents a switch-off signal.
[0002] Semiconductor memory modules are used in the form of synchronous dynamic random access memories (SDRAMs), for example, for storing a large number of data with a fast access time. By way of example, memory cells with capacitors are used to store the data. The information is stored in the charge of the storage capacitor of the memory cell. Since the charge in the storage capacitor decreases over time, the charge state of the storage capacitor has to be regularly refreshed.
[0003] Semiconductor memory modules are increasingly used in mobile devices, too, such as e.g. a laptop or a mobile radio device. Since the mobile devices themselves usually carry only a limited current capacity, a low current consumption of the semiconductor memory modules is of substantial importance particularly in these applications.
[0004] A semiconductor module of the generic type that has two evaluation circuits that monitor a switching signal is already known. The evaluation circuits switch the internal voltage supply on or off depending on the signal state of the switching signal. In this way, it is possible to adapt the functionality of the internal voltage supply circuit to the actual current requirement. This procedure affords the advantage that the internal voltage supply circuit consumes less current in the switched-off state than in the switched-on state.
[0005] Published, Non-Prosecuted German Patent Application DE 4 028 175 A1, corresponding to U.S. Pat. No. 5,167,024, discloses an energy management configuration for a portable computer. The energy management configuration is provided for managing and distributing the energy which is drawn from a battery and used to supply a central unit, a memory and a plurality of peripheral devices including a user-interactive device. The energy management configuration has a control device coupled to the central unit for receiving commands from the central unit and also to the user-interactive device for receiving user inputs. The control device is additionally coupled to the battery for controlling the energy distribution between various computer units. In order to reduce the current consumption, the clock frequency of an internal clock generator is varied. Less current is consumed by prescribing a lower clock frequency.
SUMMARY OF THE INVENTION
[0006] It is accordingly an object of the invention to provide a semiconductor memory module with a low current consumption that overcomes the above-mentioned disadvantages of the prior art devices of this general type, which has a reduced current consumption.
[0007] With the foregoing and other objects in view there is provided, in accordance with the invention, a semiconductor memory module. The semiconductor memory module containing a memory array having memory cells, an addressing circuit for addressing the memory cells of the memory array, an amplifier circuit connected to the memory cells for amplifying a signal read from the memory cells, an input/output circuit connected to the memory array for reading data to/from the memory cells, a voltage supply circuit providing an internal voltage for components of the semiconductor memory module and having an input, and a first evaluation circuit having an input receiving a switching signal. The first evaluation circuit has an output coupled to the voltage supply circuit and outputs a switch-off signal for switching off the voltage supply circuit if the switching signal represents a switch-off state. A second evaluation circuit has an input receiving the switching signal. The second evaluation circuit has an output connected to the voltage supply circuit. The second evaluation circuit receives a voltage made available to the semiconductor memory module from an external voltage source. The second evaluation circuit outputs a switch-on signal to the voltage supply circuit if the switching signal represents a switch-on state.
[0008] One advantage of the invention consists in providing two evaluation circuits, a first evaluation circuit being supplied with current by an internal voltage supply and a second evaluation circuit being supplied with current by an external voltage supply. The second evaluation circuit monitors a switch-on signal for the internal voltage supply circuit. The first evaluation circuit monitors a switch-off signal for the internal voltage supply circuit. If a switch-off signal is identified by the first evaluation circuit, then the first evaluation circuit outputs a switch-off signal for switching off the voltage supply circuit. If the second evaluation circuit identifies a switch-on signal for the internal voltage supply circuit, then the second evaluation circuit switches the voltage supply circuit on again. As a result, the first evaluation circuit is also supplied with a sufficiently large supply voltage again.
[0009] The provision of two evaluation circuits makes it possible to optimally adapt the performance and the current consumption of the two evaluation circuits for the two different areas of use and tasks of the two evaluation circuits. Consequently, less current is consumed overall by the semiconductor memory module.
[0010] Preferably, the internal voltage supply circuit is switched off in the event of a deep power down command from the first supervisory circuit. In mobile devices, in particular, it is advantageous for the internal voltage supply circuit to be at least partially switched off in the event of an expected operating state in which only a very small current or hardly any current at all is required.
[0011] In one preferred embodiment, the internal voltage supply circuit is switched on or off only by the first supervisory circuit. This provides simplified driving for switching the voltage supply circuit on or off.
[0012] In a further preferred embodiment, provision is made of an amplifier circuit for receiving and forwarding the switching signal to a supervisory circuit in the second evaluation circuit. The output of the supervisory circuit forms the output of the second evaluation circuit. In this preferred embodiment, the output of the supervisory circuit is fed back to an input of the amplifier circuit. If the supervisory circuit identifies that the internal voltage supply circuit is to be switched off, then the supervisory circuit passes a switch-on signal to the amplifier circuit. Thus, the amplifier circuit of the second evaluation circuit is activated only when the internal voltage supply circuit is switched off. Consequently, no current is consumed by the amplifier circuit during an active internal voltage supply circuit. The current consumption is thus reduced overall.
[0013] In one preferred embodiment, the first supervisory circuit is configured in the form of an RS flip-flop circuit.
[0014] In a further preferred embodiment, the evaluation circuit is configured in the form of a second amplifier circuit, a command decoder and a second supervisory circuit. The second amplifier circuit is connected to the switching signal, the command decoder is connected to the output of the second amplifier circuit and the second supervisory circuit is connected to the output of the command decoder.
[0015] In one preferred embodiment, the output of the second supervisory circuit is connected to an input of the first supervisory circuit.
[0016] A further embodiment of the invention has a common amplifier circuit for the first and second evaluation circuits. As a result, overall less space is required on the semiconductor memory module in order to realize the circuit configuration according to the invention.
[0017] Other features which are considered as characteristic for the invention are set forth in the appended claims.
[0018] Although the invention is illustrated and described herein as embodied in a semiconductor memory module with low current consumption, it is nevertheless not intended to be limited to the details shown, since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims.
[0019] The construction and method of operation of the invention, however, together with additional objects and advantages thereof will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] [0020]FIG. 1 is a block circuit diagram of an SDRAM semiconductor memory module according to the invention;
[0021] [0021]FIG. 2 is a block circuit diagram of a changeover device for switching an internal voltage supply circuit on or off;
[0022] [0022]FIG. 3 is a block circuit diagram of a second embodiment of the changeover device; and
[0023] [0023]FIG. 4 is a block circuit diagram of a third embodiment of the changeover device.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0024] Referring now to the figures of the drawing in detail and first, particularly, to FIG. 1 thereof, there is shown an SDRAM semiconductor memory module 24 . However, the invention can be applied to any type of memory modules.
[0025] [0025]FIG. 1 shows a schematic construction of the SDRAM memory module 24 having an addressing circuit 11 , word line decoders 12 , column decoders 13 , amplifier circuits 14 and memory arrays 15 , in which memory cells 16 are disposed in matrix form. Furthermore, an input/output circuit 17 is provided, via which data can be read from the memory cells 16 or written to the memory cells 16 . Furthermore, a central control unit 18 is provided, which controls the functioning of the individual circuit configurations and provides for a synchronous data stream. By prescribing a word line address and a column address, it is possible for an individual memory cell 16 to be addressed and an information item to be written to the addressed memory cell 16 or read from the addressed memory cell. In a simple embodiment, a memory cell 16 has a selection transistor and a storage capacitor. The charge state of the storage capacitor represents the information stored in the memory cell 16 . When an information item is read from the memory cell 16 , the charge state is passed via a bit line to the amplifier circuit 14 . For each bit line, the amplifier circuit 14 has an amplifier unit. Through the selection of a column line, which is defined by the column address, an amplifier unit 14 is selected and the charge of the selected bit line is thus forwarded to the input/output circuit 17 .
[0026] The semiconductor memory module furthermore has a terminal pad 1 connected to a changeover device 19 . The changeover device 19 is connected to an internal voltage supply circuit 8 , which supplies the circuits of the semiconductor memory module 24 with a supply voltage via supply lines 9 .
[0027] [0027]FIG. 2 shows a first construction of the changeover device 19 . The changeover device 19 has a second amplifier circuit 2 , whose input is connected to a terminal pad 1 . An output of the second amplifier circuit 2 is connected to an input of a command decoder 3 . An output of the command decoder 3 is connected to an input of a second supervisory circuit 4 . A second input of the second supervisory circuit 4 is connected to an internal clock. An output of the second supervisory circuit 4 is connected to an input of a first supervisory (control) circuit 6 . The terminal pad 1 is connected to a non-illustrated control unit.
[0028] Furthermore, a first amplifier circuit 5 is provided, which is connected to the terminal pad 1 via a first input. Moreover, an output of the first amplifier circuit 5 is connected to a second input of the first supervisory circuit 6 . The first supervisory circuit 6 is connected to an input of the voltage supply circuit 8 via an output. Furthermore, the output of the first supervisory circuit 6 is connected to a second input of the first amplifier circuit 5 . The first amplifier circuit 5 is additionally connected to a supply terminal 7 via a supply line. The supply terminal 7 serves for the connection of an external voltage supply circuit 21 disposed outside the semiconductor memory module 24 . The command decoder 3 has a command input 20 , via which control signals such as e.g. CS, RAS, CAS, WE are passed to the command decoder 3 . The control signals serve for controlling the functions of the semiconductor memory module 24 . The second amplifier circuit 2 , the command decoder 3 and the second supervisory circuit 4 represent a first evaluation circuit. The first amplifier circuit 5 and the supervisory circuit 6 represent a second evaluation circuit. The second supervisory circuit 4 is configured in the form of a storage element and a pulse generator. The first supervisory circuit 6 is configured in the form of an RS flip-flop.
[0029] The functioning of the changeover device 19 is explained in more detail below. A switching signal is passed to the second and first amplifier circuits 2 , 5 via the terminal pad 1 . With the switching signal it is possible to communicate a switch-on or switch-off signal for switching on or switching off the internal voltage supply circuit 8 . If the second amplifier circuit 2 receives a switching signal, then the second amplifier circuit 2 forwards an amplified switching signal to the command decoder 3 . Preferably, the second amplifier circuit 2 only processes switch-off signals. The first amplifier circuit 5 is provided for processing a switch-on signal. If a switch-on signal is fed via the bonding pad 1 , then the switch-on signal is detected by the first amplifier circuit 5 , amplified and forwarded to the first supervisory circuit 6 . The first supervisory circuit 6 detects that the switch-on signal has been fed and forwards a corresponding switch-on signal to the voltage supply circuit 8 . On account of the switch-on signal, the voltage supply circuit 8 is switched into an active state in which the voltage supply circuit 8 makes more power available. In a simple embodiment, the voltage supply circuit 8 is switched, by the switch-on signal, from a switched-off state, in which no voltage is made available, into a switched-on state, in which the voltage supply circuit 8 makes a voltage available.
[0030] In a preferred embodiment, the output signal of the first supervisory circuit 6 is passed to the first amplifier circuit 5 . If the first amplifier circuit 5 receives a switch-on signal from the supervisory circuit 6 , then the first amplifier circuit 5 switches off or at least into an operating state with a reduced power consumption.
[0031] Thus, preferably during the operating mode in which the internal voltage supply circuit provides an internal voltage supply, the first amplifier circuit 5 is operated in a current-saving operating mode. In the current-saving mode, less power has to be made available by the external voltage supply circuit 21 . Thus, current is saved overall.
[0032] A switch-off signal for the internal voltage supply circuit 8 is fed to the first amplifier circuit 5 and the second amplifier circuit 2 via the terminal pad 1 , then the second amplifier circuit 2 passes an amplified switch-off signal to the command decoder 3 . In addition to the switch-off signal of the second amplifier circuit 2 , the command decoder 3 preferably also evaluates further command signals that are fed via the command input 20 . Depending on the comparison between the further command signals and the switch-off signal, the command decoder 3 forwards a switch-off signal to the second supervisory circuit 4 , if the further command signals do not oppose a switch-off of the internal voltage supply circuit 8 . In a simple embodiment, the evaluation of the further command signals can be dispensed with. This is the case, in particular, when a separate signal indicating a deep power down mode is present in the command decoder 3 .
[0033] After receiving the switch-off signal, upon the next rising edge of the internal clock signal, the second supervisory circuit 4 passes the switch-off signal to the first supervisory circuit 6 . Upon receiving the switch-off signal, the first supervisory circuit 6 forwards a corresponding switch-off signal to the internal voltage supply circuit 8 . As a result, the internal voltage supply circuit 8 is switched into an inactive state, in which the internal voltage supply circuit 8 makes less power available or is completely switched off. The voltage supply circuit 8 consumes less current in the inactive state. At the same time, the first supervisory circuit 6 passes the switch-off signal to the first amplifier circuit 5 .
[0034] In a simple embodiment illustrated in FIG. 3, the output of the second supervisory circuit 4 is directly connected to a second input of the internal voltage supply circuit 8 and switches off the internal voltage supply circuit 8 itself. In this embodiment, the first supervisory circuit 6 is connected by its output to a first input of the internal voltage supply circuit 8 and serves for switching the internal voltage supply circuit 8 into an active state, if a corresponding switch-on signal is fed to the first amplifier circuit 5 via the terminal pad 1 .
[0035] The embodiment illustrated in FIG. 2 offers a simplified drive circuit, since only one input is required for controlling the internal voltage supply circuit 8 .
[0036] [0036]FIG. 4 shows a further embodiment of the invention, in which the first and second amplifier circuits 5 , 2 are realized in a common amplifier circuit 22 . The common amplifier circuit 22 affords the advantage that less space is required on the semiconductor memory module for realizing the two functions of the first and second amplifier circuits 5 , 2 . However, a common amplifier circuit 22 is preferably to be supplied with current by the external voltage supply circuit 21 .
[0037] Depending on the embodiment, it is also possible to provide a further switch 23 , which, by way of example, is controlled by the first and/or second supervisory circuit 6 , 4 and realizes a changeover between an internal and external current supply for the common amplifier circuit 22 . The switch 23 is switched in such a way that the common amplifier circuit 22 is supplied with current by the external voltage supply circuit 21 when the internal voltage supply circuit 8 is not active. However, if the internal voltage supply circuit 8 is active and supplies a sufficient supply voltage, then the switch 23 is changed over and the common amplifier circuit 22 is supplied with current by the internal voltage supply circuit 8 . The common amplifier circuit 22 can also be formed in the circuit configurations of FIGS. 2 and 3. | A semiconductor memory module with a changeover device by which an internal voltage supply circuit can be switched on or off in a simple manner. The changeover device has two evaluation circuits, one evaluation circuit being used for switching on the voltage supply and the second evaluation circuit being used for switching off the voltage supply. In this way, the two evaluation circuits can be optimized with regard to functionality, circuit layout and current consumption. | 6 |
BACKGROUND OF THE INVENTION
The present invention pertains to a refrigeration system to provide the cooling requirements of an olefin plant. More particularly, the invention is directed to the use of a tertiary or trinary refrigerant comprising a mixture of methane, ethylene and propylene for cooling in an ethylene plant.
Ethylene plants require refrigeration to separate out desired products from the cracking heater effluent. Typically, a propylene and an ethylene refrigerant are used. Often, particularly in systems using low pressure demethanizers where lower temperatures are required, a separate methane refrigeration system is also employed. Thus three separate refrigeration systems are required, cascading from lowest temperature to highest. Three compressor and driver systems complete with suction drums, separate exchangers, piping, etc. are required. An additional methane refrigeration compressor, either reciprocating or centrifugal, can partially offset the capital cost savings resulting from the use of low pressure demethanizers.
Mixed refrigerant systems have been well known in the industry for many decades. In these systems, multiple refrigerants are utilized in a single refrigeration system to provide refrigeration covering a wider range of temperatures, enabling one mixed refrigeration system to replace multiple pure component cascade refrigeration systems. These mixed refrigeration systems have found widespread use in base load liquid natural gas plants. The application of a binary mixed refrigeration system to ethylene plant design is disclosed in U.S. Pat. No. 5,979,177 in which the refrigerant is a mixture of methane and either ethylene or ethane. However, such a binary refrigeration system cascades against a separate propylene refrigeration system to provide the refrigeration in the temperature range of −40° C. and warmer. Therefore, two separate refrigeration systems are required.
SUMMARY OF THE INVENTION
It is an object of the present invention, therefore, to provide a simplified, single refrigeration system for an olefin plant, particularly an ethylene plant having a low pressure demethanizer, utilizing a mixture of methane, ethylene and propylene as a tertiary refrigerant. This tertiary system replaces the separate propylene, ethylene and methane refrigeration systems associated with a recovery process using a low pressure demethanizer. The invention involves the separation of the tertiary refrigerant from a compressor interstage discharge and the final compressor discharge into a methane-rich vapor fraction and two levels of propylene-rich liquids so as to provide various temperatures and levels of refrigeration in various heat exchange stages while maintaining a nearly constant refrigerant composition flowing back to the compressor and with the bulk of the total return refrigerant flow going to the first stage compressor suction. This enables the tertiary refrigerant system to compete favorably on a thermodynamic basis with the use of separate compressors for separate refrigerants. This tertiary system can also be applied to an ethylene plant with a high pressure demethanizer in which case the tertiary system only supplies propylene and ethylene refrigeration temperature levels. The objects, arrangement and advantages of the refrigeration system of the present invention will be apparent from the description which follows.
BRIEF DESCRIPTION OF THE DRAWING
The drawing is a schematic flow diagram of a portion of an ethylene plant illustrating one embodiment of the refrigeration system of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention relates to an olefin plant wherein a pyrolysis gas is first processed to remove methane and hydrogen and then processed in a known manner to produce and separate ethylene as well as propylene and some other by-products. The process will be described in connection with a plant which is primarily for the production of ethylene. The separation of the gases in an ethylene plant through condensation and fractionation at cryogenic temperatures requires refrigeration over a wide temperature range. The capital cost involved in the refrigeration system of an ethylene plant can be a significant part of the overall plant cost. Therefore, capital savings for the refrigeration system will significantly affect the overall plant cost.
Ethylene plants with high pressure demethanizers operate at pressures higher than 2.76 MPa (400 psi) with an overhead temperature typically in the range of −85° C. to −100° C. Ethylene refrigeration at approximately −100 to 102° C. is typically used to chill and produce overhead reflux. An ethylene plant designed with a low pressure demethanizer which operates below about 2.41 MPa (350 psi) and generally in the range of 0.345 to 1.034 MPa (50 to 150 psi) and with overhead temperatures in the range of −110 to −140° C. requires methane temperature levels of refrigeration to generate reflux. The advantage of the low pressure demethanizer is the lower total plant power requirement and the lower total plant capital cost while the disadvantage is the lower refrigeration temperature required and, therefore, the need for a methane refrigeration system in addition to the ethylene and propylene refrigeration systems.
The tertiary refrigerant of the present invention comprises a mixture of methane, ethylene and propylene. The percentage of these components can vary depending on the ethylene plant cracking feedstock, the cracking severity and the chilling train pressure among other considerations, but will generally be in the range of 7 to 20 percent methane, 7 to 30 percent ethylene and 50 to 85 percent propylene. A typical composition for an ethylene plant with a low pressure demethanizer would be 10% methane, 10% ethylene and 80% propylene. The use of the tertiary refrigerant provides all the refrigeration loads and temperatures required for an ethylene plant while obviating the need for two or three separate refrigerant systems.
The purpose of the present invention is to provide the necessary refrigeration to separate the hydrogen and methane from the charge gas and provide the feed for the demethanizer as well as provide for the other refrigeration requirements of the entire plant. Referring to the specific embodiment of the invention shown in the drawing which is for a low. pressure demethanizer, the tertiary refrigeration system is arranged to provide all of the required levels of refrigeration for an ethylene plant in the series of heat exchangers 10 , 12 , 14 , 16 , 18 and 20 . These heat exchangers can be combined as fewer units or expanded into a greater number of units depending on the particular needs for any particular ethylene process and in particular on the specific charge gas composition. They are typically plate fin type heat exchangers and are preferably packed inside of a heavily insulated structure referred to as a cold box to prevent heat gain and to localize the low temperature operation. Before describing the tertiary refrigeration system, the flow of the charge gas through the system will be described with examples of specific temperatures for purposes of illustration only.
The charge gas feed 22 , which is the pyrolysis gas conditioned as required and cooled, is typically at a temperature of about 15 to 20° C. and a pressure of about 3.45 MPa (500 psi), and is typically a vapor stream. The charge gas contains hydrogen, methane, and C 2 and heavier components including ethylene and propylene. The charge gas 22 is progressively cooled by the refrigeration system of the present invention in the heat exchangers 10 , 12 , 14 , 16 , 18 and 20 with appropriate separations being made to produce demethanizer feeds. The charge gas 22 is first cooled in the heat exchangers 10 and 12 down to about −35° C. at 23 . In heat exchanger 14 , the charge gas is cooled from −35° C. to −60° C. at 23 . In heat exchanger 16 , it is cooled from −60° C. to −72° C. with the condensate 25 in the effluent 26 being separated at 28 . The condensate 25 is a lower feed to the demethanizer (not shown). The remaining vapor 30 is then cooled from −72° C. to −98° C. in heat exchanger 18 with the condensate 32 in the effluent 34 being separated at 36 . This condensate 32 is a middle feed to the demethanizer. The vapor 38 is then further cooled in heat exchanger 20 from −98° C. to −130° C. with the condensate 40 in the effluent 42 being separated at 44 . The condensate 40 is a top feed to the demethanizer. The remaining vapor 46 is then separated (not shown) to produce the hydrogen stream 48 and the low pressure methane stream 50 . The cooling loop 52 is for cooling and partially condensing the low pressure demethanizer overhead to generate reflux. The remaining overhead vapor from the demethanizer forms the high pressure methane-stream 54 . The hydrogen stream 48 and the low and high pressure methane streams 50 and 54 provide additional cooling in the heat exchangers. To complete the description of the charge gas, flow, it is the demethanizer bottoms which contains the C 2 and heavier components which is sent for the recovery of the ethylene and propylene and other components.
In addition to the charge gas stream and the tertiary refrigerant streams, the streams 55 , 56 , 57 and 58 are various ethylene plant streams at various temperatures which also pass through the heat exchangers for recuperation of cold. Merely as examples, stream 55 is for the recuperation of the cold from the low pressure demethanizer side reboiler. Stream 56 recuperates the cold from the deethanizer feed and the low pressure demethanizer bottom reboiler. Stream 57 is for recuperation of the deethanizer feed, the ethane recycle, the ethylene fractionator side reboiler and bottom reboiler and the ethylene product. The last stream 58 covers the recuperation of cold from the lower deethanizer feed, the ethylene product, the ethane recycle and the refrigeration consumed in a dual-pressure depropanizer system.
The maximum efficiency of heat transfer between a warm fluid and a cold fluid is achieved when the temperature difference is low. A mixed refrigerant, such as proposed in this invention, has an increasing temperature with increasing vaporization, at a fixed pressure. This is as distinguished from a pure component refrigerant which vaporizes at a constant temperature at a fixed pressure. Pure component refrigeration systems therefore tend to be more efficient when the process condensing temperatures are unchanged, or relatively unchanged, when being cooled, and relatively less efficient when process temperatures decrease when being cooled. For mixed refrigeration systems, such as proposed in this invention, the relative advantages are reversed.
In an ethylene plant, some of the cooling services requiring refrigeration are at relatively constant temperatures and some are at decreasing temperatures. In the pending U.S. patent application Ser. No. 09/862,253, entitled, Tertiary Refrigeration System for Ethylene Plants, and filed May 22, 2001, a mixed refrigerant system for ethylene plants is described which emphasizes a constant composition throughout the system. Thus, a somewhat lower efficiency in the constant temperature heat transfer services has been understood. The present invention proposes to improve the efficiency of the mixed refrigeration system by varying the composition of the mixed refrigerant used for these constant temperature heat transfer services. This invention is especially directed to the refrigeration system utilized in the separation of ethylene from ethane which has a very large refrigeration requirement. The concept can also be utilized for other constant temperature heat transfer services with lower heat transfer duty such as the deethanizer.
For the purposes of the present invention, the total duty of the ethylene fractionator condenser 59 is handled outside the coldbox with special consideration. Shell and tube exchangers are typically used for the ethylene fractionator condenser heat transfer service although platefin exchangers, as in the cold box, can also be utilized. As known from the thermodynamics, the condensation of the process stream with constant temperature, such as the ethylene fractionator overhead and the deethanizer overhead, as well as the depropanizer overhead if a single low pressure tower is employed, will be less efficient if a mixed refrigeration system is used where the vaporization curve is sloped with temperature. The wide cold-end temperature approach indicates inefficiency and results in higher power consumption for the tertiary refrigeration system. For the deethanizer condenser, the refrigeration can be supplied by the ethylene fractionator side reboiler with near constant temperature on both sides. However, there is no alternative for the ethylene fractionator condenser which is the biggest refrigeration consumer in the ethylene plant. To make the tertiary system competitive in power consumption to a system designed with separate compressors, a concept to generate a heavy refrigerant stream approaching the conventional propylene refrigeration is called for in the tertiary system of the present invention.
Turning now to the refrigeration system per se, the tertiary refrigerant as identified earlier is a mixture of methane, ethylene and propylene and is compressed by the multistage refrigeration compressor 60 . In the illustrated embodiment, there are five compressor stages 61 , 62 , 64 , 66 and 68 with two interstage coolers. The interstage cooler 70 is at the third stage discharge 72 while the interstage cooler 74 is at the fourth stage discharge 76 . The liquid in this fourth stage discharge after cooling is separated in the drum 78 , to provide the heavy refrigerant 80 . The remaining vapor 82 , from drum 78 is returned to the fifth compressor stage 68 , and extracted as the fifth stage final effluent 84 . This final effluent 84 is cooled and partially condensed at 86 and then separated in drum 88 to generate a medium refrigerant 90 and a light refrigerant 92 by phase separation. The typical operating conditions and the range of operating conditions for the compressor are as follows:
Range of Suction Pressure
Typical Suction Conditions
Mpa
Mpa
Degree C
1 st Stage
0.01-0.016
0.014
−40
2 nd Stage
0.4-0.55
0.46
9.0
3 rd Stage
0.7-0.95
0.86
47
4 th Stage
1.1-2.0
1.5
37
5 th Stage
2.8-3.2
3.0
45
The light refrigerant 92 from the drum 88 passes through all of the heat exchangers 10 to 20 and is condensed and subcooled in the process. It is subcooled to about −130° C. at the exit 94 from heat exchanger 20 and then flashed through valve 96 to provide the lowest refrigeration temperature of −140° C. to −145° C. This level of refrigeration provides the cooling of the charge gas stream at 42 down to −130° C. or lower and to provide sufficient cooling in the loop 52 to generate reflux from the demethanizer overhead.
The charge gas temperature in streams 26 and 34 are typically controlled at −72° C. and −98° C. respectively by controlling the flow of the light refrigerant in streams 98 and 100 . Typically, the refrigeration supplied by the stream 102 will meet the refrigeration demand in heat exchangers 20 , 18 and 16 . The light refrigerant is finally superheated to −45° C. in heat exchanger 14 . This provides the desired superheat temperature of 5 to 15° C. when it is mixed with portions of the heavy and medium refrigerate streams for return to the first stage suction drum 104 .
The liquid 90 from the drum 88 is the medium refrigerant which is subcooled as it passes through heat exchangers 10 , 12 and 14 . This medium refrigerant controls the temperature of the charge gas at 23 and 24 by flashing the subcooled refrigerant through valves 106 and 108 . From valve 108 , the medium refrigerate flows back through heat exchangers 14 and 12 and then to the suction drum 104 for the first stage 61 of the compressor. From valve 106 , the medium refrigerant flows back through heat exchangers 12 and 10 and then to the suction drum 112 for the third stage 64 of the compressor. The liquid level in drum 88 is controlled by adjusting the valve 110 and providing limited refrigeration to heat exchanger 10 . This portion of the medium is then fed to the suction drum 114 for the fourth stage 66 of the compressor.
The heavy refrigerant 80 from the drum 78 is about 88% propylene. This liquid supplies two major duties, i.e., the cooling for the ethylene condenser 59 and the major refrigeration demand in heat exchanger 10 to support the self-refrigeration of the tertiary refrigeration system. The degree of subcooling of the heavy refrigerant exiting the heat exchanger 12 at 116 is flexible between −10° C. and −35° C. The following table is a summary of the suction streams to the compressor and the compressor flows.
Wt % of
Ave.
Stages
Type of Refrigerant
total flow
MW
1 st Stage Suction
100% Light Refrigerant
9.0
Medium Refrigerant
3.5
Heavy Refrigerant
56.0
1 st & 2 nd Stage Flow
68.5
38.14
3 rd Stage Side Inlet
Medium Refrigerant
3.0
3 rd Stage Flow
71.5
38.14
4 th Stage Side Inlet
Medium Refrigerant
7.0
Heavy Refrigerant
21.5
4 th Stage Flow
100
38.48
5 th Stage Suction
Light & Medium
22.5
34.35
and Discharge Flow
Refrigerant
As shown by the above table, the split of the refrigerant for the purpose of energy saving and then the recombination of the refrigerants, particularly the recombination in the first compressor stage of the light and most of the heavy refrigerants along with some medium refrigerant to provide almost 70% of the total flow in the first stage stabilizes the compressor wheels. With 70% of the total flow in the first stage and a relatively uniform molecular weight throughout, a normal speed control of the turbine by the first stage suction drum pressure becomes equally applicable to the tertiary refrigerant compressor system as to a single refrigerant compressor system. After the extraction of the heavy refrigerant from the fourth stage flow, the flow and the molecular weight in the fifth stage becomes substantially lower. However, the fifth stage compression can be designed and the loading variations can be controlled by the recycle flow to the first stage to minimize the effects. With respect to the control of the process chilling duties, the variables which can be used include the control of the critical temperature, the adjustment of the overall refrigerant composition, the adjustment of the temperatures in the separation drums 78 and 88 and the adjustment of the compressor operating conditions.
The closed loop tertiary refrigeration system with one or more side draws from the compressor inter-stages of the present invention provides a versatile system in which various refrigerant compositions can be formed and various refrigeration levels can be provided. This provides precise temperature control in an efficient and economical manner. Therefore, a single closed loop tertiary refrigeration system can adequately provide all the necessary refrigeration to the entire ethylene plant with either a low pressure or high pressure demethanizer at a competitive power consumption and a lower overall plant cost. | The refrigeration system for an ethylene plant comprises a closed loop tertiary refrigerant system containing methane, ethylene and propylene. The tertiary refrigerant from a compressor is separated into an inter-stage discharge and the final compressor discharge to produce a methane-rich vapor fraction and two levels of propylene-rich liquids so as to provide various temperatures and levels of refrigeration in various heat exchange stages while maintaining a nearly constant refrigerant composition flowing back to the compressor and with the bulk of the total return refrigerant flow going to the first stage compressor section. This tertiary system can also be applied to an ethylene plant with a high pressure demethanizer. | 5 |
TECHNICAL FIELD
This invention relates to apparatus in the form of an improved orbital sanding instrument which is especially useful for processing artificial fingernails.
BACKGROUND ART
Among the developments of chemistry are polymers that have been applied by the cosmetics industry to the formation of artificial fingernails. These new materials serve as adhesives for bonding plastic extensions to a wearer's fingernails. They are strong and tough and serve both as adhesives and as fillers. Some are capable of being used to build up an extension without anything more. A shield is placed under the nail so that it serves as a form for the lower surface of an extension. The nail material is painted on to the end of the user's nail and over the shield. Drying is rapid, and the result is a hard, tough, properly flexible extension.
However, the qualities that make these materials serve as fillers serve also to produce an extension of uneven thickness and length. The dried material needs to be shaped and then the hardness and toughness are disadvantages. Smoothing and shaping the new nail requires a file or sandpaper or, more usually, a grinding tool.
The underside of the new nail is easily smoothed and polished with the side of a small rotary grinder. A simple cylindrical grinding wheel is adequate because the underside of the nail curves around such a wheel. But smoothing the upper surface and trimming and shaping the end is not so easily accomplished. Here, the nail curves the wrong way and it is more difficult to smooth the edges at the side of the nail without injuring the flesh of the finger.
The difficulty in smoothing the nail, especially on the right hand of a right-handed user, or the left hand of a left-handed user, has effectively prevented women from self treatment to rebuild and extend nails, despite the ease with which the new materials can be used to build up a nail extension.
Treatment is now largely reserved to professionals. That has not diminished the need for a better smoothing apparatus and technique even in the hand of a professional, a conventional grinding tool curves oppositely from nail curvature. However, the professional is required to work fast and is expected not to grind into a client's finger in the process. The smoothing process is primarily mechanical--filing and/or grinding. To do that rapidly generates heat. The craft and hobby kit grinders that have been the manicurists' standard tool are used in a way that concentrates rather than distributes the heat. The result is often discomfort and it has been common practice to keep a container of cooling water at the manicurist's work place to remedy misjudgments. Grinding at the edge of a rotating wheel requires a relatively high degree of skill both in guiding the tool over the work area and in controlling the pressure with which the tool is applied to the nail. Grinding at the side of such a rotating wheel requires even more skill because the tendency for the tool to "walk" is increased. The invention provides an effective and practical solution to these problems.
DISCLOSURE OF THE INVENTION
An object of the invention is to provide an improved tool for polishing, smoothing and shaping fingernails, both artificial and real.
While the invention is particularly useful for manicuring nails, it is applicable to many more tasks. One of the objects of the invention is to provide an improved orbital motion tool.
The invention discards the conventional rotational motion of the grinding surface. Instead, an "orbiting" motion is employed. The grinding surface is flat. Instead of spinning the grinding surface on an axis, the entire surface is orbited about the axis.
The orbital motion permits use of a concave cylinder sanding surface. Shaped thus, the abrating or sanding action is distributed over a greater area. The smoothing action is facilitated and heating is distributed over a wider area and, of course, is less at any particular point.
While the concave cylinder sanding surface is an advantage, it must be oriented properly in use. The invention provides a novel means for mounting the sanding surface and for driving it in orbital motion from a hand-held drive section. The drive section is generally cylindrical. In the manicurist's version, it is small enough and is shaped to be held like a pencil. The on-off switch is mounted in the eraser position, and the sanding surface is carried on a sanding head. The latter is resiliently mounted on the drive section and occupies the position of the lead of the pencil. The spring mounting is special. Drive action is transmitted to the sanding head through a resilient coupling that exhibits one spring rate. The head, whose sanding surface ordinarily lies in a plane perpendicular to the axis of the drive section, is carried on the drive section by a resilient mounting that permits tilting of the head and sanding surface, and which exhibits a different spring rate.
The resilient coupling permits the head to follow the nail contour as the drive section is manipulated like a pencil. The resilient coupling obviates the need for the concave cylindrical sanding surface shape, although in some applications it is preferred to combine those features.
In the preferred form, the on-off switch is one that can be actuated to both states by motion along the axis of the drive section toward the drive section. Thus arranged, the manicurist can turn power on-and-off while holding the unit in one hand by pressing the switch against her/his body or other surface for true one hand operation.
Orbital sanders have a tendency to orbit the user as much as the sanding surface. In the invention, the head is connected to the driving unit through a resilient coupling which, in preferred form, is a coiled spring. The eccentrically mounted weight is driven by a motor in the drive unit through a second resilient coupler which, in preferred form, is a coiled spring within the first spring and oppositely coiled. The result is an orbital motion with only minimum vibration being transmitted to the drive unit, which serves as a handle.
These and other advantages of the invention will become apparent upon a reading of the detailed description of one embodiment that follows. In that connection, it is to be understood that other embodiments are possible and that the scope of the invention is to be measured not by that embodiment but by the scope of the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a view in side elevation of a manicurist's nail finishing instrument according to the invention;
FIG. 2 is a view in elevation of the switch end of the instrument of FIG. 1;
FIG. 3 is a view in elevation of the sanding head end of the instrument;
FIG. 4 is a cross-sectional view taken on line 4--4 of FIG. 1;
FIG. 5 is a cross-sectional view taken on line 5--5 of FIG. 3, the internal parts being shown in elevation;
FIG. 6 is a cross-sectional view of the forward portion of the instrument taken on line 6--6 of FIG. 3, some of the internal parts being shown in section and others being shown in elevation;
FIG. 7 is a partly cross-sectioned view of the head of the preferred embodiment; and
FIG. 8 is a side view of a sanding head whose surface has concave prismatic shape.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The preferred embodiment of the invention is shown in FIGS. 1 through 6 of the drawing. The instrument which is generally designated 10 includes a head section 12, a driving section 14, and a resilient interconnection section 16 by which the head section is connected with the driving section. The exterior is best shown in FIG. 1. The driving section includes a housing 18. The rearward portion 20 of the housing is generally cylindrical except at its rearward end where a pair of diametrically positioned side extensions 22 are shown. Those extensions cooperate with similar extensions of the end cover 24. A pair of machine screws extend, one through each extension of the cover, into threaded openings in the extensions 22 of the body 18. The forward end of the body is also generally cylindrical, although it has reduced diameter. That forward portion is generally designated 26. It is divided into two sections to facilitate assembly of the internal elements. The rearward portion of that reduced diameter section is numbered 28 and it is integrally formed with the cylindrical portion 20. Portions 28 and 20 are joined by a conical section 30 in which a number of airflow openings are formed.
The forward portion 32 of the reduced diameter section is flared outwardly to larger diameter at its forward end. For identification, that flared region has been given the reference numeral 34.
The driving section includes a motor 36 which may be seen in the cross-sectional view of FIG. 5. Electrical power for the motor is supplied from an external source through a jack 38. As best shown in FIG. 5, the motor 36 is connected in series with a control switch 40 across the two terminals of the power input jack 38. This embodiment employs a "push-push switch" which alternately opens and closes in response to pressure applied against the actuator 42. In this embodiment of the invention, the instrument is intended to be held like a pencil by grasping it at the reduced diameter section 26 of the driving section 14 with the fingers adjacent the flared region 34. In an analogy with a pencil, the head section 12 would correspond to the pencil lead.
Except for the extensions 22 and the presence of the power inlet jack 38, the driving section of the instrument is substantially symmetrical about its central axis. The shaft 44 of the motor extends forwardly from the motor on that axis along the axis of the forward section 26.
As best shown in FIG. 6, the motor shaft 44 extends through a member 50 which serves several purposes. It has a generally cylindrical, hollow rearward section 52 which is press-fitted into the adjacent ends of sections 28 and 32 of the smaller diameter section 26 of the driving unit. The forward end of that element 50 has reduced inside and outside diameter at its forward end. A brass fitting 54 is inserted into the smaller diameter end of the element 50 where it serves as a bearing for the forward end of motor shaft 44. The exterior of that reduced diameter forward end of element 50 is formed with circumferential grooves. The several turns of the rearward end of a tilting spring 56 are turned onto the reduced diameter forward end of member 50 so that those turns fit within the grooves of that member to complete a firm connection between the rearward end of the spring 56 and, through the member 50, the drive section 14 of the instrument.
The tilting spring 56 is one of two springs which extend from the driving section 14 of the instrument to the head section 12.
In this embodiment, the head section comprises six elements. They are a cup 60, a cap 62, an eccentrically mounted weight 64, a centrally mounted eccentric shaft 66, a bearing 68 which is press-fitted into an opening at the bottom of the cup member 60 and serves as a bearing for the shaft 66, and, finally, a layer 70 of abrasive material which is bonded to the forward face of the cover 62.
In the preferred embodiment, the cap 62 is removable from the cup 60 and the cap has its side walls notched to form a finger at diametric points of its side wall. The lower end of each finger is shaped to form the catch which fits under the bottom of the cup and serves to retain the cap in place. The clips are sufficiently wide to accommodate guide ribs formed on the external surface of the cup. That construction can be understood by a comparison of FIGS. 4, 5, 7 and 8. The cap shown in FIG. 8 is a modification in that its forward face has a concave cylindrical shape, whereas the cover 62 of the other figures is flat. Except for that, the constructions are the same. In FIG. 4, the fingers of the cap are identified by the reference numeral 76, and the guide ribs of the cup are identfied by the reference numeral 78. In FIG. 8, the cup 60 is unchanged and its parts are identified by the same reference numerals as are employed in the other figures. The cap 80 has a finger 82 which is defined by the cutaway sections 84 one of which fits over a guide rib 78.
As best shown in FIGS. 7 and 8, the rearward or bottom end of the cup is provided with a rearwardly extension 86 which has reduced diameter, and the exterior of which is provided with grooves to accommodate the forward end of the tilting spring 56. It may be seen in FIG. 5 and 6 that the forward end of the tilting spring is threaded onto the grooves of the cup extension 86 so that a connection is completed through the spring from the drive section 14 to the head section 12.
As best shown in FIG. 6, a drive spring 90 which is mounted concentrically within the tilting spring 56 is coiled. At its rearward end that spring is wrapped around the forward end of the motor drive shaft 44. At its forward end the drive spring 90 is wrapped around and fixed to the shaft 66 on which the eccentric weight is mounted.
When power is applied to the motor, shaft 44 rotates, rotating the spring 90 which, in turn, rotates shaft 66 and the eccentric weight 64. The cup and the cover are prevented from rotating about the axis of the shaft by the tilt spring 56. Instead, the head orbits about the axis of the shaft 44. To accommodate that orbital movement, the spring 56 tilts in the direction, at any instant, from the axis of shaft 44 toward the center of gravity of the weight 64. As a consequence, rotation of the weight results in a tilting of the spring 56, and a tilting of the drive spring 90, in every radial direction with each turn of the weight. The spring rate of the springs 90 and 56 are different so that any tendency to oscillatory motion of the driving unit 14 in sympathy with orbital movement of the head is minimized. That effect of minimizing vibration at the handle portion of the instrument is aided by the fact that the two springs are wound in opposite direction.
It will be apparent that, when using the instrument to smooth natural and artificial nail material, the smoothing or abrating action is distributed over a wider area of the nail if that smoothing and abrasive action occurs at the forward face of the instrument head or "grinding wheel" than if the smoothing and abrating action were accomplished by the side edge of the head or grinding wheel. When the head or grinding wheel rotates and spins about its central axis, the head or grinding wheel will tend to "walk" while the tool is in use, and the degree of that "walking" increases with the amount of pressure that is applied by the tool on the nail or other work piece. That walking action is eliminated when orbital motion is used.
Because of the two-part resilient interconnection between the head and the driving unit, vibration can be virtually eliminated from the driving unit which is the hand-held portion of the instrument. That resilient interconnection can have several forms. For example, it could be made of concentrically arranged tubes of elastomeric material. Certainly that form, and other forms that have the effect of driving the head to orbital motion while permitting tilting, can be used. The springs are preferred, especially when the springs are wound in opposite direction as in this preferred embodiment.
One of the advantages of the tilting spring arrangement is that the head can be tilted away from the axis of the motor drive 44 as a consequence of interaction between the head and the work surface. That means that the head tends to follow the curvature of the nail while the nail is being shaped, even though the handle itself is not tilted in corresponding degree.
To minimize the degree in which tilting of the handle is required in shaping a fingernail, the forward face of the head, that is, the forward face of the cap and of its abrasive covering, can be curved as shown in FIG. 8. The curve is concave-cylindrical as that term is employed in the lens making art.
Although I have shown and described certain specific embodiments of my invention, I am fully aware that many modifications thereof are possible. My invention, therefore, is not to be restricted except insofar as is necessitated by the prior art. | A fingernail shaping instrument in the form of an orbital sander having a head containing an eccentrically mounted weight, a drive unit containing a drive motor, a coiled tilting spring interconnecting the head and drive unit such as to permit orbital motion of the head relative to the drive unit. A separate coiled drive spring interconnects the motor and the weight. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the catalytic isomerization of alpha-isophorone to beta-isophorone.
2. Discussion of the Background
Beta-isophorone is of great economic interest as a basic organic material for organic preparations, for example, in the perfume industry as well as a starting product for various vitamin syntheses. However, in the well-known trimerization of acetone the product is mainly alpha-isophorone in more than 90% yield. A high yield, simple conversion of the alpha-isomer to the beta-isomer is of particular interest, as it is possible to synthesize from the beta-isomer, natural products, which produce little or no problems in their effect or their degradation behavior.
The shifting of the double bond in the isophorone molecule resulting from the synthesis of alpha-isophorone produces great problems because
(1) the double bond must be shifted out of conjugation with the carbonyl group,
(2) the system easily reacts to stronger alkali or even acid catalysts with dehydration of the compounds and polymerization,
(3) the energy content of the molecule must be clearly raised and
(4) the adjustment of the equilibrium takes place only slowly.
Due to the relatively small amount of beta-isophorone existing at equilibrium, the continuous removal of the desired isomer causes considerable technical problems; however, it is not in each case a prerequisite for a practical procedure. As no changes can be made in the equilibrium for generally known thermodynamic reasons, it was possible only to attempt to influence the rate of the equilibrium adjustment without causing an increase in side reactions. ##STR1##
A number of methods for the preparation of beta-isophorone are known. However, all of these methods have considerable disadvantages, so that to date none of these methods can be converted into practice or utilized on a technically applicable scale. A molecular rearrangement can be produced, e.g., by the conversion of molar quantities of alpha-isophorone with methylmagnesiumiodide with the addition of iron(III)chloride, subsequent hydrolysis and distillative processing (A. Heymes and P. Teisseire, Recherches 1971, 18, 104-8). The isomerization also takes place upon several hours of boiling with triethanolamine, subsequent fractionation and washing of the distillate with tartaric acid and salt solution (Firmenich S. A., DE-OS No. 24 57 157). The conversion is also possible by catalysis with weakly dissociated organic acids. In one such procedure the yield is about 70% of pure beta-isophorone with the use of adipic acid (Hoffmann-La Roche & Co. AG, DE-PS No. 25 08 779).
All the known procedures have the disadvantage that either the use of large volumes of chemicals are required with the related reprocessing and waste disposal problems or that the catalysts used are too weakly alkaline or acidic to realize an acceptable space/time yield. A simple increase or reduction of the acidity of the catalyst is not possible as otherwise there is increased polymerization and dehydration by self-condensation of the isophorone.
SUMMARY OF THE INVENTION
Accordingly, one object of the present invention is a procedure for obtaining beta-isophorone from alpha-isophorone which does not have the disadvantages of the known processes, is less expensive and leads to high yields of beta-isophorone.
This and other objects which will become apparent from the following specification have been achieved by the present process for the production of beta-isophorone from alpha-isophorone which comprises
(i) heating alpha-isophorone in the presence of an isomerization catalyst, said catalyst comprising a metal acetylacetonate, wherein said metal is selected from the group consisting of aluminum and the metals of Groups IVB, VB, VIB, VIIB and VIIIB of the periodic table, to produce beta-isophorone, and
(ii) isolating said beta-isophorone.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is a procedure for the production of beta-isophorone from alpha-isophorone, wherein alpha-isophorone is eated, preferably with distillation in the presence of acetylacetonates of aluminum and the metals of groups IVB, VB, VIB, VIIB and VIIIB of the periodic table.
The group assignment is done according to the designation in Chemical Abstracts. Particularly suitable catalysts are the acetylacetonates of Fe, Co, Cr, Mn and Al.
By complex formation, the strength of the Friedel-Crafts compounds, such as AlCl 3 , FeCl 3 etc. is greatly reduced. However, the isomerization capability for double bonds in delicate system is at least in part maintained.
It has been shown in tests that, in general, transition metal acetylacetonates are particularly suited as carbon-carbon double bond shifting catalysts. Although the metal atoms are very tightly bound in these complexes, they can greatly increase the rate of adjustment of the equilibrium. For the present isomerization, only 0.01 to 10% by weight, preferably 0.1 to 1.0% by weight of the metal acetylacetonates are needed. The considerable reduction in catalyst quantity relative to known methods must be regarded as an important process improvement. In addition, the reaction time is reduced by at least 50%, which leads to a doubling of the space/time yield with comparable design of the apparatus.
The procedure of the present process is technically relatively simple and can be executed continuously or discontinuously, i.e., batchwise.
It is preferable to perform the isomerization in conjunction with a distillation process to remove the beta-isophorone as it is formed. However any other means of separating the beta-isomer from the isomerized reaction product is considered to be within the scope of the present invention.
In a preferred embodiment, fresh technical grade isophorone is continuously metered into a distillation apparatus containing alpha-isophorone and 0.1 to 1% by weight of a transition metal acetylacetonate. The addition of alpha-isophorone is made in an amount such that an overhead fraction containing beta-isophorone can be withdrawn from the fractioning column. The beta-isophorone obtained in this manner has a purity of about 95% and can be further concentrated as desired by additional fractional distillation. The heat energy required for isomerization is provided by the boiling distillation residue in the apparatus working at normal pressure. With this procedure, a heat temperature of 187° C. is easily attained. In spite of the significant progress made, the present procedure does not work completely without loss; about 5 to 7% of the isophorone collected by condensation of the overhead fraction must be rejected. However, a yield of 90 to 95% of beta-isophorone, relative to the starting material, may be expected.
It is preferable to operate at normal atmospheric pressure, in order to use the boiling point difference between alpha and beta-isomers of isophorone. When working at reduced pressure, the boiling point difference is reduced and the demands on the separation capabilities of the distillation column are increased.
Other features of the invention will become apparent in the course of the following description of exemplary embodiments which are given for illustration of the invention and are not intended to be limiting thereof.
EXAMPLES
Example 1
From a 1 L flask, 500 ml technical isophorone (GC analysis: 98.7% alpha-isophorone, 0.98% beta-isophorone) are distilled off through a fractioning column after mixing with 2 g of iron(III)acetylacetonate (corresponding to 0.43% by weight). A 1 m column with 2.5 cm diameter and "Multifil" V4A packing material, with a preheater set at 155° C. is sufficient to obtain adequate isomerization. The required distillation vessel temperature is 215° C. at the beginning, but must be raised to 250° C. towards the end of the distillation. As soon as the apparatus is at equilibrium, a temperature of 186° C. is maintained as the distillation head temperature. The system remains stable at a reduction/reflux ratio of 1:10. With the described column size it is possible to obtain 20 ml of the product per hour.
The isolated product weighed 445 g, corresponding to 89% raw yield (CG analysis: 94% beta-isophorone, 5% alpha-isophorone), with 55 g (11% by weight) residue remaining in distillation vessel. The residue consists (see example 4) of 70 to 80% alpha-isophorone and can be recycled to the apparatus after purification.
Simple distillation of the product through a 40 cm Vigreux column with a reduction of 100 ml/h resulted in 99% beta-isophorone as the raw product. If the recycled alpha-isophorone is taken into account, a pure yield of 97 to 98% beta-isophorone is obtained with this procedure.
Examples 2 to 9
In the same manner as in Example 1, isomerization is conducted with different catalysts. The results are shown in the following table:
TABLE______________________________________Exam- Cata- Product Yield Yield Resi-ple Catalyst lyst yield raw pure dueNo. metal (%) (ml/h) (%) (% conv.) (%)______________________________________2 Fe(III) 0.44 20 80 95.4 20.sup.a3 Co(III) 1.0 20 77 93.9 22.sup.a4 Co(III) 1.0 20 77 94.7 23.sup.a5 Cr(III) 1.0 10 74 93.3 25.sup.a6 Al(III) 1.0 10-15 77 94.7 23.sup.a7 Ni(II).sup.b 1.0 10 48 -- --8 Mn(II) 1.0 20-10 73 93.0 26.sup.a9 Ti(IV).sup.b 1.0 20 44 -- --______________________________________ .sup.a The residue is 77% (GC analysis) alphaisophorone which can be recycled. .sup.b The catalyst lost its activity in the course of the test.
Example 10
Analogous to Example 1, 1800 g alpha-isophorone are isomerized with 0.11% by weight iron(III)acetylacetonate when the distilled raw product is continuously replaced by fresh starting product. A raw yield of 84% is attained with 15% retained as residue.
Obviously, numerous variations and modifications of the invention are possible in light of the above teachings. Therefore, in light of the above teachings, it is to be understood that the invention may be practiced other than as specifically described herein. | A process for the production of beta-isophorone from alpha-isophorone, comprising the steps of:
(i) heating alpha-isophorone in the presence of an isomerization catalyst, said catalyst comprising a metal acetylacetonate, wherein said metal is selected from the group consisting of aluminum and the metals of Groups IVB, VB, VIB, VIIB and VIIIB of the periodic table, to produce beta-isophorone, and
(ii) isolating said beta-isophorone. | 2 |
FIELD OF THE INVENTION
The present invention relates to a system, method and computer instruction code for wagering. Although not exclusively, the invention is particularly useful for implementing a “unified” wagering system.
BACKGROUND TO THE INVENTION
The terms “gambling” and “betting” refer to a risking of something, typically money, with respect to the outcome of a future event. Typically, two or more people gamble on different outcomes of the event, and the winner, or winners, collect all, or a substantial portion of a prize pool. The event may be a sporting, racing, or political event, for example. The ratio between the risked amount and a return is typically referred to as “odds”. Typically, the odds of an outcome correlate with the likelihood of an outcome occurring.
A horse for example, may have odds of 50 to 1 to win a particular race. If $1 is wagered on this outcome, the return is $50 in the event the horse wins the race. The likelihood of the horse winning is considered to be approximately 1/50.
Betting is typically coordinated between gamblers by a third party entity. In horse racing, for example, this coordination has been traditionally satisfied by bookmakers at a race track. More recently, bookmakers have been replaced by larger companies offering gambling external to where an event occurs, sometimes via the Internet.
There are a number of betting products on the market, some specific to a type of event, others more generic. For example, a trifecta is a betting product where an outcome is the horses, for example, that finish in first, second and third places. Another, more generic betting product, is simply betting on a win for a horse, team, or political party, for example.
Another category of betting products relates to the calculation of odds. These forms include “pari-mutuel” betting and “fixed odds” betting.
Pari-mutuel betting is a form of betting in which the odds are not known to a gambler when placing a bet. The odds are determined after new bets are no longer allowed. The odds change as bets are placed on an event. In other words, the odds are dependent upon the other bets in the pool as the total pool is split among the winners. In pari-mutuel betting, the bookmaker has no risk as the betters are effectively betting against each other with the winners sharing the combined pool.
Fixed-odd betting is a form of betting where the odds are known to a better when placing a bet. The bookmaker chooses the odds for the event. These odds may be continually updated, but a gambler is provided the odds offered at the time the bet is placed, irrespective of any later changes. The bookmaker may base the odds upon previous bets, his own knowledge and/or other factors.
Modern gambling has generally moved from the traditional bookmakers to larger companies running complex information technology systems. Services are often provided directly over the Internet, or via communications means to a number of smaller outlets. As these systems are typically large, the odds provided/offered are typically accurate.
A disadvantage of the above described prior art systems is that separate systems are required for different betting products. For example, fixed-odd and pari-mutuel betting, if both offered by a betting provider, are provided by specific and dedicated systems. This results in higher acquisition and maintenance costs as compared with a single system as multiple systems must be purchased, developed and maintained. The ongoing additional cost of maintaining numerous systems is considerable and represents a significant cost to a business offering both fixed odds and pari-mutuel betting products.
A further disadvantage of known systems is that they are not easily extensible to allow for the addition of new products. Products and the events to which a product refers, are inseparable in known systems. Thus the addition of a new product requires substantial system modification which usually incurs a significant cost in the form of high skilled labour costs to attend to any requisite modifications.
Therefore, there is a need to overcome or alleviate one or more of the above identified problems associated with known wagering systems.
SUMMARY OF THE INVENTION
According to one aspect, the present invention provides a computer-implemented method of wagering, wherein a computer system manages an electronic data store, having stored therein, a plurality of events, a plurality of products and a plurality of customer accounts, all of which are independently defined, the method including: receiving, via a communications network, a wager from a customer in respect of an event of the plurality of events, a product of the plurality of products and a customer account of the plurality of customer accounts; and storing the wager, in the electronic data store, and associating the wager with the event, the product and the customer account.
By independently defining various entities such as events, products and customer accounts, the system and method of the present invention can record and manage any type of wager including pari-mutuel and fixed odds. Effectively, the method and system of the present invention is configured to treat the wager as the primary entity with relationships between the wager and other entities, such as specific products and the customer account, being formed according to the particular circumstances of the wager. Adopting this approach allows a unified wagering system to be established that accommodates a range of different types of betting including pari-mutuel and fixed odds wagering.
According to an embodiment, the computer-implemented method of wagering further includes receiving, via a communications network, information relating to an outcome of the event; determining, on a computer processor, an outcome of the wager; and transmitting, via a communications network, the outcome of the wager.
According to another embodiment, the computer-implemented method of wagering further includes receiving, via a communications network, a request for event information from the customer; selecting, on a computer processor, and retrieving, from the data store, one or more events; and transmitting, via a communications network, an event list including information relating to the one or more events, to the customer; wherein the event is an event of the one or more events in the event list.
The request and the wager may be received from the customer via a channel, the channel including one of a purpose built kiosk, a computer application, and a browser based application.
The one or more events may be selected according to at least one of customer or account preference, jurisdiction and location. Additionally, or alternatively, the event list is sorted according to at least one of customer or account preference, jurisdiction and location.
According to another embodiment, the computer-implemented method of wagering further includes: retrieving, from the data store, a plurality products; and associating each of the one or more events with one or more products of the plurality of products.
The one or more products associated with each event may be included in the event list. Alternatively, links to the one or more products associated with each event may be included in the event list.
The plurality of products may include fixed odds and pari-mutuel products.
According to another aspect, the present invention provides a computer system including: a database for maintaining data associated with at least one event, a plurality of products, and at least one customer account, wherein the at least one event and the at least one customer account are stored independently to the plurality of products; and a computer coupled to the database, wherein the computer includes a processor and a memory, the processor and memory configured to: generate, based upon input from a customer associated with a customer account of the at least one customer account, records pertaining to a betting instance including the at least one event, a product from the plurality of products, and the customer account; wherein the plurality of products includes pari-mutuel and fixed odds products.
According to an embodiment, the processor and memory are additionally configured to: retrieve information relating to the at least one event from the database; and associate the at least one event with one or more of the plurality of products.
According to yet another aspect, the present invention provides a computer implemented wagering system, the wagering system including: an event module for storing a plurality of events; a product catalogue module for storing a plurality of products, the plurality of products including at least pari-mutuel and fixed odds products; a customer data module for storing customer account data for a plurality of customers; and a betting instance module, for generating betting instances, the betting instances including an association to an event from the event module, to a product from the product catalogue module, and to a customer account from the customer data module.
The event module may include, for each of the plurality of events at least one contestant, and the betting instance module an association to a contestant from the event module.
The customer data module may include, for a customer, a plurality of accounts, and the betting instance module includes an association between the customer and an account of the plurality of accounts.
According to an embodiment, the computer implemented wagering system further includes an event-product rule module, which includes rules relating to which products from the plurality of products may be associated with an event.
According to another embodiment, the computer implemented wagering system further includes an account-event rule module, which includes rules relating to which events from the plurality of events may be associated with a customer account.
The computer implemented wagering system may include a channel module, for storing information relating to a plurality of channels. The system may include a customer account-channel rule module, which includes rules relating to which channels from the plurality of channels a customer account has access.
The computer implemented wagering system may include a product-channel rule module, which includes rules relating to which channels from the plurality of channels a product is available.
The computer implemented wagering system may include an event channel rule module, which includes rules relating to which channels from the plurality of channels an event is available.
According to another aspect, the invention provides a computer program embodied on a computer readable medium including software code adapted, when executed on a data processing apparatus, to provide a method of wagering as described above.
BRIEF DESCRIPTION OF THE DRAWINGS
To assist in understanding the invention and to enable a person skilled in the art to put the invention into practical effect, embodiments of the invention are described below by way of example only with reference to the accompanying drawings, in which:
FIG. 1 is a diagrammatic illustration of a computer system, with which the present invention may be implemented;
FIG. 2 is a diagrammatic illustration of a unified wagering system according to an embodiment of the present invention;
FIG. 3 illustrates a wagering system, according to an embodiment of the invention;
FIG. 4 is a diagrammatic illustration of a method of wagering, from the view of a computer system, according to an embodiment of the present invention;
FIG. 5 is a diagrammatic illustration of a method of wagering, from the view of a computer system, according to an embodiment of the present invention;
FIG. 6 is a diagrammatic illustration of a wagering system, according to an embodiment of the present invention;
FIG. 7 is a diagrammatic illustration of a database, according to an embodiment of the present invention;
FIG. 8 is an illustration of an event list, according to an embodiment of the present invention; and
FIG. 9 is a diagrammatic illustration of a wagering system, according to an embodiment of the present invention.
Skilled readers will appreciate that minor deviations from the layout of components as illustrated in the drawings will not detract from the proper functioning of the disclosed embodiments of the present invention.
DETAILED DESCRIPTION OF EMBODIMENTS
Embodiments of the present invention include a wagering system, method and computer software. Elements of the invention are illustrated in concise outline form in the drawings, showing only those specific details that are necessary for understanding the embodiments of the present invention, but so as not to clutter the disclosure with excessive detail that will be obvious to a skilled reader.
FIG. 1 is a diagrammatic illustration of a computer system 100 , with which the present invention may be implemented.
The computer system 100 includes a central processor 102 , a system memory 104 and a system bus 106 that couples various system components including the system memory 104 to the central processor 102 . The system bus 106 may be any of several types of bus structure including a memory bus or memory controller, a peripheral bus, and a local bus using any of a variety of bus architectures. The structure of system memory 104 is well known to those skilled in the relevant field of technology and may include a basic input/output system (BIOS) stored in a read only memory (ROM) and one or more program modules such as operating systems, application programs and program data stored in random access memory (RAM).
The computer system 100 may also include a variety of interface units and drives for reading and writing data. In particular, the computer system 100 includes a hard disk interface 108 and a removable memory interface 110 respectively coupling a hard disk drive 112 and a removable memory drive 114 to system bus 106 . Examples of removable memory drives 114 include magnetic disk drives and optical disk drives. The drives and their associated computer-readable media, such as a Digital Versatile Disc (DVD) 116 provide non-volatile storage of computer readable instructions, data structures, program modules and other data for the computer system 100 . A single hard disk drive 112 and a single removable memory drive 114 are shown for illustration purposes only and with the understanding that the computer system 100 may include several of such drives. Furthermore, the computer system 100 may include drives for interfacing with other types of computer readable media.
The computer system 100 may include additional interfaces for connecting devices to system bus 106 . FIG. 1 shows a universal serial bus (USB) interface 118 which may be used to couple a device to the system bus 106 . An IEEE 1394 interface 120 may be used to couple additional devices to the computer system 100 .
The computer system 100 can operate in a networked environment using logical connections to one or more remote computers or other devices, such as a server, a router, a network personal computer, a peer device or other common network node, a wireless telephone or wireless personal digital assistant. The computer 100 includes a network interface 122 that couples system bus 106 to a local area network (LAN) 124 . Networking environments are commonplace in offices, enterprise-wide computer networks and home computer systems.
A wide area network (WAN), such as the Internet, can also be accessed by the computer system 100 , for example via a modem unit connected to serial port interface 126 or via the LAN 124 .
It will be appreciated that the network connections shown and described are exemplary and other ways of establishing a communications link between the computers can be used. The existence of any of various well-known protocols, such as Frame Relay, Ethernet, TCP/IP, FTP, HTTP and the like, is presumed, and the computer system 100 can be operated in a client-server configuration to permit a user to retrieve web pages from a web-based server. Furthermore, any of various conventional web browsers can be used to display and manipulate data on web pages.
The operation of the computer system 100 can be controlled by a variety of different program modules. Examples of program modules are routines, programs, objects, components, and data structures that perform particular tasks or implement particular abstract data types. The present invention may also be practiced with other computer system configurations, including hand-held devices, multiprocessor systems, microprocessor-based or programmable consumer electronics, mainframe computers, personal digital assistants and the like. Furthermore, the invention may also be practiced in distributed computing environments where tasks are performed by remote processing devices that are linked through a communications network. In a distributed computing environment, program modules may be located in both local and remote memory storage devices.
FIG. 2 is a diagrammatic illustration of a unified wagering system 200 according to an embodiment of the present invention.
A customer interacts with the system 200 through a channel 204 connected to the system 200 . The channel 204 allows the customer to access his or her account 206 and to place a bet on an event 208 . Examples of channels 204 include a mobile phone, a kiosk located at a betting location, and a web browser running on a computer.
The account may, for example, include customer preferences, customer jurisdiction, or other details of the customer. The customer may obtain access to his or her account through an authorization module that authorises the credentials of the customer. Examples of credentials include a username, password, smart card or digital certificate. Authorization modules and authentication are well known in the art.
Each customer may be associated with one or more accounts. If a customer is associated with more than one account, the authorization module may also select an account based upon credentials, for example.
After authentication, the customer may view an event 208 to which a bet can be placed. Rather than a single event 208 , as shown in FIG. 2 , a plurality of events 208 are typically offered for betting. The plurality of events 208 may be filtered based upon preferences of the customer, a location, the channel used, account preferences, account jurisdiction, or by other means. The events 208 are advantageously sorted, for example by event date or alphabetically.
The system 200 includes a plurality of products 210 . Examples of products 210 include betting on a win, a place, quinella, trifecta, etc. The plurality of product 210 includes both fixed odds and pari-mutuel (variable odds) products.
Each event 208 is matched with a product 210 or a plurality of products 210 that are allowed for that event. For example, a sports match may allow betting on a win, but not a place. The products 210 available for an event 208 may advantageously change over time. For example, for sporting events, certain products 210 may be made available after the event 208 has begun.
The customer may then select to gamble an amount of money on an outcome of an event 208 . A bet instance 212 is generated including a product instance, an event instance, and a customer/account instance.
The products 210 , the events 208 and the accounts 206 are stored in a database. The products 210 , the events 208 and the accounts 206 are stored separately in the database. In other words, the products 210 are defined independently from the events 208 and accounts 206 , and the events 208 are defined independently from the accounts 206 .
The database is designed using an object oriented approach, which includes product objects, event objects and customer objects. The product object allows for the inclusion of both fixed odds and Pari-mutuel (variable odds) products.
The independent definitions, especially of the events 208 and products 210 , allows for new products to easily be defined. Additionally, multiple products 210 for a single event 208 are easily added to the system without a large amount of redundancy.
FIG. 3 illustrates a wagering system 300 , according to an embodiment of the invention. The system 300 includes an account module 302 , an event module 304 , a product module 306 , and a channel module 308 . Each of the modules 302 , 304 , 306 , 308 defines the data structures of the system 300 . The system 300 additionally includes a betting instance module 384 which includes instances of the data structures of the modules 302 , 304 , 306 , 308 .
The account module 302 specifies fields or parameters of an account. The account module 302 includes an account type 310 . The account type 310 is associated with a jurisdiction 312 and a tier 314 . Examples of jurisdictions 312 include country (e.g. Australia) and state (e.g. New South Wales, NSW). Examples of tiers 314 include Bronze, Silver and Platinum and indicate a membership status of the account. The account type 310 is associated with one or more account specifications 316 which include a blackbook 318 and one or more preferences 320 .
The account module 302 includes a customer type 322 . The customer type is associated with one or more customer specifications 324 , an affiliate 326 , a third party 328 and a physical person 330 .
The account module 302 is connected to the event module 304 . An event type 332 of the event module 304 is connected to the account type 310 of the account module 302 via an account-event rule configuration 342 .
The account-event rule configuration 342 may specify rules which govern whether an account has access to an event. For example, premium events, such as pay per view boxing, may only be available to Platinum members. Additionally, certain events may be illegal to gamble on in certain jurisdictions.
The event type 332 provides information about an event through a categorisation. Examples of event types 332 include race, match, game, round and fight. The event type 332 may be associated with event specifications 334 . The event type 332 is associated with a contestant type 338 through one or more event-contestant rule configurations 336 . A contestant type 338 may be, for example, a team, a player, or a horse. The contestant type 338 may be associated with contestant specifications 340 .
The event module 304 is connected to the product module 306 . A product type 344 of the product module 306 is connected to the event type 332 of the event module 304 , through an event-product rule configuration 346 . The event-product rule configuration 346 may specify products types 344 that are compatible with an event type 332 . This may include, for example, that a trifecta product, i.e. first, second and third placing in a race, may only relate to horse or greyhound racing events, and not to other events such as sporting matches.
The product module 306 may include product bundles 348 associated with a product type 344 , and product specifications 350 . The product specifications 350 includes the type of odds offered for a product, including fixed odds and pari-mutuel (variable) odds.
The event module 304 , the product module 306 , and the account module 302 are connected to the channel module 308 . The channel module provides information regarding access to the wagering system 300 , through device descriptions, for example.
A channel type 352 of the channel module is connected to the product type 344 of the product module 306 via a product-channel rule configuration 354 . The product-channel rule configuration 354 may specify a channel type 352 that is available for a certain product type 344 . For example, a live odds product may only be available via the Internet.
The channel type 352 of the channel module is connected to the event type 332 of the event module 304 via a channel-event rule configuration 356 . The channel-event rule configuration 356 may specify a channel type 352 over which an event type 332 is available. For example, a local horse race event type may only have products available via a local outlet.
The channel type 352 of the channel module 308 is connected to the account type 310 of the account module 302 via an account-channel rule configuration 358 . The account-channel rule configuration 358 may specify a channel type 352 that is available to an account type 310 . For example, gambling via the internet may not be available to certain account types 310 depending on their jurisdiction 312 , for example.
The channel module 308 may include channel specifications 360 associated with a channel type 352 . Additionally, a device type 364 may be associated with a channel type 352 via a channel-device rule configuration 362 . The device type 364 may also have associated device specifications 366 .
The betting instance module 384 is central to the system 300 , and includes instances of each of the major features described above that are associated with a bet. A customer instance 368 is associated with a customer type 322 , an account instance 370 is associated with an account type 310 , a product instance 376 is associated with a product type 344 , an event instance 374 is associated with an event type 332 , and a contestant instance 372 is associated with a contestant type 338 .
The customer instance 368 is associated with one or more account instances 370 . One or more contestant instances 372 are associated with a product instance 376 , and an event instance 374 is associated with a product instance 376 . The betting instance module 384 additionally includes an event result 378 associated with the event instance 374 . Additionally, a dividend and prices 380 are associated with a product instance 376 .
The account instance 370 and the product instance 376 , along with their associated data as described above, together make a ‘bet ticket’ 382 .
FIG. 4 is a diagrammatic illustration of a method of wagering 400 , from the view of a computer system, according to an embodiment of the present invention.
The computer system manages an electronic data store. The electronic data store has a plurality of events, a plurality of products and a plurality of customer accounts stored thereon, all of which are independently defined.
At step 405 , a wager is received, via a communications network and from a customer, in respect of a wagered event and a wagered product.
The communications network may, for example, include the Internet, but as will be readily understood by a skilled reader, any suitable communications network may be used.
The wager may include explicit reference to an event, a product, an outcome, and an account, for example. Alternatively, the wager may include an identifier associated with wager details known by the system. This may include a ‘favourite’ wager type, a suggested wager, or a response to a list of predetermined wagers, for example.
At step 410 , the wager is stored in the electronic data store. The wager is associated with the wagered event, the wagered product and the customer.
The wagered product, the wagered event and the customer are stored in a database as instances of a product definition, an event definition and a customer definition. The products are thus defined independently from the events and the customers, and the events are defined independently from the customers, through their separate definitions.
FIG. 5 is a diagrammatic illustration of a method of wagering 500 , from the view of a computer system, according to an embodiment of the present invention.
The method of wagering 500 is similar to the method of wagering 400 , and includes a similar electronic data store.
At step 505 , a request for event information is received, via a communications network, from a customer. The request may include requesting a web page containing the event information, or any other suitable form of data request.
At step 510 , one or more events are selected, on a computer processor, and retrieved from the data store. The one or more events may be selected based upon a location of a customer, a preference of the customer, a jurisdiction of the customer, or based upon any other suitable parameter.
At step 515 , an event list, including the one or more events from step 510 , is transmitted, via a communications network, to the customer. The event list may include a web page, or raw data to be presented by an application.
The event list may include links to products which are available for each event. The event list may, for example, comprise a list of events with associated products. The products may be directly part of the event list, or accessible via one or more additional lists or pages.
At step 520 , a wager is received, via a communications network and from the customer, in respect of a wagered event and a wagered product.
The wager may be received as an identifier embedded in the event list, for example, or through explicit identification.
At step 525 , the wager is stored in the electronic data store. The wager is associated with the wagered event, the wagered product and the customer.
The wagered product, the wagered event and the customer are stored in a database as instances of a product definition, an event definition and a customer definition. The products are thus defined independently from the events and the customers, and the events are defined independently from the customers, through their separate definitions.
At step 530 , information relating to an outcome of the event is received, via a communications network. The information may include a winning person, horse or team, for example, but may include further details such as a time, placements, a score, or similar information.
At step 535 , an outcome of the wager is determined on a computer processor.
The outcome may be determined using the outcome information 520 alone, or in combination with other information. The outcome may, for example, be calculated as a wagered amount multiplied by an odds of the outcome. The odds may be determined at the time the wager was placed, i.e. fixed odds betting, and stored in a data store associated with the wager. Alternatively, the odds may be determined when no further wagering is allowed for the event, e.g. pari-mutuel wagering, and stored in a data store associated with the event.
At step 540 , the outcome of the wager is transmitted via the communications network. The outcome may be transmitted to the customer, possibly including information on how to redeem a winnings. The outcome may be transmitted to a gambling agent, or other person, which may handle payouts for the event.
FIG. 6 is a diagrammatic illustration of a wagering system 600 , according to an embodiment of the present invention.
The wagering system includes a computer 605 and a database 610 . The database 610 may be part of the computer, or alternatively connected to the computer via a computer interface.
The computer 600 includes a central processor 615 connected to a memory 620 . The memory includes a betting instance 625 .
The database 610 includes an events table 630 , a products table 635 and a customers table 640 . The database 610 is accessible to the central processor 615 of the computer 605 . The database 610 may have an SQL query interface, or any other suitable interface.
By independently defining events table 630 , a products table 635 and a customers table 640 , the system of the present invention can record and manage any type of wager including pari-mutuel and fixed odds, efficiently.
FIG. 7 is a diagrammatic illustration of a database 700 , according to an embodiment of the present invention.
The database 700 includes an events table 705 , a products table 710 and a customers table 715 .
The events entity 705 includes a plurality of entries 705 a - c , each entry 705 a - c corresponding to an event. Each entry 705 a - c may include fields identifying an event type, an event location, and event identifier, and an event date, for example.
The products entity 710 includes a plurality of entries 710 a - c , each entry 710 a - c corresponding to an event. Each entry 710 a - c may include fields identifying an outcome that is being bet on, and a product type.
The accounts entity 715 includes a plurality of entries 715 a - c , each entry 715 a - c corresponding to a customer account. Each entry 715 a - c may include fields identifying a name of the customer, and a jurisdiction.
As will be readily understood by a person skilled in the art, the entries 705 a - c , 715 a - c , 720 a - c may include more or fewer fields that those described above. For example, each entry may be associated with a unique key.
The database 700 may additionally including betting instance information. The betting instance information is advantageously stored as a separate table which references the events table 705 , a products table 710 and a customers table 715 .
FIG. 8 is an illustration of an event list 800 , according to an embodiment of the present invention.
The event list 800 includes a plurality of events identifiers 805 a - c , and each event identifier is associated with a plurality of betting product links 810 a - i.
The plurality of event identifiers 805 a - c is advantageously sorted according to user preferences, location or jurisdiction.
The plurality of betting product links 810 a - i include links to both pari-mutuel and fixed odds products. The plurality of betting product links 810 a - l provide links specific to their associated event. For example, betting product link 810 c , linking to a fixed odd trifecta product, would not be suitable for the event associated with event identifier 805 c.
FIG. 9 is a diagrammatic illustration of a wagering system 900 , according to an embodiment of the present invention.
The wagering system includes a wagering server 905 connected to a database 910 . The database may, for example, be the database 700 of FIG. 7 , or any other suitable database.
The wagering server is connected to a plurality of devices 915 a - c via a communications network 920 .
The plurality of devices 915 a - c include a purpose built kiosk device 915 a , a personal computer 915 b and a mobile device 915 c.
The purpose built kiosk device 915 a may be running an application on a computer processor, for example. The application may receive raw data via the communications network 920 which is displayed on a screen of the purpose built kiosk device 915 a.
The personal computer 915 b may provide access to the wagering system via a web browser, as will be readily understood by a person skilled in the art.
The mobile device 915 c may include a purpose built application, such as an application for an iPhone device, manufactured by Apple Computer Inc. California, USA, as is known in the area of technology.
The above description of various embodiments of the present invention is provided for purposes of description to one of ordinary skill in the related art. It is not intended to be exhaustive or to limit the invention to a single disclosed embodiment. As mentioned above, numerous alternatives and variations to the present invention will be apparent to those skilled in the art of the above teaching. Accordingly, while some alternative embodiments have been discussed specifically, other embodiments will be apparent or relatively easily developed by those of ordinary skill in the art. Accordingly, this patent specification is intended to embrace all alternatives, modifications and variations of the present invention that have been discussed herein, and other embodiments that fall within the spirit and scope of the above described invention. | A disadvantage of existing betting operations is the implementation of fixed odds and pari-mutuel betting on specific and dedicated systems. This results in higher acquisition and maintenance costs as compared with a single system. According to the present invention, a single system allows both fixed odds and pari-mutuel betting to be offered on a single system wherein the system effects a computer-implemented method of wagering, including: receiving, via a communications network, a wager from a customer in respect of a wagered event and a wagered product; storing the wager, in an electronic data store, and associating the wager with the wagered event, the wagered product and a customer account, wherein the computer system manages the electronic data store, having stored therein, a plurality of events, a plurality of products and a plurality of customers, all of which are independently defined. | 6 |
BACKGROUND OF THE INVENTION
This invention relates to a control system for a fuel fired furnace and more specifically to the control of the stoichiometric ratio within the combustion process occurring within the furnace of a steam generating power plant. Control of the stoichiometric ratio is accomplished by regulating the distribution of air flow to the combustion process in such a manner that the formation of oxides of nitrogen are maintained at consistent levels while simultaneously maintaining carbon in fly ash and carbon monoxide at acceptable levels.
In recent years oxides of nitrogen, also known as NO x , have been implicated as one of the elements in contributing to the generation of acid rain and smog. Now, due to very strict state and federal environmental regulations demanding that NO x emissions be maintained at acceptable levels, the control of the formation of NO x during the combustion process is of critical importance and a major concern in the design and operation of a power plant. As a consequence, combustion control systems must improve to meet these demands.
Oxides of nitrogen are a byproduct of the combustion of hydrocarbon fuels, such as pulverized coal in air, and are found in two main forms. If the nitrogen originates from the air in which the combustion process occurs, the NO x is referred to as `thermal NO x .` Thermal NO x forms when very stable molecular nitrogen, N 2 , is subjected to temperatures above about 2800 F. causing it to break down into elemental nitrogen, N, which can then combine with elemental or molecular oxygen to form NO or NO 2 . The rate of formation of thermal NO x downstream of the flame front is extremely sensitive to local flame temperature and somewhat less so to the local mole concentration of oxygen. Thermal NO x concentration can be reduced by lowering the mole concentrations of N 2 and O 2 , reducing the peak flame temperature and reducing the amount of time that N 2 is subjected to these temperatures.
If the nitrogen originates as organically bound nitrogen within the fuel, the NO x is referred to as `fuel NO x .` The nitrogen content of coal is comparatively small and, although only a fraction is ultimately converted to NO x , is the primary source of the total NO x emissions from a steam generating power plant. The formation rate of fuel NO x is strongly affected by the rate of mixing of the fuel and air stream in general, and by the local oxygen concentration in particular. The formation of fuel NO x is a multi-stage process. During initial coal particle heat up the coal is broken down into both volatile matter consisting of reactive cyanogens, oxycyanogens and amine species and char consisting of unburned carbon, hydrocarbons and ash. In an oxygen rich environment the volatile matter will convert largely to NO x and in a fuel rich environment it can be reduced to N 2 . The remaining fuel bound nitrogen is released during char combustion. For char combustion to approach completion, an oxygen rich process is required. As with the volatile released NO x , the eventual fate of char released nitrogen is dependent upon the specific time, temperature and stoichiometric history.
The stoichiometric ratio, φ, of a combustion process is defined here as the number of moles of oxygen supplied to combust a given quantity of fuel divided by the number of moles of oxygen theoretically necessary to combust a the same quantity of fuel. Typically, the stoichiometric ratio in a fossil fuel fired steam generating power plant is a quantity greater than or equal to one and can be expressed as a percentage in which case it is referred to as percent theoretical air, τ=φ×100. A related term is excess air which is (φ-1)×100 or τ-100.
From the preceding it should be apparent that by controlling the distribution and mass flow rate of air to the combustion process the stoichiometric ratio of the process is controlled and thus the formation of NO x . One method of controlling the mass flow rate of air to the combustion process within a tangentially fired furnace in order to effect a low NO x condition is through the use of staged combustion. Typically a main burner zone is defined wherein pulverized coal is combusted in a fuel rich environment. This is accomplished by withholding a portion of the total air required for complete combustion. This portion of air, which may appear in multiple segments and is commonly known as overfire air (OFA), is instead introduced above the main burner zone and mixed with the products of incomplete combustion after the O 2 content in the main burner zone is consumed. Staged combustion minimizes NO x formations via two mechanisms. First, by having a fuel rich atmosphere during the first stage, the initial amount of fuel NO x formed is reduced because less oxygen is available to combine with the fuel bound nitrogen. Second, lower fuel NO x results because of the reduced air concentrations during the initial firing stage, thus, primary stage residence time increases. Residence time is the amount of time necessary for a coal particle to combust. The increased residence time provides an environment which is conducive to the reduction of any oxidizable N 2 volatiles that have been formed such as NH 3 or HCN. This is done by entraining and reducing NO x compounds and the volatiles into their elemental components, oxygen and nitrogen, and combusting the hydrocarbons. Furthermore, staged combustion reduces the peak flame temperatures, resulting in lower thermal NO x formation.
In a typical configuration for a staged firing system utilizing OFA, combustion air is supplied by a forced draft fan to a common vertical plenum, known as the windbox, and then distributed to the furnace through a number of parallel ducts. Flow rates of combustion air are modulated by individual dampers. For control purposes the dampers are grouped into three categories: fuel/air dampers, adjacent to the fuel elevations, auxiliary air dampers, located between fuel elevations, and overfire air dampers, located above the fuel elevations. The OFA dampers can be further divided into two groups: close-coupled overfire air dampers which feed directly off of the top of the windbox and separated overfire air dampers which supply air to the upper levels of the furnace. Total flow of secondary air to the furnace is controlled by the forced draft fans. The auxiliary air dampers are used to control the windbox-to-furnace pressure differential, dp, as a function of total unit air flow. The fuel/air damper positions are set as a function of the coal feeder speed and the overfire air damper positions are set as a function of unit load or in some cases unit air flow.
Typical prior art combustion control systems consist of a means by which to measure total air flow to the furnace coupled with a means by which, in a preprogrammed manner, overfire air dampers are sequentially opened as unit air flow and unit load are increased; and in a reverse manner are sequentially closed as unit air flow and unit load decrease. This sequencing is based upon the designer's experience and must be field adjusted for a particular unit, at a given load, burning a given fuel. Thus, current combustion control technology makes no attempt to monitor or control main burner zone stoichiometry.
Achieving low NO x emissions comes at a cost, i.e. as NO x emissions diminish there is a concomitant increase in carbon monoxide and the presence of carbon in fly ash. The carbon monoxide and carbon in fly ash parallel one another as air is apportioned amongst the various overfire air levels. Theoretically, the ability to achieve low NO x emissions while simultaneously maintaining acceptable levels of carbon monoxide and carbon conversion efficiency depends heavily upon maintaining the proper main burner zone stoichiometric ratio. This has been substantiated by both field and laboratory testing. However, there are inherent difficulties in controlling main burner zone stoichiometry using the existing control methodology outlined above. The deficiencies include:
1. The main burner zone stoichiometry and the unit stoichiometry can not be adjusted independently. With the existing control method, if the flow of air through the forced draft fan is increased, so as to increase the excess air, the control action of the windbox-to-furnace pressure differential control loop will tend to redistribute a portion or all of the additional air to the main burner zone. Thus, the main burner zone stoichiometry will also increase as the excess air is increased. Corresponding decreases in main burner zone stoichiometry will result when excess air is decreased.
2. There is no means for directly setting a prescribed value of main burner zone stoichiometry. In fact, the nonlinear relationship between overfire air damper positions and main burner zone stoichiometry makes it difficult to even anticipate the amount of position adjustment required to produce a desired amount of change in stoichiometry. These factors increase the difficulty in field tuning the unit to obtain a desired system performance.
3. Changes in the windbox-to-furnace pressure differential setpoint schedule will change the main burner zone stoichiometry unless the overfire air damper positions are also adjusted. Thus, adjustments to the windbox-to-furnace pressure differential which may be made to vary firing conditions can become coupled to optimum overfire air damper settings, increasing the difficulty in field tuning the unit.
The new control method addresses these problems by providing a means for directly setting and maintaining main burner zone stoichiometry. By current methods, maintaining main burner zone stoichiometry is problematic in that fuel flow is not accurately measured, air flow to the main burner zone is typically not measured. Furthermore, fuel analysis, and therefore theoretical air requirements, is not accurately known. The conventional approach is to use trial and error to find a damper position versus boiler load curve that gives an "optimal" main burner zone stoichiometry. But this approach gives a main burner zone stoichiometry under fixed operating conditions, i.e.:
1. the same fuel is used
2. the fuel flow is constant for a given load
3. the same windbox to pressure differential exists
4. the same total air is present for a given load
5. the same boiler cleanliness exists
The proposed method solves the problem of maintaining main burner zone stoichiometry by first calculating the unit stoichiometry from the measured % O 2 in the flue gas. From the unit stoichiometry it is determined how much overfire air is needed for a desired main burner zone stoichiometry. Finally, the air requirements for the main burner zone are determined by subtraction and thus the main burner zone stoichiometry can be calculated.
SUMMARY OF THE INVENTION
In accordance with one aspect of the present invention there is provided a control system operable for the purpose of maintaining a required stoichiometric ratio of a combustion process occurring within the main burner zone of a fuel fired furnace. The subject control system includes a stoichiometry subsystem, an overfire air subsystem and an override protection subsystem.
The stoichiometry subsystem is designed so as to be operable to calculate the mass flow rate of overfire air required to maintain the desired stoichiometric ratio within the main burner zone of a fuel fired furnace. The stoichiometry subsystem accepts as input, signals originating from sensors strategically located throughout the boiler complex that measure unit load, % O 2 and total unit air flow, as well as an override protection signal originating from the override protection subsystem. The stoichiometry subsystem operates on these input signals in a manner so as to provide as output a signal, representative of the required mass flow rate of overfire air, which in turn acts as one input to the overfire air subsystem.
The overfire air subsystem is designed so as to be operable to apportion the total overfire air, OFA, amongst close coupled overfire air, CCOFA, and separated overfire air, SOFA, levels. The overfire air subsystem accepts as input the signal originating from the stoichiometry subsystem which is representative of the required mass flow rate of overfire air as well as signals originating from sensors strategically located throughout the boiler complex that measure windbox-to-furnace pressure differential, windbox pressure, windbox temperature and total separated overfire air flow. The overfire air subsystem operates upon these signals in such a manner that a damper controller subsystem, incorporated within the overfire air subsystem, provides as output the required overfire air damper positions in such a manner that air is properly apportioned amongst the close coupled overfire air and separated overfire air levels and the main burner zone stoichiometric ratio is maintained.
The override protection subsystem is designed so as to be operable to ensure that the control of the windbox-to-furnace pressure differential maintains precedence over the stoichiometry subsystem in the event that these two control schemes have conflicting requirements. The override protection subsystem accepts as input a signal originating from a sensor located at the auxiliary air dampers that measures auxiliary air damper positions. The override protection subsystem operates upon this signal in a manner so as to provide as output an override protection signal which in turn acts as one input to the stoichiometry subsystem. The need for such additional logic can be understood by considering the effect of an excessive reduction in the main burner zone stoichiometry set point, φ mbz . As the demanded main burner zone stoichiometry is reduced, more air is diverted to the overfire air compartments and the auxiliary air dampers must close in order to maintain windbox-to-furnace pressure differential. Depending upon the total air flow into the furnace, if φ mbz is set too low then, without additional control logic, the auxiliary air dampers would fully close and windbox-to-furnace pressure differential would no longer be controlled. To automatically prevent the above scenario, override protection logic is implemented which modifies φ mbz as required to maintain a minimum opening for the auxiliary air dampers.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic representation in the nature of a vertical sectional view of a fuel-fired furnace embodying a tangential firing system in cooperation with a fuel and air supply means.
FIG. 2 is a generalized schematic representation in the nature of a main burner zone stoichiometric control system constructed in accordance with the present invention which is applicable for the use with the fuel-fired furnace depicted in FIG. 1.
FIG. 3 is a schematic representation depicting the nature of the main burner zone stoichiometric control system of FIG. 2 as consisting of a stoichiometry subsystem, an overfire air subsystem and an override protection subsystem, and constructed in accordance with the present invention.
FIG. 4 is a schematic representation of the stoichiometry subsystem of FIG. 3 constructed in accordance with the present invention.
FIG. 5 is a schematic representation of the override protection subsystem of FIG. 3 constructed in accordance with the present invention.
FIG. 6 is a schematic representation of the overfire air subsystem of FIG. 3 constructed in accordance with the present invention.
FIG. 7 is a schematic representation of the damper controller subsystem of FIG. 6 constructed in accordance with the present invention.
FIG. 8 is a schematic representation of an alternative configuration of the overfire air subsystem constructed in accordance with the present invention.
FIG. 9 ms a schematic representation of an alternative configuration of the stoichiometry subsystem constructed in accordance with the present invention.
FIG. 10 is a generalized schematic representation of an alternative configuration of the overfire air subsystem constructed in accordance with the present invention.
FIG. 11 is a schematic representation of the overfire air subsystem of FIG. 10 constructed in accordance with the present invention.
FIG. 12 is a graphical depiction of unit stoichiometric ratio as a function of measured % O 2 in the flue gas leaving the furnace.
FIG. 13 is a graphical depiction of a representative main burner zone stoichiometric ratio as a function of unit air flow.
FIG. 14 is a graphical representation of percent damper demand as a function of percent damper capacity.
FIG. 15 is a graphical representation of damper sequencing as a function of percent damper demand.
FIG. 16 is a graphical representation of the percent damper opening as a function of total unit air flow.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 1 there is depicted a fuel fired furnace, generally designated by reference numeral 2. In as much as the nature of the construction and mode of operation of fuel fired furnaces are well known to those skilled in the art, it is deemed not necessary to set forth a detailed description of the fuel fired furnace 2. Rather, for purposes of obtaining an understanding of a fuel fired furnace it is deemed to be sufficient that there be presented herein merely a description of the nature of the components of the fuel fired furnace with which a tangential firing system cooperates. For a more detailed description of the nature of the construction and the mode of operation of the fuel fired furnace one may reference U.S. Pat. No. 4,719,587, which issued on Jan. 12, 1987 to F. J. Bette and which is assigned to the same assignee as the present patent application.
Referring further to FIG. 1 the fuel fired furnace 2 includes a main burner zone, generally designated by reference numeral 4. It is within the main burner zone 4 of the fuel fired furnace 2 that, in a manner well known to those skilled in the art, combustion of fuel and air is initiated. The hot gases that are produced from this combustion rise upwardly within the furnace and give up heat to the fluid passing through the furnace tubes (not shown for clarity of illustration) which in a conventional manner line all four walls of the furnace 2. Then the hot combustion gases exit the furnace 2 through the horizontal pass, generally designated by reference numeral 6 within the fuel fired furnace 2. This in turn leads to the rear gas pass of the furnace, generally designated by reference numeral 8. Both the horizontal pass 6 and the rear pass 8 commonly contain other heat exchange surfaces (not shown for clarity) for generating and super heating steam in a manner well known to those skilled in the art. Thereafter, the steam commonly is made to flow to a turbine (not shown), which forms one component of a turbine/generator set (not shown). The steam provides the motive power to drive the turbine which thence drives the generator, which in known fashion is cooperatively associated with the turbine such that electricity is produced from the generator.
Referring further to FIG. 1 there is also depicted a schematic representation of a means, generally designated by the numeral 10, for supplying fuel and air to the furnace 2. Said fuel and air supply means 10 consists of various ducts 12 so designed and constructed as to transport fuel and air, separately or if need be in combination, from a fuel source 14 and an air source 16 to a main windbox 18 which includes a set of close coupled overfire air (CCOFA) compartments 20, and a set of separated overfire air (SOFA) compartments 22, thence to the furnace 2 so as to support the aforesaid combustion. Also depicted in FIG. 1 are various sensors 26, 28, 30, 32, 34, 36, 38 mounted by conventional means and strategically located throughout the ductwork 12, furnace 2 and rear pass 8 so as to measure the % O 2 concentration in the exhaust gases, total unit air flow to the furnace, auxiliary air damper position, furnace pressure, windbox pressure and windbox temperature. Said sensors 26, 28, 30, 32, 34, 36, 38 are in communication by electrical signals with the main burner zone stoichiometry control system 100 shown in FIG. 2. For a more detailed description of the nature of construction and the mode of operation of the fuel and air supply means one may reference U.S. Pat. No. 5,315,939, which issued on May 31, 1994 to M. Rini et. al. and which is assigned to the same assignee as the present patent application.
Referring now to FIG. 2 there is depicted a generalized schematic diagram of the main burner zone stoichiometric control system 100 subject to stimulation by signals 40, 42, 44, 46, 48, 50, 52, 54 originating from the array of sensors 24, 26, 28, 30, 32, 34, 36, 38 strategically located throughout the boiler complex and in communication in accordance with conventional practice with the main burner zone stoichiometric control system 100. The main burner zone stoichiometry control system 100 is designed and constructed in accordance with the present invention so as to provide as output, due to said stimulation, a set of signals 548, 548', 548" which are representative of the required positions of the close coupled overfire air dampers 550 and separated overfire air dampers 550', 550" necessary to maintain the main burner zone stoichiometric ratio, φ mbz and which position the dampers accordingly.
Referring now to FIG. 3 there is depicted the main burner zone stoichiometric control system 100 as it is comprised of the stoichiometry subsystem 200, the override protection subsystem 300, and the over fire air subsystem 400 and their interconnecting signal paths. It is seen in FIG. 3 that the override protection subsystem 300 is subject to stimulation by a signal 46 originating from the auxiliary air damper position sensor 30 and representative of the auxiliary air damper position. Furthermore, the override protection subsystem 300 which is in communication in accordance with conventional practice with the stoichiometry subsystem 200 provides as output, resulting from said stimulation, an override protection signal 324 which acts as one input to the stoichiometry subsystem 200. It is further seen in FIG. 3 that the stoichiometry subsystem 200 is subject to stimulation by signals 40, 42, 44, 324 originating from the unit load sensor 24, % O 2 sensor 26, total air flow sensor 28 and the override protection subsystem 300. These signals are respectively representative of unit load on the boiler, % O 2 concentration in the exhaust gases, total unit air flow into the furnace, and the override protection signal. The stoichiometry subsystem 200, which is in communication in accordance with conventional practice with the overfire air subsystem 400, then provides as output, due to said stimulation, a signal 228 which acts as one input to the overfire air subsystem 400 and is representative of the mass flow rate of overfire air required to maintain the main burner zone stoichiometric ratio, φ mbz .
It is also seen in FIG. 3 that the overfire air damper subsystem 400 is subject to stimulation by signals 48, 50, 52, 54 originating from the separated overfire air flow sensor 32, the windbox pressure sensor 34, the windbox temperature sensor 36 and the furnace pressure sensor 38, respectively. These signals are respectively representative of the total mass flow rate of separated overfire air, windbox pressure, windbox temperature and furnace pressure. The overfire air subsystem 400 then provides as output, due to said stimulation, a set signals 548, 548', 548" which are representative of the close coupled and separated overfire air damper positions required to maintain the main burner zone stoichiometric ratio and which position those dampers accordingly.
To further elaborate, reference is now made to FIG. 4 depicting a more detailed schematic diagram of the stoichiometry subsystem 200 showing the arrangement of the functional equivalents of its component parts and their interconnecting signal paths. Said signal paths are made operable in accordance with conventional practice. More specifically, the stoichiometry subsystem 200 is comprised of a first signal adder 210, a second signal adder 218, a signal multiplier 226 and a signal divider 214, all of which are operable in accordance with conventional practice. Furthermore, said stoichiometry subsystem 200 includes a first signal generator 202, a second signal generator 206 and a third signal generator 220 each of which is operable in accordance with conventional practice.
The second signal generator 206, whose input/output relationship is as generically shown by curve 206a in FIG. 13, is subject to stimulation by a signal 40 originating from the unit load sensor 24 and representative of the percentage of the Maximum Continuous Rating (MCR) at which the boiler operates. The second signal generator 206 then provides as output, due to all of said stimulation, a signal 208 representative of the main burner zone stoichiometric ratio set point, which may also be established by a closed loop supervisory control system to optimize performance based upon measurements of NOX emissions and unburned combustibles or other boiler performance variables. Said signal 208 is then added, by way of the first signal adder 210, to the override protection signal 324 originating from the override protection subsystem 300 to yield a signal 212 representative of the modified main burner zone stoichiometric ratio set point. Continuing, the first signal generator 202, whose input/output relationship is as generically shown by curve 202a in FIG. 12, is subject to stimulation by a signal 42 originating from the % O 2 sensor 26 and representative of % O 2 in the flue gases. Said first signal generator 202 then provides as output, due to said stimulation, a signal 204, representative of the unit stoichiometric ratio. Continuing further in FIG. 4, the modified main burner zone stoichiometric ratio set point signal 212 is divided by the unit stoichiometric ratio signal 204 by way of the signal divider 214 to yield as output a signal 216 representative of the fraction of total unit air allocated to the main burner zone 4. Said output signal 216 is then subtracted, by way of the second signal adder 218, from a constant signal 222 which is equal to unity and originates from the third signal generator 220 to yield a signal 224 representative of the fraction of total unit air allocated to overfire air. Continuing still further, said signal 224 is multiplied, via the signal multiplier 226, by a signal 44 originating from the air flow sensor 28 and representative of the total unit air flow to the furnace to yield a signal 228 representative of the mass flow rate of overfire air required to maintain main burner zone stoichiometric ratio, φ mbz .
Referring now to FIG. 5 there is depicted a more detailed schematic diagram of the override protection subsystem 300 showing the arrangement of the functional equivalents of its component parts and their interconnecting signal paths. Said signal paths are made operable in accordance with conventional practice. More specifically the override protection subsystem 300 is comprised of a signal adder 302, a proportional-plus-integral (PI) controller 310, a signal generator 304, a low limiter 314, a high limiter 316 and a gain multiplier 320, all of which are operable made by conventional practice. The override protection subsystem 300 is subject to stimulation by a signal 46 originating from the auxiliary air damper sensor 30 and representative of the auxiliary damper position. Said signal 46 is added, by way of the signal adder 302, to a modified feedback signal 322, later described, and to a constant signal 306 originating from the signal generator 304 and representative of a preset minimum allowable value, `A`, for the auxiliary air damper position. Said addition yields an error signal 308 which is integrated, in a manner known and understood by those skilled in the art, by the PI controller 310 generating an override protection signal 312. The override protection signal 312 acts first as input to a low limiter 314 and secondly as a feedback signal passed through a high limiter 316 and a gain multiplier 320. The output of the gain multiplier 320 and high limiter 316 is a modified feedback signal 322 which is added to the auxiliary air damper position signal 46 and the minimum allowable auxiliary air damper position signal 306 via the signal adder 302.
As the main burner zone stoichiometric ratio set point decreases the auxiliary air dampers begin to close and the overfire air dampers 548, 548', 548" begin to open. However, the windbox-to-furnace pressure differential must be maintained as this happens. If the auxiliary air dampers close too far such that the auxiliary air damper position signal 46 falls below the minimum allowable value, `A`, the error signal 308 becomes positive and a positive override protection signal 324 is generated which acts as one input to the stoichiometry subsystem 200. Said input signal 324 acts to increase the main burner zone stoichiometric ratio set point causing the overfire air dampers to close. Now, the windbox-to-furnace pressure differential increases, causing the auxiliary air dampers to open and the auxiliary air damper position signal 46 to return to the minimum allowable value. As long as the windbox-to-furnace pressure differential is maintained no override protection signal 324 is generated. To satisfy this requirement, the low limiter 314 ensures that the override protection signal 312 is never less than zero.
The modified feedback signal 322 prevents `wind-up` in the PI controller 310 when the auxiliary air dampers are sufficiently open. By making the feedback gain, `K`, sufficiently large, `wind-up` is minimized. The override protection subsystem 300 may also be implemented by the use of binary logic, binary logic being known and understood by those skilled in the art.
Referring now to FIG. 6 there is depicted a more detailed schematic diagram of the overfire air subsystem 400 showing the arrangement of the functional equivalents of its component parts and their interconnecting signal paths. Said signal paths are made operable in accordance with conventional practice. More specifically the overfire air subsystem 400 is comprised of two signal multipliers 402 430, a signal adder 422, four signal differencers 410, 414, 436, 440 three damper controllers 500, 500', 500", and two signal generators 404, 426, all of which are made operable by conventional practice. The overfire air subsystem 400 is subject to stimulation by a signal 228 originating from the stoichiometry subsystem 200 and representative of the mass flow rate of overfire air required to maintain the main burner zone stoichiometric ratio. The overfire air subsystem 400 is also subject to stimulation by a signal 48 originating from the separated overfire air flow sensor 32 and representative of the total mass flow rate of air carried by the SOFA dampers. The overfire air subsystem 400 is subject to still further stimulation by a plurality of signals 50, 52, 54, originating from the windbox pressure sensor the windbox temperature sensor 36 and the furnace pressure sensor 38 and are respectively representative of the windbox pressure, windbox temperature and furnace pressure. The overfire air subsystem 400 provides as output, due to all of said stimulation, a plurality of signals 548, 548', 548" which are respectively representative of the close coupled, low separated and high separated overfire air damper positions required to maintain the main burner zone stoichiometric ratio and which position those dampers accordingly. The purpose of the overfire air subsystem 400 is to apportion air amongst the close coupled overfire air dampers 550 and the low separated and high separated overfire air dampers 550', 550". To that end, that signal 228 representative of the mass flow rate of air required to maintain the main burner zone stoichiometric ratio, φ mbz , is multiplied, via the first signal multiplier 402, by that signal 406, originating from the first signal generator 404 and representative of the desired ratio, R1, of the mass flow rate of close coupled overfire air (CCOFA) to the mass flow rate of total overfire air (OFA). Said signal 406 can be established by a closed loop supervisory control system to optimize performance based upon measurements of NO x emissions and unburned combustibles or other boiler performance variables. Continuing, said signal multiplier 402 provides as output a signal 408 representative of the mass flow rate of CCOFA and which acts as one input to the CCOFA damper controller 500, later described.
Said CCOFA damper controller 500 provides as one output a capacity error signal 542, representative of the amount by which the CCOFA mass flow rate exceeds the CCOFA damper capacity. If the amount of the CCOFA mass flow rate exceeds the fully open capacity of the CCOFA dampers 550 then the CCOFA mass flow rate will be clipped, within the damper controller 500, at the maximum capacity of the CCOFA dampers. Said capacity error signal 542 is subtracted, via the first signal differencer 410, from that signal 408 representative of mass flow rate of CCOFA to yield a signal 412 representative of the commanded mass flow rate of CCOFA. If the capacity of the CCOFA dampers is not exceeded then the capacity error signal 542 is zero. The commanded mass flow rate signal 412 is subtracted, via the second signal differencer 414, from that signal 228 representative of the mass flow rate of OFA required to maintain the main burner zone stoichiometric ratio, φ mbz , yielding a signal 416 representative of the mass flow rate of air allocated to separated overfire air. Continuing with the overfire air subsystem 400, the PI controller 418 is first subject to stimulation by a signal 48 which originates from the separated overfire air (SOFA) air flow sensor 32 and is representative of the total flow rate of air carried by the low SOFA and high SOFA dampers 550', 550" and secondly by that signal 416 which is representative of the mass flow rate of air allocated to the low SOFA and high SOFA dampers 550', 550". Specifically the PI controller 418 acts upon the difference between the signal 416 representative of the mass flow rate of air allocated to SOFA and the signal 48 which is representative of the total flow rate of air carried by the low SOFA and high SOFA dampers 550', 550" to provide as output a corrective feedback signal 420. Said corrective feedback signal 420 is then added, via the signal adder 422, to that signal 416 representative of the mass flow rate of air allocated to the low SOFA and high SOFA dampers 550', 550" to yield a further signal 424 that compensates for any inaccuracies in damper characterization.
Continuing with the overfire air subsystem 400, determining the allocation of the mass flow rate of overfire air between the low SOFA and high SOFA dampers 550', 550" is accomplished in a fashion identical to that utilized in determining the allocation of the total mass flow rate of overfire air between the CCOFA dampers 550 and the low SOFA and high SOFA dampers 550', 550" Specifically that signal 442 representative of the mass flow rate of air distributed to the high SOFA 550" dampers is determined in a manner functionally identical to that used in determining that signal 416 representative of the mass flow rate of air allocated to both sets of SOFA dampers 550', 550". In keeping with this fact it is noted that that signal 428 originating from the second signal generator 426 and representative of the desired ratio, R2, of the mass flow rates of air between the two SOFA levels may also be established by a closed loop supervisory control system to optimize performance based upon measurements of NOX emissions and unburned combustibles or other boiler performance variables.
Referring now to FIG. 7 there is depicted a more detailed schematic diagram representative of the damper controllers 500, 500', 500" shown in FIG. 6. Said damper controllers 500, 500', 500" are identical in function. Thus, for purposes of simplification, FIG. 7 depicts the arrangement of the functional equivalents of the component parts and interconnecting signal paths of the CCOFA damper controller 500 only and its description will similarly serve as a description for the low SOFA and high SOFA damper controllers 500', 500". Said signal paths of the damper controllers are made operable in accordance with conventional practice. More specifically, the damper controller 500 is comprised of a signal converter 502, three signal multipliers 510, 518, 540, two signal dividers 514, 536, a high limiter 526, a signal differencer 532, a first signal generator 506, a second signal generator 520, a third signal generator 530 and a plurality of signal generators each of which is designated by the reference numeral 546. All of the said functional equivalents are operable in accordance with conventional practice.
The damper controller 500 is subject to stimulation by a signal 408 originating from the signal multiplier 402 within the overfire air subsystem 400 and representative of the mass flow rate of air allocated to the CCOFA level. The CCOFA damper controller 500 is further stimulated by a signal 54 originating from the furnace pressure sensor 38 and representative of the furnace pressure, a signal 50 originating from the windbox pressure sensor 34 and representative of the absolute windbox pressure and a signal 52 originating from the windbox temperature sensor 36 and representative of the windbox temperature. Said CCOFA damper controller 500 provides as output, due to said stimulation, a capacity error signal 542, described above, and signals 548 representative of the CCOFA damper position which activates said dampers 550 accordingly.
Continuing, a signal 504 representative of a correction factor and based upon measurements of furnace pressure, absolute windbox pressure and windbox temperature is computed via said signal converter 502 in a manner that would be understood by those skilled in the art. The signal 504 is multiplied, via the first signal multiplier 510, by a signal 508 originating from the first signal generator 506 and representative of a reference mass flow rate of air to yield as output a signal 512 representative of the maximum mass flow rate capacity of the CCOFA dampers 550. Said signal 512 acts in turn first as input to the first signal divider 514 and secondly as input to the second signal multiplier 540, later described. Furthermore, that signal 408 originating from the first signal multiplier 402 shown in FIG. 6 and representative of the mass flow rate of air allocated to the CCOFA dampers is divided, via the first signal divider 514, by that signal 512 representative of the maximum mass flow rate capacity of the CCOFA dampers 550 to yield as output a signal 516 representative of the flow of air to CCOFA ratioed to the maximum flow capacity of the CCOFA dampers under the given conditions of windbox-to-furnace pressure differential, absolute windbox pressure and windbox temperature. Said signal 516 is multiplied, via the third signal multiplier 518, by a constant signal 522 originating from the second signal generator 520 and representative of a multiplicative factor of 100 to yield as output a signal 524 representative of the percentage of the maximum flow capacity of the CCOFA dampers 550. Said signal 524 acts as input first to the high limiter 526 and secondly to the signal differencer 532. The high limiter 526 clips this input signal 524 such that the high limiter provides as output a signal 528 which is representative of the percentage of the maximum flow capacity of the CCOFA dampers and will not exceed 100% of that quantity. The high limiter output signal 528 in turn acts as input first to the signal differencer 532 along with the high limiter input signal 524 and secondly to the third signal generator 530, later described. The signal differencer 532 takes the difference between the two input signals 524, 528 and provides as output a signal 534 representative of the percent by which air flow to the CCOFA dampers 550 exceeds their capacity. The output signal 534 of the signal differencer 532 further acts as a first input to the second signal divider 536 which also accepts, as a second input, a constant signal 522 originating from the second signal generator 520 and representative of a multiplicative factor of 100. Said second signal divider 536 divides the first input signal 534 by the second input signal 522 to yield as output a signal 538 which is representative of the fraction by which air flow to the CCOFA dampers is in excess of their capacity. This output signal 538 is in turn multiplied, via the second signal multiplier 540, by that signal 512 which acts as the output signal of the first signal multiplier 510 and is representative of the maximum mass flow rate capacity of the CCOFA dampers to yield, as output, the aforementioned capacity error signal 542.
Returning now to the output signal 544 of the high limiter, that signal acts as input to the third signal generator 530 which characterizes the CCOFA damper demand as a function of the percentage of the maximum flow capacity of the CCOFA dampers. The input/output relationship of the third signal generator 530 is as generically shown by curve 530a in FIG. 14. The third signal generator 530 provides as output a signal 544 which is representative of the percent demand placed upon the CCOFA dampers 550 and which acts as input to the plurality of signal generators S46. The signal generators S46 act as a sequencing mechanism. As the demand, h(x), placed upon the CCOFA dampers 550 increases the dampers are sequentially opened in a predetermined fashion as is generically shown by curves pl x through pn x in FIG. 15. The signal generators 546 each provide as output a signal S48 representative of the respective positions of the corresponding CCOFA dampers 550 required to the maintain main burner zone ratio, φ mbz , and which act so as to position the dampers accordingly. The number, n, of dampers utilized is variable and based upon the specific design of the firing system.
Referring now to FIG. 8 there is depicted a detailed schematic diagram of an alternative configuration 600 for the overfire air subsystem 400 shown in FIG. 6. FIG. 8 shows the arrangement of the functional equivalents of this configuration's component parts and their interconnecting signal paths. Said signal paths are made operative in accordance with conventional practice. More specifically the air alternative configuration 600 of the overfire subsystem 400 is comprised of a first signal generator 602, a second signal generator 622, a signal multiplier 606, a signal adder 610, a low signal selector 614, and a signal divider 618. The alternative configuration 600 is subject to stimulation by a signal 40 originating from the unit load sensor 24 and representative of the load upon the boiler expressed as a fraction of the Maximum Continuous Rating at which the boiler operates. The alternate configuration 600 is also subject to stimulation by a conventional signal 228' originating from a second low signal selector 640, later described. Said input signal 228' is representative of the mass flow rate of overfire air required to maintain the main burner zone stoichiometric ratio, φ mbz . The alternate configuration 600 is subject to still further stimulation by a signal 634 originating from the proportional-plus-integral controller 632, later described, and representative of a capacity error in the plurality of overfire air dampers 626, 626', 626". The alternate configuration 600 of the overfire air subsystem 400 is designed and constructed in accordance with the present invention to provide as output, due to all of said stimulation, a signal 624 representative of the overfire air damper position which also acts to position the overfire air damper 626 accordingly. Said output signal 624 may also act as input to the signal generator 546 of FIG. 7. The alternate configuration 600 of the overfire air subsystem 400 also provides as output, due to all of said stimulation, a signal 616 which is representative of the portion of total overfire air carried by the overfire air damper 626. Furthermore, said alternate configuration 600 provides as output, a signal 512 originating from the signal multiplier 510 described above, in context with the damper controller 500, and representative of the maximum mass flow rate capacity of the overfire air damper 626. In this configuration the total quantity of overfire air available is controlled such that a specified fraction of the total overfire air is allocated to each damper as a function of unit load. The alternate configuration 600 is coupled with possibly numerous like configurations which are depicted by reference numerals 600' and 600" in FIG. 8 such that any demand placed upon a damper in excess of its capacity is evenly divided amongst other available dampers. The number, n, of dampers required is variable and based upon the specific design of the firing system. More specifically said first signal generator 602 is subject to stimulation by a signal 40 originating from the unit load sensor 24 and representative of the load placed upon the boiler expressed as a fraction of the maximum continuous rating of the boiler. The input/output relationship of the first signal generator 602 relates the fraction of overfire air to the unit load. It is a functional relationship that is unit specific and experimentally determined and may be adjusted to meet the needs of the boiler operator. The first signal generator 602 thus provides as output a signal 604 representative of the fraction of overfire air allocated to the overfire air damper 626. Said output signal 604 is then multiplied, via the first signal multiplier 606, by that signal 228', described above, originating from the stoichiometry subsystem 200, to yield an output signal 608 representative of that portion of the total mass flow rate of overfire air allocated to the overfire air damper 626. Said output signal 608 is then added, via the first signal adder 610, to a capacity error signal 634 originating from the PI controller 632, later described, to yield as output a signal 612 representative of the total mass flow demand placed upon the overfire air damper 626. The total mass flow rate demand signal 612 is compared, via the low signal selector 614, with the maximum mass flow rate damper capacity signal 512, described above, and the lesser quantity provided as output. Said output signal 616 is therefore representative of the demand of that fraction of the total mass flow rate of overfire air placed upon the overfire air damper 626, though not exceeding the maximum mass flow rate capacity of the damper 626. Said signal 616 is then divided, via the first signal divider 618, by the maximum mass flow rate damper capacity signal 512 to yield as output a signal 620 representative of the demand placed upon the overfire air damper expressed as a fraction of the maximum capacity of the overfire air damper 626. Said signal 620 then acts as input to the second signal generator 622 which characterizes the percent by which the overfire air damper is open as a function of the demand placed upon the damper expressed as a fraction of the mass flow rate damper capacity. The second signal generator 622 thus provides as output a signal 624 which is representative of the percent by which the overfire air damper 626 is open and which also acts so as to position the damper 626 accordingly.
As stated above the alternate configuration 600 of the overfire air subsystem 400 provides as output a signal 616 representative of the portion of total overfire air carried by the overfire air damper and is also subject to stimulation by signal 634 originating from the PI controller 632 and representative of the damper capacity error. It was also stated above that this configuration 600 is coupled with possibly numerous like control loops 600', 600" Explanation will now be made as to the functional interrelation of said signals and control loops. A second signal adder 628 accepts as input that signal 616 originating from the alternate configuration 600 and which is representative of the demand of that portion of the total mass flow rate of overfire air placed upon the overfire air damper 626. Said signal adder 628 also accepts like signals 616', 616" which originate from like control loops 600', 600" but are now representative of the demand of that portion of the total mass flow rate of overfire air placed upon their respective dampers 626', 626". Thus the second signal adder 628 provides as output a signal 630 representative of the total mass flow rate demand placed upon all dampers and which then acts as one input to the PI controller 632. Said PI controller 632 also accepts as input that signal 228' which originates from the second low signal selector 640 and is representative of the mass flow rate of overfire air required to maintain the main burner zone stoichiometric ratio, φ mbz . The PI controller 632 acts upon said input signals 228' 630 in a manner which would be understood by those skilled in the art so as to provide as output a capacity error signal 634. Said output signal 634 is of such a character that when the total mass flow rate demand signal 630 is less than the required mass flow rate signal 228' the capacity error signal 634 seeks to increase the demand signal 612 to each damper via the first signal adder 610 until the total mass flow rate demand equals the required mass flow rate. If the required fraction of overfire air allocated to all of the overfire air dampers 626, 626', 626" is within their capacity limit, then the total mass flow rate demand will equal the required mass flow rate and no corrective action occurs. Whenever the required mass flow rate is less than the total mass flow rate demand the capacity error signal 634 seeks to decrease the demand signal 612 via the first signal adder 610, again until the total mass flow rate demand equals the required mass flow rate. It is further seen in FIG. 8 that the capacity error signal 634 acts as one input to any like control loops 600', 600" as well. The result is to achieve the desired apportionment of overfire air amongst the various dampers by distributing any flow which exceeds the capacity of an individual damper equally amongst the other available dampers.
It is also seen in FIG. 8 that the alternate configuration 600 of the overfire air subsystem 400 provides as output a signal 512 originating from the second signal multiplier 510, described above, and representative of the maximum mass flow rate capacity of the overfire air damper 626. Similar signals also act as output from any like overfire air control loops 600', 600". Said output signals 512, 512', 512" act as input to a third signal adder 636 which provides as output a signal 638 representative of the total mass flow rate capacity of all overfire air dampers 626, 626', 626". Said output signal 638 then acts as input to a second low signal selector 640 which also accepts as input that signal 228 originating from the stoichiometry subsystem 200 and is representative of the mass flow rate of overfire air required to maintain the main burner zone stoichiometric ratio, φ mbz . The second low signal selector 640 thus provides as output a signal 228' which is the lesser of the two input signals and still representative of φ mbz such that the mass flow rate demand does not exceed the maximum mass flow rate capacity of all dampers 626, 626', 626".
As a further alternative to apportioning air flow amongst the OFA levels reference is now made to FIGS. 9, 10 and 11. More specifically in FIG. 9 there is depicted the arrangement of the stoichiometry subsystem 200', the override protection subsystem 300, the load change subsystem 700, the dynamic ratio subsystem 800 and their interconnecting signal paths. Said signal paths are made operable in accordance with conventional practice. It is seen in FIG. 9 that the stoichiometry subsystem 200' is subject to stimulation by signals 44, 324, 802 originating from the unit air flow sensor 28, the override protection subsystem 300, by and the dynamic ratio subsystem 800. Said signals are representative of the total flow of air into the furnace 2, the override protection signal 324 and the stoichiometric ratio of the unit, PHI (unit). Said stoichiometry subsystem 200' is designed and constructed in accordance with the present invention and in a fashion which would be understood by those skilled in the art to provide as output, due to all of said stimulation, a signal 228" which is representative of the mass flow rate of separated overfire air necessary to maintain the main burner zone stoichiometric ratio, φ mbz , and which further acts as one input to the dynamic ratio subsystem 800, later described.
It is also seen in FIG. 9 that the load change subsystem 700 is subject to stimulation by the signal 44 originating from the unit air flow sensor 28 and which is representative of the total flow of air to the furnace 2. The load change subsystem 700 is also subject to stimulation by a signal 58 originating from the fuel sensor 56 and which is representative of the total flow of fuel to the furnace 2. Said load change subsystem 700 is designed and constructed in accordance with the present invention in a fashion which would be understood by those skilled in the art, to provide as output, due to said stimulation, a signal 702 which is representative of the change with respect to time of either the total air flow to the furnace or the total fuel flow to the furnace; whichever is greater. Said output signal 702 thence acts as one input to the dynamic ratio subsystem 800.
It is further seen in FIG. 9 that the dynamic ratio subsystem 800 is subject to stimulation by the signal 44 originating from the air flow sensor 28 and representative of the total air flow to the furnace 2. The dynamic ratio subsystem 800 is also subject to stimulation by a signal 42 originating from the % O 2 sensor 26 and representative of percent concentration of oxygen in the combustion exhaust gases. The dynamic ratio subsystem 800 is also subject to stimulation by the signal 228" originating from the stoichiometry subsystem 200' and representative of the mass flow rate of separated overfire air necessary to maintain the main burner zone stoichiometric ratio, φ mbz . The dynamic ratio subsystem 800 is subject to still further stimulation by the signal 702 originating from load change subsystem 700 and representative of the change with respect to time of either the total air flow to the furnace or total fuel flow to the furnace; whichever is greater. Said dynamic ratio subsystem 800 is designed and constructed in accordance with the present invention and in a manner which would be understood by those skilled in the art, to provide as output, due to all of said stimulation, a first signal 802, a second signal 804 and a third signal 806. The first output signal 802 is representative of the unit stoichiometric ratio, PHI (unit), and acts as one input to the stoichiometry subsystem 200', described above. The second output signal 804 is representative of that fraction of the total mass flow rate of air to the furnace allocated to the low SOFA dampers, seen at 926, 926', 926" in FIG. 11, and acts as one input to the overfire air subsystem 900. The third output signal 806 is representative of that fraction of the total mass flow rate of air to the furnace allocated to the high SOFA dampers, seen at 954, 954', 954" in FIG. 11 and also acts as one input to the overfire air subsystem 900.
Referring now to FIG. 10 there is depicted therein a generalized schematic diagram of the overfire air subsystem 900 subject to stimulation by signals 44, 62, 66, 804, 806 originating from an array of sensors 28, 60, 64 as well as the dynamic ratio subsystem 800. Said sensors are strategically located throughout the boiler complex and are in communication by conventional means with the overfire air subsystem 900. The overfire air subsystem 900 is designed and constructed in accordance with the present invention to provide as output, due to all of said stimulation, a set of signals 924, 924', 924", 952, 952', 952", 968, 968' which are representative of the positions of the low SOFA dampers 926, 926', 926" high SOFA dampers 954, 954', 954" and the CCOFA dampers 970, 970' and which position said dampers accordingly.
To further elaborate reference is now made to FIG. 11 wherein there is depicted a more detailed schematic diagram of the overfire air subsystem 900 showing the arrangement of the functional equivalents of its component parts and their interconnecting signal paths. Said components and signal paths are made operable in accordance with conventional practice. The overfire air subsystem 900 is comprised of a first signal adder 902, a second signal adder 930, a third signal adder 962, a first PI controller 910, a second PI controller 938, a first two state signal monitor 914, a second two state signal monitor 942, a first three state signal monitor 918, a second three state signal monitor 946, a first sequencer 922 and a second sequencer 950. Said overfire air subsystem 900 is further comprised of a low SOFA overload circuit 906, a high SOFA overload circuit 934, a signal transfer device 958 and a first signal generator 966.
It is further seen in FIG. 11 that the first signal adder 902 accepts as input first that signal 804 originating from the dynamic ratio subsystem 800 which is representative of the desired fraction of the total mass flow rate of air to the furnace to be allocated to the low SOFA dampers 926, 926', 926"; and secondly that signal 976 originating from the signal transfer device 958 which is representative of the overload in mass flow rate of air suffered by the high SOFA dampers 954, 954', 954". Said first signal adder 902 then provides as output a signal 904 which is representative of the desired total mass flow rate of air to be allocated to the low SOFA dampers 926, 926', 926" and which further acts as one input to the low SOFA overload circuit 906. Said low SOFA overload circuit 906 also accepts as input a feedback signal 916, later described, and provides as output a first signal 908 which is representative of the desired mass flow rate of air to be delivered to the low SOFA dampers 926, 926', 926"; and a second signal 928 which is representative of the overload in mass flow rate of air suffered by the low SOFA dampers 926, 926', 926". Said first signal output 908 acts as one input to the PI controller 910 which is also subject to stimulation by that signal 62 originating from the low SOFA airflow sensor 60 and representative of the actual mass flow rate of air delivered to the low SOFA dampers 926, 926', 926". Said PI controller 910 acts upon the aforesaid input signals 62, 908 in a fashion that would be understood by those skilled in the art so as to provide as output a capacity error signal 912 which acts as input first in feedback to the first two state signal monitor 914, secondly in feedforward to the first three state signal monitor 918 and thirdly to the first sequencer 922. Said capacity error signal 912 is of such a character that when the actual mass flow rate of air delivered to the low SOFA dampers 926, 926', 926" is less than the desired mass flow rate of air, the capacity error signal 912 is an increasing signal. Furthermore, when the actual mass flow rate of air delivered to the low SOFA dampers 926, 926', 926" is equal to the desired mass flow rate of air, within specified limits, the capacity error signal remains constant. Finally, when the actual mass flow rate of air delivered to the low SOFA dampers 926, 926', 926" is greater than the desired mass flow rate of air the capacity error signal 912 is a decreasing signal.
The first two state signal monitor 914 is made operable such that an input signal 912 with a value, V 1 , less than a predetermined value, V 0 , generates no output signal 916 and thus the low SOFA overload circuit 906 generates no overload signal 928. An input signal 912 with a value, V 2 , greater than or equal to V 0 generates an output signal 916 which acts as one input to the low SOFA overload circuit 906. The low SOFA overload circuit then generates an overload signal 928 which acts as one input to the second signal adder 930, later described. As a consequence, that amount of air in excess of the capacity of the low SOFA dampers 926, 926', 926" is then shifted to the high SOFA dampers 954, 954', 954".
Continuing now with the first signal sequencer 922 it is seen that it accepts as input a first signal 912, described above and again below, and a second signal 920, later described, which originates from the first three state signal monitor 918. The first signal sequencer 922 provides as output multiple signals 924, 924', 924" which activate the low SOFA dampers 926, 926', 926" and position them so as to maintain the main burner zone stoichiometric ratio, φ mbz . The number of output signals depends upon the number of low SOFA dampers, i.e. each output signal 924, 924', 924" is dedicated to a single damper 926, 926', 926".
The purpose of the first signal sequencer 922 is to open and close the low SOFA dampers in a predetermined order.
The first three state signal monitor 918 is made operable such that an input position error signal 912 with a value, V 3 , lying between a predetermined lower and upper limit generates no output signal 920. Under these circumstances the sequencer 922 maintains the low SOFA dampers in their current status, i.e. opened or closed. If the input signal 912 has a value, V 4 , which is less than the aforesaid lower limit an output signal 920 is generated which acts as one input to the first signal sequencer 922. Under these circumstances the sequencer 922 closes the low SOFA dampers in a predetermined order such as from top to bottom. Furthermore, if the input signal 912 has a value, V 5 , which is greater than the aforesaid upper limit an output signal 920 is generated which acts as one input to the first signal sequencer 922. Under these circumstances the sequencer 922 opens the low SOFA dampers in a predetermined order, such as from bottom to top. The first signal sequencer 922 accepts as input the position error signal 912 concurrent with the output signal 920 originating from the first three state signal monitor 918. When the position error signal 912 is increasing it acts to more fully open the low SOFA dampers 926, 926', 926". When said signal 912 is constant no corrective action is taken with respect to the low SOFA dampers and when said signal 912 is decreasing it acts to more fully close the low SOFA dampers.
Continuing further in FIG. 11 it is seen that the low SOFA overload signal 928 which originates from the low SOFA overload circuit 906 and is representative of the overload in mass flow rate of air suffered by the low SOFA dampers 926, 926', 926" acts as one input to the second signal adder 930. Said signal adder also accepts as input that signal 806 which originates from the dynamic ratio subsystem 800 and is representative of the desired fraction of the total mass flow rate of air to the furnace allocated to the high SOFA dampers 954, 954', 954". The second signal adder 930 then provides as output a signal 932 which is representative of the desired mass flow rate of air to be allocated to the high SOFA dampers 954, 954', 954".
In continuing the explanation of the operative nature of the overfire air subsystem 900 reference is now made in FIG. 11 to the high SOFA control boundary designated by the reference numeral 900b. Said control boundary 900b encloses the high SOFA overload circuit 934, the second PI controller 938, the second three state signal monitor 946, the second signal sequencer 950 and the second two state signal monitor 942 as well as their interconnecting signal paths 936, 940, 944, 948. It can be seen that said components and signal paths enclosed within the high SOFA control boundary 900b are identical in function and arrangement to those components and signal paths enclosed by the low SOFA control boundary designated by the reference numeral 900a. More specifically, those signals 932, 66 entering the high SOFA control boundary 900b are analogous to those signals 904, 62 entering the low SOFA control boundary 900a. In particular, that signal 932 which is representative of the desired total mass flow rate of air allocated to the high SOFA dampers is analogous to that signal 904 which is representative of the desired mass flow rate of air allocated to the low SOFA dampers. Also, that signal 66 which originates from the high SOFA air flow sensor 64 and is representative of the actual mass flow rate of air delivered to the high SOFA dampers is analogous to that signal 62 which is representative of actual mass flow rate of air delivered to the low SOFA dampers. Furthermore, those signals 952, 952', 952", 956 exiting the high SOFA control boundary 900b are analogous to those signals 924, 924', 924", 928 exiting the low SOFA control boundary 900a. In particular those signals 952, 952', 952" that originate from the second signal sequencer 950 and which activate the high SOFA dampers 954, 954', 954" and position them accordingly are analogous to those signals 924, 924', 924" described above which activate the low SOFA dampers 926, 926', 926" and position them accordingly. Also, that signal 956 that originates from the high SOFA overload circuit 934 and which is representative of the overload in mass flow rate of air suffered by the high SOFA dampers is analogous to that signal 928 originating from the low SOFA overload circuit 906 and representative of overload in mass flow rate of air suffered by the low SOFA dampers. Thus, the high SOFA dampers 954, 954', 954" are opened, closed and modulated so as to maintain the required main burner zone stoichiometric ratio, φ mbz , in a manner that is functionally identical to that of the low SOFA dampers 926, 926', 926" differing only in the specific nature of activating signals 952, 952', 952",
Continuing with reference to FIG. 11 it can be seen therefrom that that signal 956 which originates from the high SOFA overload circuit 934 and is representative of the overload in mass flow rate of air suffered by the high SOFA dampers acts as a sole input to the first signal transfer device 958. Said signal transfer device 958 is made operative by conventional logic and acts to direct the high SOFA overload signal 956 to either the first signal adder 902, described above, or the third signal adder 962, described below, depending upon the available mass flow rate capacity of the low SOFA dampers 926, 926', 926" or of the close coupled OFA dampers 970, 970'. The logic of the signal transfer device 958 preferably is such that priority is given first to the low SOFA dampers and then to the close coupled OFA dampers. Consequently, any overload in mass flow rate of air suffered by the high SOFA dampers is shifted first to the low SOFA dampers 926, 926', 926" thence to the close coupled OFA dampers 970, 970'.
Continuing with reference to FIG. 11 it is further seen therefrom that the signal transfer device 58 provides as output either a first signal 960 or a second signal 976. The signal 960 directed to the close coupled OFA dampers 970, 970' acts as one input to the third signal adder 962 and is representative of the overload in mass flow rate of air suffered by the high SOFA dampers 954, 954', 954". Said third signal adder 962 also accepts as input that signal 44 which originates from the total air flow sensor 28 and is representative of the total mass flow rate of air delivered to the boiler. Said third signal adder 964 then provides as output that signal 964 which is representative of the percentage of the total mass flow rate of air into the furnace 2 and which acts as input first to the first signal generator 966 and secondly to the second signal generator 966'. The input/output relationship of said signal generators 966, 966' is as generically shown by curves 966a and 966'a in FIG. 16. Thus, said signal generators 966, 966' provide as output those signals 968, 968' which activate the close coupled OFA dampers and position them accordingly.
While several embodiments of my invention have been shown, it will be appreciated that modifications thereof, some of which have been alluded to hereinabove, may still be readily made thereto by those skilled in the art. I, therefore, intend by the appended claims to cover the modifications which fall within the true spirit and scope of my invention. | A control system for a fuel-fired furnace and more specifically the control of the stoichiometric ratio of the combustion process occurring within the furnace of a steam generating power plant. The control system, when so employed, is capable of regulating the distribution of air flow to the combustion process such that the formation of oxides of nitrogen are maintained at acceptable levels. The control system includes in general a stoichiometric subsystem that determines the mass flow rate of air required to maintain the stoichiometric ratio within the combustion process; an override protection subsystem which ensures control precedence of the windbox-to-furnace pressure differential over the stoichiometry subsystem; and an overfire air subsystem that acts to apportion air flow amongst the various levels of overfire air within the boiler. | 5 |
This application is a continuation application of and claims priority under 35 U.S.C. § 120 to application Ser. No. 09/870,366, filed May 30, 2001 now U.S. Pat. No. 7,020,093. Application Ser. No. 09/870,366 is incorporated herein by reference.
FIELD OF INVENTION
This invention relates to delivery of streaming media.
BACKGROUND
Streaming media refers to content, typically audio, video, or both, that is intended to be displayed to an end-user as it is transmitted from a content provider. Because the content is being viewed in real-time, it is important that a continuous and uninterrupted stream be provided to the user. The extent to which a user perceives an uninterrupted stream that displays uncorrupted media is referred to as the “Quality of Service”, or QOS, of the system.
A content delivery service typically evaluates its QOS by collecting network statistics and inferring, on the basis of those network statistics, the user's perception of a media stream. These network statistics include such quantities as packet loss and latency that are independent on the nature of the content. The resulting evaluation of QOS is thus content-independent.
BRIEF DESCRIPTION OF THE FIGURES
FIGS. 1 and 2 show content delivery systems.
DETAILED DESCRIPTION
As shown in FIG. 1 , a content delivery system 10 for the delivery of a media stream 12 from a content server 14 to a client 16 includes two distinct processes. Because a media stream requires far more bandwidth than can reasonably be accommodated on today's networks, it is first passed through an encoder 18 executing on the content server 14 . The encoder 18 transforms the media stream 12 into a compressed form suitable for real-time transmission across a global computer network 22 . The resulting encoded media stream 20 then traverses the global computer network 22 until it reaches the client 16 . Finally, a decoder 24 executing on the client 16 transforms the encoded media stream 20 into a decoded media stream 26 suitable for display.
In the content delivery system 10 of FIG. 1 , there are at least two mechanisms that can impair the media stream. First, the encoder 18 and decoder 24 can introduce errors. For example, many encoding processes discard high-frequency components of an image in an effort to compress the media stream 12 . As a result, the decoded media stream 26 may not be a replica of the original media stream 12 . Second, the vagaries of network transmission, many of which are merely inconvenient when text or static images are delivered, can seriously impair the real-time delivery of streaming media.
These two impairment mechanisms, hereafter referred to as encoding error and transmission error, combine to affect the end-user's subjective experience in viewing streaming media. However, the end-user's subjective experience also depends on one other factor thus far not considered: the content of the media stream 12 itself.
The extent to which a particular error affects an end-user's enjoyment of a decoded media stream 26 depends on certain features of the media stream 12 . For example, a media stream 12 rich in detail will suffer considerably from loss of sharpness that results from discarding too many high frequency components. In contrast, the same loss of sharpness in a media stream 12 rich in impressionist landscapes will scarcely be noticeable.
Referring to FIG. 2 , a system 28 incorporating the invention includes a content-delivery server 30 in data communication with a client 32 across a global computer network 34 . The system 28 also includes an aggregating server 36 in data communication with both the client 32 and the content-delivery server 30 . The link between the aggregating server 36 and the client 32 is across the global computer network 34 , whereas the link between the aggregating server 36 and the content-delivery server 30 is typically over a local area network.
An encoder 38 executing on the content-delivery server 30 applies an encoding or compression algorithm to the original media stream 39 , thereby generating an encoded media stream 40 . For simplicity, FIG. 2 is drawn with the output of the encoder 38 leading directly to the global computer network 34 , as if encoding occurred in real-time. Although it is possible, and sometimes desirable, to encode streaming media in real-time (for example in the case of video-conferencing applications), in most cases encoding is carried out in advance. In such cases, the encoded media 40 is stored on a mass-storage system (not shown) associated with the content-delivery server 30 .
A variety of encoding processes are available. In many cases, these encoding processes are lossy. For example, certain encoding processes will discard high-frequency components of an image under the assumption that, when the image is later decoded, the absence of those high-frequency components will not be apparent to the user. Whether this is indeed the case will depend in part on the features of the image.
In addition to being transmitted to the client 32 over the global computer network 34 , the encoded media 40 at the output of the encoder 38 is also provided to the input of a first decoder 42 , shown in FIG. 2 as being associated with the aggregating server 36 . The first decoder 42 recovers the original media stream to the extent that the possibly lossy encoding performed by the encoder 38 makes it possible to do so.
The output of the decoding process is then provided to a first feature extractor 44 , also executing on the aggregating server 36 . The first feature extractor 44 implements known feature extraction algorithms for extracting temporal or spatial features of the encoded media 40 . Known feature extraction methods include the Sarnoff JND (“Just Noticeable Difference”) method and the methods disclosed in ANSI T1.801.03-1996 (“American National Standard for Telecommunications—Digital Transport of One Way Video Signals—Parameters for Objective Performance Specification”) specification.
A typical feature-extractor might evaluate a discrete cosine transform (“DCT”) of an image or a portion of an image. The distribution of high and low frequencies in the DCT would provide an indication of how much detail is in any particular image. Changes in the distribution of high and low frequencies in DCTs of different images would provide an indication of how rapidly images are changing with time, and hence how much “action” is actually in the moving image.
The original media 39 is also passed through a second feature extractor 46 identical to the first feature extractor 44 . The outputs of the first and second feature extractors 44 , 46 are then compared by a first analyzer 48 . This comparison results in the calculation of an encoding metric indicative of the extent to which the subjective perception of a user would be degraded by the encoding and decoding algorithms by themselves.
An analyzer compares DCTs of two images, both of which are typically matrix quantities, and maps the difference to a scalar. The output of the analyzer is typically a dimensionless quantity between 0 and 1 that represents a normalized measure of how different the frequency distribution of two images are.
The content-delivery server 30 transmits the encoded media 40 to the user by placing it on the global computer network 34 . Once on the global computer network 34 , the encoded media 40 is subjected to the various difficulties that are commonly encountered when transmitting data of any type on such a network 34 . These include jitter, packet loss, and packet latency. In one embodiment, statistics on these and other measures of transmission error are collected by a network performance monitor 52 and made available to the aggregating server 36 .
The media stream received by the client 32 is then provided to a second decoder 54 identical to the first decoder 42 . A decoded stream 56 from the output of the second decoder 54 is made available for display to the end-user. In addition, the decoded stream 56 is passed through a third feature extractor 58 identical to the first and second feature extractors 44 , 46 . The output of the third feature extractor 58 is provided to a second analyzer 60 .
The inputs to both the first and third feature extractor 44 , 58 have been processed by the same encoder 38 and by identical decoders 42 , 54 . However, unlike the input to the third feature extractor 58 , the input to the first feature extractor 44 was never transported across the network 34 . Hence, any difference between the outputs of the first and third feature extractors 44 , 58 can be attributed to transmission errors alone. This difference is determined by second analyzer 60 , which compares the outputs of the first and third feature extractors 44 , 58 . On the basis of this difference, the second analyzer 60 calculates a transmission metric indicative of the extent to which the subjective perception of a user would be degraded by the transmission error alone.
The system 28 thus provides an estimate of a user's perception of the quality of a media stream on the basis of features in the rendered stream. This estimate is separable into a first portion that depends only on encoding error and a second portion that depends only on transmission error.
Having determined a transmission metric, it is useful to identify the relative effects of different types of transmission errors on the transmission metric. To do so, the network statistics obtained by the network performance monitor 52 and the transmission metric determined by the second analyzer 60 are provided to a correlator 62 . The correlator 62 can then correlate the network statistics with values of the transmission metric. The result of this correlation identifies those types of network errors that most significantly affect the end-user's experience.
In one embodiment, the correlator 62 averages network statistics over a fixed time-interval and compares averages thus generated with corresponding averages of transmission metrics for that time-interval. This enables the correlator 62 to establish, for that time interval, contributions of specific network impairments, such as jitter, packet loss, and packet latency, toward the end-user's experience.
Although the various processes are shown in FIG. 1 as executing on specific servers, this is not a requirement. For example, the system 28 can also be configured so that the first decoder 42 executes on the content-delivery server 30 rather than on the aggregating server 36 as shown in FIG. 1 . In one embodiment, the output of the first feature extractor is sent to the client and the second analyzer executes at the client rather than at the aggregating server 36 . The server selected to execute a particular process depends, to a great extent, on load balancing.
Other embodiments are within the scope of the following claims. | A method for evaluating an end-user's subjective assessment of streaming media quality includes obtaining reference data characterizing the media stream, and obtaining altered data characterizing the media stream after the media stream has traversed a channel that includes a network. An objective measure of the QOS of the media stream is then determined by comparing the reference data and the altered data. | 7 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation under 35 U.S.C. §§120 and 365(c) of international application PCT/EP20061012096, filed on Dec. 15, 2006. This application also claims priority under 35 U.S.C. §119 of DE 10 2006 005 988.3, filed on Feb. 8, 2006 and DE 10 2006 021 553.2, filed May 8, 2006.
BACKGROUND OF THE INVENTION
[0002] The invention concerns a fluid reservoir based on a polymer substrate, its applications, and a process for manufacturing such fluid reservoir
[0003] For many applications, there is a need for particulate carriers that can absorb fluids and, depending on the application, also store them and release them again when needed.
[0004] There are many models for this at the state of the art. As a general rule, certain core materials, such as zeolites, are impregnated with appropriate fluids, such as perfume oil. Often such a system is later coated to prevent undesired loss of the fluid.
DESCRIPTION OF THE INVENTION
[0005] There is, to be sure, a further need for corresponding systems that can absorb preferably even high proportions of fluids, store them reliably, and release them again only after a time delay. Satisfaction of such needs was the objective of this invention.
[0006] This objective was attained, surprisingly, by the subject of the invention. That is a particulate fluid reservoir made of a porous, particulate polymer substrate, which is charged with 5% by weight to 95% by weight, based on the total weight of the charged polymer substrate, of, an inclusion mixture. This inclusion mixture:
a) is, as such, highly viscous or solid at temperatures ≦20° C., b) containing fluids, and contains at least one additive that can flow at elevated temperature, having a melting point or flow point in the range of 25° C. to 120° C., c) c) transforms, essentially without decomposition, into a molten state even at temperatures below 120° C.
[0010] The particulate fluid reservoir is, therefore, understood to be a porous polymer substrate in which high proportions of fluid, such are perfume, are immobilized reliably and stably. Release of the fluid can be accomplished, for instance, by temperature elevation and/or mechanical stress. Thus it is possible to create a sort of liquid depot that can be opened if needed.
[0011] The fluid reservoir can advantageously be incorporated into various matrices without a problem, even in liquid matrices, without there being any significant disadvantageous interaction with the matrix.
[0012] The concept “essentially without decomposition” takes into consideration the fact that many materials or compounds or substances can decompose due to input of thermal energy. That means that in such a case the material in consideration is so altered in its structure by the influence of the temperature that it is transformed into a state that is no longer suitable for its originally intended use.
[0013] In contrast, the inclusion mixtures are preferably distinguished by the fact that they transform into a molten state essentially without decomposition. That means that, at the particular temperature stress that is required to convert them to the molten state, they are not subject to any major degradation reactions, so that a inclusion mixture according to the invention preferably remains unaltered, in the greatest part, even after its transformation to a molten state and the subsequent transformation back into the solid state. That is in contrast to an object that suffers decompositions in transformation into the molten state, so that the object, after returning to the solid state, clearly differs from its initial condition, such as with respect to its appearance, its feel, its odor, or other aspects.
[0014] An inclusion mixture is preferably considered highly viscous if the Brookfield viscosity at 25° C. is greater than 2500 mPas, preferably 5,000 mPas, especially 7,500 mPas, preferably 10,000 mPas and particularly preferably 25,000 mPas. (Viscosity measurement in a Brookfield Model DV II Viscosimeter with Spindle 3 at 20 rpm).
[0015] The fluid is preferably a liquid (at T=20° C.), preferably comprising
a) liquid fragrances (perfume oils and/or b) liquid ingredients of laundry detergents and cleaners, such as preferably surfactants, particularly nonionic surfactants, silicone oils, paraffins and/or c) liquid cosmetic ingredients, such as preferably oils, and/or d) liquid non-pharmaceutical additives or active ingredients and/or e) mixtures of the above.
[0021] Fragrances and nonionic surfactants are most highly preferred, especially in mixtures. In the sense of this invention, the terms “fragrance” and “perfume oil” are used synonymously. They mean, particularly, all those substances, or mixtures of them, which are perceived by humans and animals as odors, especially those perceived by humans as fragrances.
[0022] Individual fragrance compounds such as the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon types can be used as perfume oils. Examples of ester-type fragrance compounds include, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether. The aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, cittronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal. The ketones include, for example, the ionones, isomethylionone and methyl cedryl ketone. The alcohols include anethol, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The principal hydrocarbons are the terpenes and balsams. However, it is preferable to use mixtures of different fragrances which together produce a pleasant fragrance note.
[0023] The perfume oils can, obviously, also contain natural mixtures of fragrances, such as are available from plant or animal sources, such as pine, citrus, jasmine, lily, rose or ylang-ylang oil. Ethereal oils of low volatility that are used primarily as aroma components are also suitable perfume oils, such as sage oil, camilla oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, galbanum oil, and labdanum oil.
[0024] According to the invention, particular fragrances that can be used are selected from fragrances with
(a) almond-like odor, such as preferably benzaldehyde, pentanal, heptenal, 5-methylfurfural, methylbutanal, furfural and/or acetophenone; or (b) apple-like odor, such as preferably (S)-(+)-ethyl 2-methylbutanoate, diethyl malonate, ethyl butyrate, geranyl butyrate, geranyl isopentanoate, isobutyl acetate, linalyl isopentanoate, (E)-β-damascone, heptyl 2-methylbutyrate, methyl 3-methylbutyrate, 2-hexenal pentylmethylbutyrate, ethylmethylbutyrate and/or methyl 2-methylbutanoate; or (c) apple-peel-like odor, such as preferably ethyl hexanoate, hexyl butanoate and/or hexyl hexanoate; or (d) apricot-like odor such as preferably γ-undecalactone, or (e) banana-like odor, such as preferably isobutyl acetate, isoamyl acetate, hexenyl acetate and/or pentyl butanoate; or (f) bitter-almond-like odor such as preferably 4-acetyltoluene, or (g) black-currant-like odor such as preferably mercaptomethyl pentanone and/or methoxymethylbutanethiol, or (h) citrus-like odor, such as preferably linalyl pentanoate, heptanal, linalyl isopentanoate, dodecanal, linalyl formate, α-p-dimethylstyrene, p-cymenol, nonanal, β-cubebene, (Z)-limonene oxide, cis-6-ethenyl-tetrahydro-2,2,6-trimethylpyran-3-ol, cis-pyranoid linalool oxide, dihydrolinalool, 6(10)-dihydromyrcenol, dihydromyrcenol, β-farnesene, (Z)-β-farnesene, (Z)-ocimene, (E)-limonene oxide, dihydroterpinyl acetate, (+)-limonene, (epoxymethylbutyl)-methylfuran and/or p-cymene; or (i) cocoa-like odor, such as preferably dimethylpyrazine, butyl methylbutyrate and/or methylbutanal; or (j) coconut-like odor, such as preferably γ-octalactone, γ-nonalactone, methyl laurate, tetradecanol, methyl nonanoate, (3S,3aS,7aR)-3a,4,5,7a-tetrahydro-3,6-dimethylbenzofuran-2(3H)-one, 5-butyldihydro-4-methyl-2-(3H)-furanone, ethyl undecanoate and/or δ-decalactone; or (k) cream-like odor such as preferably diethyl acetal, 3-hydroxy-2-butanone, 2,3-pentanedione and/or 4-heptanal; or (l) flower-like odor such as preferably benzyl alcohol, phenylacetic acid, tridecanal, p-anisyl alcohol, hexanol, (E,E)-farnesylacetone, methyl geranate, trans-crotonaldehyde, tetradecyl aldehyde, methyl anthranilate, linalool oxide, epoxylinalool, phytol, 10-epi-γ-eudesmol, nerol oxide, ethyl dihydrocinnamate, γ-dodecalactone, hexadecanol, 4-metcapto-4-methyl-2-pentanol, (Z)-ocimene, cetyl alcohol, nerolidol, ethyl (E)-cinnamate, elemicin, pinocarveol, α-bisabolol, (2R,4R)-tetrahydro-4-methyl-2-(2-methyl-1-propenyl)-1H-pyran, (E)-isoelemecin, methyl 2-methylpropanoate, trimethylphenyl butenone, 2-methylanisol, β-farnesol, (E)-isoeugeol, nitrophenylethane, ethyl vanillate, 6-methoxyeugenol, linalool, β-ionone, trimethylphenyl butenone, ethyl benzoate, phenylethyl benzoate, isoeugenol and/or acetophenone; or fresh odor, such as preferably methyl hexanoate, undecanone, (m) fresh odor, such as preferably methyl hexanoate, undecanone, (Z)-limonene oxide, benzyl acetate, ethyl hydroxyhexanoate, isopropyl hexanoate, pentadecanal, β-elemene, α-zingiberene, (E)-limonene oxide, (E)-p-mentha-2,8-dien-1-ol, menthone, piperitone, (E)-3-hexenol and/or carveol; or (n) fruit odor, such as preferably ethyl phenyacetate, geranyl valerate, γ-heptalactone, ethyl propionate, diethyl acetal, geranyl butyrate, ethyl heptanoate, ethyl octanoate, methyl hexanoate, dimethylheptenal, pentanone, ethyl 3-methylbutanoate, geranyl isovalerate, isobutyl acetate, ethoxypropanol, methyl-2-butenal, methyl nonanedione, linalyl acetate, methyl geranate, limonene oxide, hydrocinnamyl alcohol, diethyl succinate, ethylhexanoate, ethylmethylpyrazine, Nryletat, citronellyl butyrate, hexyl acetate nonyl acetate; butyl methylbutyrate, pentenal, isopentyldmethylpyrazine, p-menth-1-en-9-ol, hexadecanone, octyl acetate, γ-dodecalactone, epoxy-β-ionone, ethyl octenoate, ethyl isohexanoate, isobornyl propionate, cedrenol, p-menth-1-en-9-yl acetate, cadinadiene, (Z)-3-hexenyl hexanoate, ethyl cyclohexanoate, 4-methylthio-2-butanone, 3,5-octadienone, methyl cyclohexanecarboxylate, 2-pentyithiophene, α-ocimene, butanediol, ethyl valerate, pentanol, isopiperitone, butyl octanoate, ethyl vanillate, methyl butanoate, 2-methylbutyl acetate, propyl hexanoate, butyl hexanoate, isopropyl butanoate, spathulenol, butanol, δ-dodecalactone, methylquinoxaline, sesquiphellandrene, 2-hexenol, ethyl benzoate, isopropyl benzoate, ethyl lactate and/or citronellyl isobutyrate; or (o) geranium-like odor, such as preferably geraniol, (E,Z)-2,4-nonadienal, octadienone and/or o-xylene; or (p) grape-like odor, such as preferably ethyl decanoate and/or hexanone; or (q) grapefruit-like odor such as preferably (+)-5,6-dimethyl-8-isopropenylbicyclo[4.4.0]dec-1-en-3-one and/or p-menthenethiol; or (r) grass-like odor such as preferably 2-ethylpyridine, 2,6-dimethyl-naphthalene, hexanal, and/or (Z)-3-hexenol; or (s) green note, preferably 2-ethylhexanol, 6-decenal, dimethylheptenal, hexanol, heptanol, methyl-2-butenal, hexyl octanoate, nonanoic acid, undecanone, methyl geraniate, isobornyl formate, butanal, octanal, nonanal, epoxy-2-decenal, cis-linalool, pyrane oxide, nonanol, alpha,gamma-dimethylallyl alcohol, (Z)-2-penten-1-ol, (Z)-3-hexenyl butanoate, isobutylthiazol, (E)-2-nonenal, 2-dodecanal, (Z)-4-decenal, 2-octenal, 2-hepten-1-al, bicyclogermacrene, 2-octenal, α-thujene, (Z)-β-farnesene, (−)-γ-elemene, 2,4-octadienal, fucoserratene, hexenyl acetate, geranyl acetone, valencene, β-eudesmol, 1-hexenol, (E)-2-undecenal, Artemisia ketone, viridiflorol, 2,6-nonadienal, trimethylphenyl butenone, 2,4-nonadienal, butyl isothiocyanate, 2-pentanol, elemol, 2-hexenal, 3-hexenal, (+)-(E)-limonene oxide, cis-isocitral, dimethyloctadienal, bornyl formate, bornyl isovalerate, isobutyraldehyde, 2,4-hexadienal, trimethylphenyl butenone, nonanone, (E)-2-hexenal, (+)-cis-rosene oxide, menthone, coumarin, (epoxymethylbutyl)-methylfuran, 2-hexenol, (E)-2-hexenol and/or carvyl acetate; or (t) green-tea-like odor, preferably (−)-cubenol, or (u) herb-like odor, preferably octanone, hexyl octanoate, caryophyllene oxide, methylbutenol, safranal, benzyl benzoate, bornyl butyrate, hexyl acetate, β-bisabolol, piperitol, β-selinene, α-cubebene, p-menth-1-en-9-ol, 1,5,9,9-tetramethyl-12-oxabicyclododeca-4,7-diene, T-muuroloi, (−)-cubenol, levomenol, ocimene, α-thujene, p-menth-1-en-9-yl acetate, dehydrocarveol, Artemisia alcohol, γ-muurolene, hydroxypentanone, (Z)-ocimene, β-elemene, δ-cadinol, (E)-β-ocimene, (Z)-dihydrocarvone, α-cadinol, calamenene, (Z)-piperitol, lavandulol, β-bourbonene, (Z)-3-hexenyl 2-methylbutanoate, 4-(1-methylethyl)-benzenemethanol, Artemisia ketone, methyl-2-butenol, heptanol, (E)-dihyrocarvone, p-2-menthen-1-ol, α-curcumene, spathulenol, sesquiphellandrene, citronellyl valerate, bornyl isovalerate, 1,5-octadiene-3-ol, methyl benzoate, 2,3,4,5-tetrahydroanisol and/or hydroxycalamenene; or (v) honey-like odor, preferably ethyl cinnamate, β-phenylethyl acetate, phenylacetic acid, phenylethanal, methyl anthranilate, cinnamic acid, β-damascenone, ethyl-(E)-cinnamate, 2-phenylethyl alcohol, citronellyl valerate, phenylethyl benzoate and/or eugenol; or (w) hyacinth-like odor, preferably hotrienol, or (x) jasmine-like odor, preferably methyl jasmonate, methyl dihydroepijasmonate and/or methyl epijasmonate, or (y) lavender-like odor, preferably linalyl valerate and/or linalool, or (z) citron-like odor, preferably neral, octanal, δ-3-carene, limonene, geranial, 4-mercapto-4-methyl-2-pentanol, citral, 2,3-dihydro-1,8-cineol and/or α-terpinene; or (aa) lily-like odor, preferably dodecanal, or (bb) magnolia-like odor, preferably geranyl acetone, or (cc) mandarin-like odor, preferably undecanol, or (dd) melon-like odor, preferably dimethylheptenal, or (ee) mint-like odor, preferably menthone, ethyl salicylate, p-anisaldehyde, 2,4,5,7a-tetrahydro-3,6-dimethylbenzofuran, epoxy-p-menthene, geranial, (methylbutenyl)-methylfuran, dihydrocarvyl acetate; β-cyclocitral, 1,8-cineol, β-phellandrene, methylpentanone, (+)-limonene, dihydrocarveol, (−)-carvone, (E)-p-mentha-2,8-dien-1-ol, isopulegyl acetate. piperitone, 2,3-dihydro-1,8-cineol, α-terpineol, DL-carvone and/or α-phellandrene, or (ff) nut-like odor, preferably 5-methyl-(E)-2-hepten-4-one, γ-heptalactone, 2-acetylpyrrol, 3-octen-2-one, dihydromethylcyclopentapyrazine, acetylthiazol, 2-octenal, 2,4-heptadienal, 3-octenone, hydroxypentanone, octanol, dimethylpyrazine, methylquinoxaline and/or acetylpyrroline; or (gg) orange-like odor, preferably methyl octanoate, undecanone, decyl alcohol, limonene and/or 2-decenal; or (hh) orange-peel-like odor, preferably decanal and/or β-carene; or (ii) peach-like, preferably γ-nonalactone, (Z)-6-dodecene-γ-lactone, δ-decalactone, R-δ-decenolactone, hexyl hexanoate, 5-octanolide, γ-decalactone and/or δ-undecalactone; or (jj) peppermint-like odor, preferably methyl salicylate and/or I-menthol; or (kk) pine-like flavor, preferably α-p-dimethylstyrene, β-pinene, bornyl benzoate, δ-terpinene, dihdroterpinyl acetate and/or α-pinene; or (ll) pineapple-like odor, preferably propyl butyrate, propyl propanoate and/or ethyl acetate; or (mm) plum-like odor, preferably benzyl butanoate; or (nn) raspberry-like odor, preferably β-ionone, or (oo) rose-like odor, preferably β-phenethyl acetate, 2-ethylhexanol, geranyl valerate, geranyl acetate, citronellol, geraniol, geranyl butyrate, geranyl isovalerate, citronellyl butyrate, citronellyl acetate, isogeraniol, tetrahydro-4-methyl-2-(2-methyl-1-propenyl)-2,5-cis-2H-pyran, isogeraniol, 2-phenylethyl alcohol, citronellyl valerate and/or citronellyl isobutyrate; or (pp) green mint-like odor, preferably carvyl acetate and/or carveol; or (qq) strawberry-like odor, preferably hexylmethyl butyrate, methyl cinnamate, pentenal, methyl cinnamate; or (rr) sweetish odor, preferably benzyl alcohol, ethylphenyl acetate, tridecanal, nerol, methyl hexanoate, linalyl isovalerate, undecanaldehyde, carophyllene oxide, linalyl acetate, safranal, uncineol, phenylethanal, p-anisaldehyde, eudesmol, ethylmethylpyrazine, citronellyl butyrate, 4-methyl-3-penten-2-one, nonyl acetate, 10-epi-γ-eudesmol, β-bisabolol, (Z)-6-dodecen-γ-lactone, β-farnesene, 2-dodecanal, γ-dodecalactone, epoxy-β-ionone, 2-undecenal, styrene glycol, methyl furaneol, (−)-cis-rosene oxide, (E)-β-ocimene, dimethylmethoxyfuranone, 1,8-cineole, ethylbenzaldehyde, 2-pentylthiophene, α-farnesene, methionol, 7-methoxycoumarin, (Z)-3-hexenyl-2-methylbutanoate, o-aminoacetophenone, viridiflorol, isopiperitone, β-sinensal, ethyl vanillate, methyl butanoate, p-methoxystyrene, 6-methoxyeugeol, 4-hexanolid, δ-dodecalactone, sesquiphellandrene, diethylmalate, linalyl butyrate, guaiacol, coumarin, methyl benzoate, isopropyl benzoate, safrole, durene, γ-butyrolactone, ethyl isobutyrate and/or furfural; or (ss) vanilla-like odor, preferably vanillin, methyl vanillate, acetovanillone and/or ethyl vanillate;or (tt) watermelon-like odor, preferably 2,4-nordienal, or (uu) wood-like odor, preferably α-muurolene, cadina-1,4-dien-3-ol, isocaryophyllene, eudesmol, α-ionone, bornyl butyrate, (E)-α-bergamotene, linalool oxide, ethylpyrazine, 10-epi-γ-eudesmol, germacrene B, trans-sabinene hydrate, dihydrolinalool, isodihydrocarveol, β-farnesene, β-sesquiphellandrene, d-elemene, α-calacorene, epoxy-β-ionone, germacrene D, bicyclogermacrene, alloaromadendrene, α-thujene, oxo-β-ionone, (−)-γ-elemene, γ-muurolene, sabinene, α-guainene, α-copaene, γ-cadinene, nerolidol, β-eudesmol, α-cadinol, δ-cadinene, 4,5-dimethoxy-6-(2-propenyl)-1,3-benzodioxol, [1ar-(1a-alpha, 4a alpha, 7 alpha, 7a beta 7b alpha)]-decahydro-1,1,7-trimethyl-4-methylene-1H-cycloprop[e]azulene, α-gurjunene, guaiol, α-farnesene, γ-selinene, 4-(1-methylethyl)-benzenemethanol, perillene, elemol, α-humulene, b-caryophyllene and/or β-guaiene;
or mixtures of the above.
[0072] The fluid is preferably an essentially hydrophobic liquid. Typical hydrophobic groups are, for example, long-chain or aromatic hydrocarbon groups. Perfume oils are as a general rule hydrophobic liquids.
[0073] The fluid can preferably contain liquid cosmetic ingredients, such as oils. Preferred oils can advantageously be completely synthetic oils such as silicone oils, vegetable and/or animal fat oils triglycerides of medium or unsaturated fatty acids) and/or ethereal oils (such as from plant parts).
[0074] The inclusion mixture, advantageously the fluid, can preferably contain one or more skin-care and/or skin-protective active substances.
[0075] Skin-care active substances are all those active substances that give the skin a sensory and/or cosmetic advantage. Active skin-care substances are preferably selected from the following substances:
a) waxes, such as, for example, carnauba, spermaceti, beeswax, lanolin and/or derivatives of those and others b) hydrophobic plant extracts c) hydrocarbons, such as squalene and/or squalane d) higher fatty acids, preferably those with at least 12 carbon atoms, such as lauric acid, stearic acid, behenic acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, isostearic acid and/or multiply unsaturated fatty acids and others e) higher fatty alcohols, preferably those with at least 12 carbon atoms, such as lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, cholesterol and/or 2-hexadecanol and others f) esters, preferably those such as cetyl octanoate, lauryl lactate, myristyl lactate, cetyl lactate, isopropyl myristate, myristyl myristate, isopropyl palmitate, isopropyl adipate, butyl stearate, decyl oleate, cholesterol isostearate, glycerol monostearate, glycerol distearate, glycerol tristearate, alkyl lactates, alkyl citrates and/or alkyl tartrates and others. g) lipids, such as, for example, cholesterol, ceramide and/or sucrose esters and others h) vitamins such as Vitamins A and E, vitamin alkyl esters, including Vitamin C alkyl esters and others i) sunscreens j) phospholipids k) derivatives of alpha-hydroxyacids l) odorants m) germicides for cosmetic use, both synthetic such as salicylic acid and/or others, as well as natural ones such as neem oil and/or others. n) silicones
and mixtures of components named above.
[0090] The inclusion mixture, advantageously the fluid, can preferably contain oil with antiseptic action, preferably ethereal oil, selected in particular from the group of Angelica fine— Angelica archangelica, Anis—Pimpinella anisum, Benzoe siam—Styrax tokinensis, Cabreuva—Myrocarus fastigiatus, Cajeput—Melaleuca leucadendron, Cistrose—Cistrus ladaniferus, Copaiba balsam—Copaifera reticulata, costus root—Saussurea discolor, silver fir needles— Abies alba, elemi— Canarium luzonicum; fennel— Foeniculum dulce; spruce— Picea abies; geranium— Pelargonium graveolens; ho leaves— Cinnamonum camphora; immortelle (straw flowers)— Helichrysum ang.; ginger extra— Zingiber off.; Saint John's wort— Hypericum perforatum; jojoba, German camomile— Matricaria recutita; blue fine camomile: Matricaria chamomilla; Roman camomile: Anthemis nobilis; wild camomile: Ormensis multicaulis; carrot: Daucus carota; dwarf pine— Pinus mugho; lavender: Lavendula hybrida; Litsia cubeba —(May Chang), Manuka—Leptospermum scoparium; melissa—Melissa officinalis; maritime pine— Pinus pinaster; myrrh— Commiphora molmol; myrtle— Myrtis communis; neem— Azadirachta; Niaouli —(MQV) Melaleuca quin. viridiflora; palmarosa— Cymbopogom martini; patchouli— Pogostemon patschule; Peru balsam—Myroxylon balsmaum var. pereirae; raventsara aromatics, rose wood— Aniba rosae odora, sage— Salvia officinalis; horsetail— Equisetaceae; milfoil extra— Achille millefolia; ribwort plantain— Plantago lanceolata; styrax— Liquidambar orientalis; French marigold (marigold)— Tagetes patula; tea tree— Melaleuca alternifolia; tolu balsam— Myroxylon balsamum L.; Virginia cedar— Juniperus virginiana; frankincense (Olibanum)— Boswellia carteria; silver fir— Abies alba.
[0091] The inclusion mixture, advantageously the fluid, can preferably contain skin-protective active substances, advantageously skin-protecting oil. The skin-protecting substance is advantageously a skin-protecting oil, for example, also a carrier oil, particularly selected from the group of algal oil, Oleum phaeophyceae, Aloe vera oil, Aloe vera brasiliana, apricot kernel oil, Prunus armeniaca, arnica oil, Arnica montana, avacodo oil Persea americana, borage oil Borago officianalis, calendula oil Calendula officinalis, camellia oil Camellia oleifera, thistle oil Carthaqmus tinctorius, peanut oil Arachis hypogaea, hemp oil Cannabis sativa, hazelnut oil Corylus avellana, Saint John's wort oil Hypericum perforatum, jojoba oil Simondsia chinensis, carrot oil Daucus carota, coconut oil Cocos nucifera, pumpkin seed oil Curcubita pepo, kukui nut oil Aleurites moluccana, macadamia nut oil Macadamia ternifolia, almond oil Prunus dulcis, olive oil Olea europaea, peach seed oil Prunus persica, rapeseed oil Brassica oleifera, castor oil Ricinus communis, nutmeg oil Nigella sativa, sesame oil Sesamium indicum, sunflower oil Helianthus annus, grapeseed oil Vitis vinifera, walnut oil Juglans regia, wheat germ oil Triticum sativum, with borage oil, hemp oil and almond oil particularly advantageous of these.
[0092] The inclusion mixture, advantageously the fluid, can preferably contain humidity control factors, such as those selected from the following group: amino acids, chitosan or chitosan salts/derivatives, ethylene glycol, glucosamine, glycerol, diglycerol, triglycerol, uric acid, honey and hardened honey, creatinine, hydrolysis products of collagen, lactitol, polyols and polyol derivatives (such as butylene glycol, erythritol, propylene glycol, 1,2,6-hexanetriol, polyethylene glycols such as PEG-4, PEG-6, PET-7, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14, PEG-16, PEG-18, PEG-20), pyrrolidine carboxylic acid, sugars ‘and sugar derivatives (such as fructose, glucose, maltose, maltitol, mannitol, inositol, sorbitol, sorbityl silanediol, sucrose, trehalose, xylose, xylitol, glucuronic acid and its salts), ethoxylated sorbitol (Sorbeth-6, Sorbeth-20, Sorbeth-30, Sorbeth-40), hardened starch hydrolysates and mixtures of hardened wheat protein and PEG-20-acetate copolymer, especially panthenol.
[0093] According to a preferred embodiment the polymer substrate is hydrophobic.
[0094] According to a further preferred embodiment, the longitudinal diameter of the fluid reservoir, measured at its longest dimension, is between 20 um and 30 cm. Lower limits can also be 30 μm, 40 μm, 50 μm, 60 μm, 70 um, 80 μm or 100 μm, or even higher values such as 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, etc. Upper limits can also be 20 cm, 15 cm, 10 cm, 5 cm, 3 cm, 1 cm, 0.5 cm, 0.25 cm, 0.1 cm or 0.01 cm or even lower values such as 0.005 cm, etc.
[0095] According to a preferred embodiment the polymer substrate is at least partially built up of polymers selected from polyolefins, fluoropolymers, styrene polymers, copolymers of those polymers and/or mixtures of the polymers named above.
[0096] For example, polypropylenes, polyethylenes, etc. are particularly preferred. Hydrophobic polymer substrates are used preferably. HDPE, LDPE, LLDPE, or UHMW-PE are particularly advantageous polyethylenes. Poly(4-methyl-1-pentene), poly(1-butene) or polyisobutene are particularly preferred, and, as copolymers, ethylene-propylene copolymers or ethylene-vinyl acetate copolymers. Examples of preferred fluoropolymers include polyvinylidene fluoride and polyvinyl fluoride and the copolymers poly(tetrafluoroethylene-co-hexafluoropropylene), poly(tetrafluoroethylene-co-perfluoroalkyl vinyl ether) and poly(ethylene-co-tetrafluoroethylene). Of the styrene polymers, polystyrene and styrene-acrylonitrile copolymers, styrene-butadiene copolymers and acrylonitrile butadiene styrene copolymers are preferred. However, polymer substrates based on polyolefins, and especially based on polypropylene or polyethylene are particularly preferred. In particular, cross-linked (co-) polymers are likewise preferred.
[0097] According to a preferred embodiment, the polymer substrate has at least partially an open-pore structure with a mean pore diameter preferably between 1 μm and 300 μm before charging with the inclusion mixture. The lower limit can also have values such as 5 μm, 10 μm, 15 μm, 20 μm, 25 μm or 30 μm, etc. The upper limits can also be at values such as 280 μm, 260 μm, 240 μm or 220 μm, etc.
[0098] A usable porous particulate polymer substrate with at least partially open-pore structure can have a spongy cellular or even a network-like or coral-like microstructure. The pore structure should be at least partially open-pore. That is, the pores in the polymer substrate must be in fluid contact with each other, at least in subregions of the substrate structure, and the particles of the polymer substrate should be open-pored in at least subregions of their external surface. That allows adequate permeability to the fluids. Thus use of a particulate polymer substrate with at least partial open-pore structure allows extensive fluid uptake. In a preferred embodiment the polymer substrate used according to the invention has a mean pore diameter in the range between 4 and 110 μm. A mean pore diameter in the range of 5 to 50 μm is especially preferred. Polymer substrates with such preferred pore diameters exhibit good charging ability.
[0099] According to a preferred embodiment the inclusion mixture transforms essentially without decomposition into a molten state at temperatures below 100° C., advantageously below 90° C., in an advantageous manner below 80° C., especially below 70° C.
[0100] According to a further preferred embodiment, the inclusion mixture comprises at least 20% by weight, preferably at least 30% by weight, advantageously at least 40% by weight, in a very advantageous manner at least 50% by weight, in an especially advantageous manner at least 60% by weight, in an extremely advantageous manner at least 70% by weight, in the utmost advantageous manner at least 80% by weight, in an even more advantageous manner at least 90% by weight, particularly at least 95% by weight, but in the most advantageous manner 100% by weight of the components fluid and additive(s) having melting points or flow points in the range of 25° C. to 120° C.
[0101] According to another preferred embodiment the additives contained in the inclusion mixture having a melting point or flow point in the range of 25° C. to 120° C. are at least partially soluble in the fluid, preferably essentially completely soluble in the fluid near their particular flow point.
[0102] According to another preferred embodiment the inclusion mixture is highly viscous or particularly solid at temperatures up to ≦22° C., advantageously up to ≦28° C., in a very advantageous manner up to ≦32° C., in a particularly advantageous manner up to ≦38° C., in a quite particularly advantageous manner up to ≦42° C., in a further advantageous manner up to ≦48° C., in a still further advantageous manner up to ≦55° C., in an even more advantageous manner up to ≦60° C.
[0103] According to a further preferred embodiment, the flow point of the additive that is able to flow at elevated temperatures, or of the mixture of these additives, is greater than 25° C., preferably in the range of 30 to 90° C., advantageously in the range of 35 to 70° C. and particularly in the range of 40 to 60° C.
[0104] According to a further preferred embodiment, the inclusion mixture comprises up to 90% by weight, preferably 10 to 80% by weight, but especially preferably less than 70% by weight, that is, advantageously 15 to 65% by weight, in a very advantageous manner up to 55% by weight, in an even more advantageous manner 28 to 50% by weight of additives that are able to flow at elevated temperatures (that is, additives with flow points or melting points in the range of 25° C. to 120° C.), based on the total inclusion mixture with which the polymer substrate is charged.
[0105] According to a further preferred embodiment, the inclusion mixture comprises more than 5% by weight of fluid(s), preferably more than 10% by weight, advantageously 15 to 90% by weight, in a very advantageous manner 20 to 80% by weight, in an even more advantageous manner 25 to 75% by weight, especially 30 to 72% by weight of fluid(s), based on the total inclusion mixture with which the polymer substrate is charged.
[0106] According to a further preferred embodiment, the fluid reservoir contains less than 25% by weight, preferably less than 15% by weight, advantageously less than 10% by weight, even more advantageously less than 5% by weight of water, based on the total fluid reservoir, and in particular it is completely free of water.
[0107] According to a further preferred embodiment, the additives contained in the inclusion mixture, which have flow points in the temperature range of 25° C. to 120° C., are selected from the group of fatty alcohols, fatty acids, silicones (silicone oils), paraffins, nonionic surfactants, esterquats, glycerides of fatty acids (natural oils), waxes, mono, di or tri-glycerides, carbohydrates and/or polyalkylene glycols.
[0108] As carbohydrates, sugars can be used here to advantage. Some examples are alpha-D-glucose monohydrate (melting point in the range of 83-86° C.), alpha-D-galactose monohydrate (melting point in the range of 118-120° C.) or maltose monohydrate (melting point in the range of 102-103° C.). The derivatives are also suitable, for instance, amino sugars such as D-glucosamine (melting point of the α-form: 88° C.) or deoxysugars such as rhamnose monohydrate (melting point 92-94° C.).
[0109] Suitable paraffins can be, for instance, octadecane, nonadecane, eicosane, docosane, tricosane, tetracosane, pentacosane, hexacosane, octacosane, nonacosane or triacosan, to name some examples.
[0110] Suitable fatty alcohols can be, for instance, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 9-trans-octadecen-1-ol, 1-nonadecanol, 1-eicosanol, 1-heneicosanol, 1-docosanol, 12-cis-docosen-1-ol, or 3-trans-docosen-1-ol, to name some examples. They also include the so-called wax alcohols, fatty alcohols with about 24-36 carbon atoms, such as triacontanol-1 or melissyl alcohol. They also include unsaturated fatty alcohols such as elaidyl alcohol, eruca alcohol or brassidyl alcohol. They also include Guerbet alcohols such as C 32 H 66 O or C 36 H 74 O. They also include alkanediols such as undecane-1,11-diol or dodecane-1,12-diol.
[0111] Suitable nonionic surfactants can be, for instance, fatty alcohol polyglycol ethers, such as C 14 H 29 —O—(CH 2 CH 2 O) 2 H, C 10 H 21 —O—(CH 2 CH 2 O) 8 H, C 12 H 25 —O—(CH 2 CH 2 O) 6 H, C 14 H 29 —O—(CH 2 CH 2 O) 4 H, C 16 H 33 —O—(CH 2 CH 2 O) 12 H, or C 18 H 37 —O—(CH 2 CH 2 O) 4 H, to name some examples.
[0112] Suitable fatty acids can be, for instance, capric acid, undecanoic acid, lauric acid, tridecanoic add, tetradecanoic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotinic acid, crotonic acid, erucic acid, eleostearic acid, or melissic acid, to name some examples.
[0113] Esters of fatty acids, such as the methyl or ethyl esters of behenic or arachidic acid can also be suitable, to name some examples.
[0114] Mono, di or triglycerides, such as the corresponding glycerides of lauric acid, palmitic acid or capric acid, are also suitable, to name some examples.
[0115] Suitable waxes can be natural waxes such as carnauba wax, candelilla wax, esparto wax, guaruma wax, Japan wax, cork wax or montane wax; also animal waxes such as beeswax, wool wax, shellac wax or spermaceti wax; also synthetic waxes such as polyalkylene waxes or polyethylene glycol waxes, likewise chemically modified waxes such as hydrogenated jojoba wax or montane ester wax.
[0116] The inclusion mixture can also contain other additional substances having a melting point above 120° C., such as appropriate carbohydrates, advantageously sugars, such as sucrose (melting point 185-186° C.).
[0117] If the inclusion mixture contains other solids, preferably solids commonly used in laundry detergents, that is likewise a preferred embodiment.
[0118] If the proportion of solids in the inclusion mixture is less than 50%, preferably less than 30%, advantageously less than 25%, especially less than 15%, in an entirely preferred manner less than 10%, based on the total inclusion mixture with which the polymer substrate is charged, this is a further preferred embodiment.
[0119] According to a preferred embodiment the solids contained in the inclusion mixture have a d50 value of less than 0.2 mm, preferably less than 0.1 mm, especially less than 0.05 mm.
[0120] If the inclusion mixture contains solids selected from the group of zeolites, bentonites, silicates, phosphates, urea and/or its derivatives, sulfates, carbonates, citrates, citric acid, acetates and/or salts of the anionic surfactants, this is a further preferred embodiment:
[0121] According to a further preferred embodiment, the fluid reservoir has a size such that it can be grasped by human hands and can be used for manual treatment of objects. For instance, one can rub surfaces with a fluid reservoir in stick form, as in hand washing of textiles.
[0122] The fluid reservoir can have any desired form. It can preferably be rather spherical, oval, cylindrical, or granular, or have any other regular or irregular shape.
[0123] A fluid reservoir that contains at least one, preferably two or more substances usually contained in laundry detergents or cleaners, preferably a substance from the group of surfactants, builder substances (inorganic and organic builders), bleaching agents, bleach activators, bleach stabilizers, bleach catalysts, enzymes, special polymers (for example, those with co-builder properties), antiredeposition agents, optical brighteners, UV-protecting substances, soil repellents, electrolytes, coloring agents, odorants, scents, perfume carriers, pH-adjusting agents, complexing agents, fluorescence agents, foam inhibitors, anti-wrinkling agents, antioxidants, quaternary ammonium compounds, antistatics, ironing aids, UV absorbers, antiredeposition agents, germicides, antimicrobially active substances, fungicides, viscosity regulators, luster agents, color transfer inhibitors, shrinkage inhibitors, corrosion inhibitors, preservatives, plasticizers, softening rinses, protein hydrolysates, phobing and impregnating agents, hydrotropes, silicone oils as well as anti-swelling and anti-slip agents, is a preferred embodiment of the invention.
[0124] It turns out that preferably the following proportions, each based on the total fluid reservoir proportions, each based on the total fluid reservoir, can be particularly advantageous:
porous polymer substrate: preferably 40-75% by weight, especially 40-60% by weight fluid in the polymer substrate: preferably 1-30% by weight, especially 20-30% by weight additive that can flow at elevated temperatures: preferably 1-30% by weight, especially 20-30% by weight
[0128] The fluid reservoir according to the invention is characterized advantageously by the fact that high proportions of liquid, such as perfume, for instance, are reliably immobilized for long periods in the porous polymer substrate and are not released until there is an external stimulus, such as a temperature increase and/or mechanical stress.
[0129] Although the external, visible, surface of the polymer substrate can preferably be occupied by the inclusion mixture, so that one can also advantageously speak of a coated polymer substrate, it is further possible according to a preferred embodiment to give the fluid reservoir according to the invention, that is, the polymer substrate charged with the inclusion mixture, an additional coating. According to a preferred embodiment of the invention, the fluid reservoir is coated.
[0130] Coating agents can be used for the coating. These are substances that give the outer surface of the object to be coated a glossy appearance and/or form a coating (an envelope) on the outer surface. Solid and/or liquid substances can be used as coating agents. They are preferably those that prevent or delay penetration of moisture or prevent or delay loss of aroma.
[0131] Suitable coating agents can contain water-soluble, water-dispersible and/or water-insoluble (co)-polymers. The layer of coating itself can be soluble or insoluble in water.
[0132] Water soluble polymers contain a proportion of hydrophilic groups sufficient for water solubility, and are advantageously not cross-linked. The hydrophilic groups can be nonionic, anionic, cationic or zwitterionic, for instance: —NH 2 , —OH, —SH, —O—, —COOH, —COO— −M + , —SO 3 −M + , —PO 3 −2 M +2 , —NH 3 + .
[0000]
[0000] etc.
[0133] The individual polymers can contain different hydrophilic groups at the same time, such as ionic and nonionic and/or anionic and cationic groups.
[0134] Preferred water-soluble polymers can be, for example, natural polysaccharides and/or peptides, such as starches, alginates, pectins, plant gums, caseins, gelatins, etc.
[0135] Preferred water-soluble polymers can be, for example, semisynthetic polymers, such as cellulose ethers or starch ethers.
[0136] Preferred water-soluble polymers can be, for example, biotechnologically produced products, such as pullulan, curdlan or xanthan.
[0137] Preferred water-soluble polymers can be, for example, synthetic polymers, such as homopolymers and/or copolymers of (meth)acrylic acid and its derivatives, of maleic acid, vinylsulfonic acid, vinylphosphonic acid, polyvinyl alcohol, polyethyleneimine, polyvinylpyrrolidone and the like.
[0138] Preferred coating agents contain water-soluble (co)-polymers, especially those having a melting point or softening point in the range of 48° C. to 300° C., advantageously in the range of 48° C. to 200° C., and in a further advantageous manner in the range of 48° C. to 200° C.
[0139] Suitable water-soluble (co)-polymers with an appropriate melting or softening point can advantageously be selected from the group comprising polyalkylene glycols, polyethylene terephthalates, polyvinyl alcohols and mixture of them.
[0140] The coating can contain, aside from the actual coating agent, or independently of it, other ingredients, such as, advantageously, textile-softening compounds and/or perfume.
[0141] It is also possible to coat the fluid reservoir multiply, such as by first coating the, fluid reservoir with a first coating, e. g., one containing a textile-softening compound and then giving the resulting object a further coating, such as one containing water-soluble polymer and perfume.
[0142] According to a preferred embodiment the coating of the fluid reservoir comprises lipids and/or silicone oils. Preferred lipids are
(a) lipophilic hydrocarbons (such as triacontane, squalene or carotenoids, etc.) (b) lipophilic alcohols (such as wax alcohols, retinol or cholesterol, etc.) (c) ether lipids (d) lipophilic carboxylic acids (fatty acids) (e) lipophilic esters [such as neutral fats—that is, monoacyl glycerols, diacyl glycerols, triacyl glycerols (triglycerides), sterol esters, etc.] (f) lipophilic amides (such as ceramides, etc.) (g) waxes (h) lipids having more than 2 hydrolysis products, such as glycolipids, phospholipids, sphingolipids and/or glycerolipids, etc. (i) lipids in the form of higher-molecular-weight conjugates having more than 2 hydrolysis products, such as lipoproteins and/or lipopolysaccharides, etc. (j) phosphorus-free glycolipids, such as glycosphingolipids (such as, preferably, cerebrosides, gangliosides, sulfatides) or such as glycoglycerolipids (such as preferably glycosyldiglycerides and glycosylmonoglycerides), etc. (k) carbohydrate-free phospholipids, such as sphingophospholipids (such as preferably sphingomyelins) or such as glycerophospholipids (such as preferably lecithins, cephalins, cardiolipids, phosphatidyl inositol and phosphatidyl inositol phosphates, etc.) (l) mixtures of those named above.
[0155] In a further preferred embodiment, the optional coating has colored substances or dyes, brighteners and/or pigments, advantageously in the nanoscale range or in the micrometer range, preferably white pigments, particularly selected from titanium dioxide pigments, such as, in particular, anatase pigments and/or rutile pigments, zinc sulfide pigments, zinc oxide (zinc white), antimony trioxide (antimony white), basic lead carbonate (white lead), 2PbCO 3 .Pb(OH) 2 , or lithopone, ZnS+BaSO 4 . It can preferably also contain white additives such as preferably calcium carbonate, talc, 3MgO.4SiO 2 .H 2 O and/or barium sulfate.
[0156] In a further preferred embodiment, the pigments that can preferably be components of an optional coating can be
(a) colored pigments (preferably inorganic colored pigments, especially iron oxide pigments, chromate pigments, iron blue pigments, chromium oxide pigments, ultramarine pigments, pigments of oxide solid solution pigments and/or bismuth vanadate pigments. (b) black pigments (e. g., aniline black, perylene black, iron oxide pigments, manganese black and/or spinel black) (c) luster pigments (preferably lamellar effect pigments, metal effect pigments such as aluminum pigments (silver bronze), copper pigments and copper/zinc pigments (gold bronzes) and zinc pigments, pearlescent pigments, such as magnesium stearate, zinc stearate, lithium stearate or ethylene glycol distearate or polyethylene terephthalate, interference pigments such as metal oxide mica pigments) and/or (d) luminescent pigments such as azomethine fluorescent yellow, silver-dosed and/or copper-dosed zinc sulfide pigments.
[0161] The optional coating can preferably also comprise the following substances:
(a) carbonates, such as preferably chalk, ground limestone, calcite and/or precipitated calcium carbonate, dolomite and/or barium carbonate (b) sulfates, such as preferably barite, blanc fixe and/or calcium sulfate. (c) silicates such as preferably talc, pyrophyllite, chlorite, hornblende, mica, or kaolin (d) silicic acids, such as preferably quartz, fused silica, cristobalite, diatomaceous earth, Neuberg silica, precipitated silicic acid, pyrogenic silicic acid, ground glass, pumice flour, perlite, calcium metasilicate and/or fibers from melts of glass, basalts, or slags (e) oxides, such as especially aluminum hydroxide and/or magnesium hydroxide (f) (organic fibers, such as especially textile fibers, cellulose fibers, polyethylene fibers, polypropylene fibers, polyamide fibers, polyacrylonitrile fibers and/or polyester fibers, especially with lengths in the nanometer or micrometer range and/or (g) powders, such as powdered starch.
[0169] According to a further preferred embodiment, the optional coating of the fluid reservoir according to the invention is sensitive to pH and/or temperature and/or ionic strength or contains materials sensitive to pH and/or temperature and/or ionic strength.
[0170] The term ‘pH sensitivity, temperature sensitivity and/or ionic strength sensitivity’ means here that the coating or the materials making up the coating
(a) experience(s) a change (increase or decrease) of solubility (preferably in water); and/or (b) experience(s) a change (increase or decrease) of the diffusion density; and/or (c) experience(s) a change (acceleration or deceleration) of the rate of dissolution; and/or (d) experience(s) a change (increase or decrease) of mechanical stability
if there is a change if the pH, the temperature, or the ionic strength of the medium to which the coating is exposed (e. g., a wash liquor).
[0175] For the temperature sensitivity, there is, aside from the options (a) to (d) named above also the additional option (e) according to which the coating or the materials making up the coating experience(s) a change of the state of aggregation from solid to liquid or the reverse on a change of the temperature; that is, the materials melt or solidify.
[0176] In the sense of the invention, all those materials for which the integrity is a function of the temperature and/or the pH and/or the ionic strength, or also those materials that lose their integrity because of mechanical stress, such as occurs in the coarse of an automatic laundry washing process serve as suitable materials.
[0177] The pH sensitivity of the (optional) coating can be utilized advantageously. The (optional) coating can, for example, be of such a nature that it dissolves, partially or completely, if the pH drops below a critical level. That can occur in a laundering process, for instance, if the alkaline wash water is removed from the machine and fresh water is supplied to the machine, preferably in the rinsing portion of the washing process. Then on contact with the fresh water the coating partially or completely loses its integrity, making the granulation penetrable by the water. The particular pH at which the coating disintegrates partially or completely can be adjusted arbitrarily, so that, for example, the material loses its integrity partially or completely if, for example, the pH drops below 9.0 but remains essentially inert as long as the pH is greater than 10.
[0178] The concept “inert” is to be understood according to the invention in the usual sense, that is, that there is essentially no physical or chemical reaction of the material of the coating with its environment but that the material of the coating is physically and chemically resistant to it, so that the granulation is essentially protected from penetration of the environment, such as the wash liquor.
[0179] Preferred coating materials can be
(a) polymers containing carboxylate groups (polycarboxylates), preferably homopolymers of acrylic acid and/or copolymers of acrylic acid and maleic acid, (b) polyethylene glycols, especially those having molecular weights less than about 25,000 g/mole, preferably less than about 10,000 g/mole, advantageously less than about 6,000 g/mole, such as PEG 4000, (c) (acetalized) polyvinyl alcohols (d) (modified) carbohydrates, preferably mono-, oligo-, and/or poly-saccharides, especially glucose (e) polyvinylpyrrolidones
or mixtures of those.
[0185] “Polyvinyl alcohols” (abbreviated PVAL, or occasionally also PVOH) is the designation for polymers having the general structure
[0000] [—CH 2 —CH(OH)—] n
[0000] which also contain in small proportions structural units of the type
[0000] [—CH 2 —CH(OH)—CH(OH)—CH 2 ]
[0186] The usual commercial polyvinyl alcohols, which are marketed as yellowish-white powders or granulations having degrees of polymerization in the range of about 100 to 2500 (molecular weights of about 4,000 to 100,000 g/mole) have degrees of hydrolysis of 98-99 or 87-89 mole-%, thus containing a residual content of acetyl groups. Manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the initial polymer, the degree of hydrolysis, the saponification number, or the viscosity of the solution.
[0187] Depending on their degree of hydrolysis, polyvinyl alcohols are soluble in water and the less polar organic solvents (formamide, dimethylformamide or dimethylsulfoxide). They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classifed as toxicologically unobjectionable and are at least partially biodegradable. The water solubility can be reduced by post-treatment with aldehydes (acetalization), complexing with nickel or copper salts, or treatment with dichromates, boric acid or borax. Polyvinyl alcohol coatings are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen or carbon dioxide, but allow water vapor to penetrate.
[0188] In the context of the present invention, those coatings are preferred that comprise, at least in part, a polyvinyl alcohol with a degree of hydrolysis advantageously 70 to 100 mole % preferably 80 to 90 mole-%, especially preferably 81 to 89 mole-%, and particularly 82 to 88 mole-%. In a preferred embodiment the film material used comprises at least 20% by weight, especially preferably at least 40% by weight, quite particularly preferably at least 60% by weight, and particularly at least 80% by weight of a polyvinyl alcohol for which the degree of hydrolysis is 70 to 100 mole-%, preferably 80 to 90 mole-%, especially preferably 81 to 89 mole-%, and particularly 82 to 88 mole-%. It is preferable for the total coating to contain at least 20% by weight, especially preferably at least 40% by weight, quite particularly preferably at least 60% by weight and particularly at least 80% by weight of a polyvinyl alcohol for which the degree of hydrolysis is 70 to 100 mole-%, preferably 80 to 90 mole-%, especially preferably 81 to 89 mole-%, and particularly 82 to 88 mole-%.
[0189] Polyvinyl alcohols of a particular molecular weight molecular range are used preferably as coating materials. It is preferred according to the invention that the film material comprise a polyvinyl alcohol having a molecular weight in the range of 10,000 to 100,000 g/mol, preferably 11,000 to 90,000 g/mol, especially preferably 12,000 to 80,000 g/mol, and particularly 13,000 to 70,000 g/mol.
[0190] The polyvinyl alcohols described above are broadly available commercially, as under the Mowiol® trade name (Clariant). Polyvinyl alcohols particularly suitable in the context of the present invention include, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88, Mowiol® 8-88 and L648, L734, Mowiflex LPTC 221 from KSE and compounds from Texas Polymers, such as Vinex 2034.
[0191] Other polyvinyl alcohols that are especially suitable as coating materials can be found in the table below:
[0000]
Degree of
Molecular weight
Melting point
Designation
hydrolysis [%]
[kDa]
[° C.]
Airvol ® 205
88
15-27
230
Vinex ® 2019
88
15-27
170
Vinex ® 2144
88
44-65
205
Vinex ® 1025
99
15-27
170
Vinex ® 2025
88
25-45
192
Gohsefimer ® 5407
30-28
23,600
100
Gohsefimer ® LL02
41-51
17,700
100
[0192] Other polyvinyl alcohols suitable as coating materials are ELVANOL® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (DuPont trademarks), ALCOTEX® 72.5, 78, B72, F80/40, F88/4, F88/26, F88/40, F88/47 (trademarks of Harlow Chemical Co.), Gonozoïde® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (trademarks of Nippon Gohsei K. K.). ERKOL types from Wacker are also suitable.
[0193] The water-solubility of PVAL can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols that have been acetalized or ketalized with the aldehyde or ketone groups of saccharides or polysaccharides or mixture of them have proven particularly advantageous because of their outstandingly good solubility in cold water and are specially preferred. The reaction products of PVAL and starch are used as extremely advantageous.
[0194] The water solubility can be further altered by complexing with nickel or copper salts or by treatment with dichromates, boric acid, or borax, so that it can be adjusted deliberately to desired values. Films of PVAL are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, and carbon dioxide, but allow water vapor to penetrate.
[0195] Other preferred coating materials are characterized in that they comprise polyvinylpyrrolidones. Polyvinylpyrrolidones, abbreviated PVP, can be described by the following general formula
[0000]
[0000] PVPs are produced by radical polymerization of 1-vinylpyrollidone. Typical commercial PVPs have molecular weights in the range of preferably about 2,500 to 750,000 g/mol and are marketed as white hygroscopic powders or as aqueous solutions.
[0196] Other preferred coating materials are characterized in that they comprise polyethylene oxides. Polyethylene oxides, abbreviated PEOX, are polyalkylene glycols having the general formula
[0000] H—[O—CH 2 —CH 2 ] n —OH
[0000] They are produced industrially by base-catalyzed polyaddition of ethylene oxide (oxirane) with ethylene glycol as the starting molecule in systems usually containing traces of water. They have molecular weights in the range of about 200 to 5,000,000 g/mol, and corresponding degrees of polymerization of about 5 to >100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxyl terminal groups, and have only weak properties of glycols.
[0197] Other preferred coating materials are characterized in that they comprise gelatins. Gelatin is a polypeptide (molecular weight: about 15,000 to >250,000 g/mol) obtained primarily by hydrolysis of collagen contained in animal skin and bones under acidic or alkaline conditions. The amino acid composition of gelatin largely corresponds to that of the collagen from which it was obtained, and varies, depending on the source.
[0198] Coating materials that comprise a polymer from the group of starches and starch derivatives, cellulose and cellulose derivatives, especially methylcellulose and mixture of those are preferred in the context of the present invention.
[0199] Starch is a homoglycan, in which the glucose units are joined by α-glycoside bonds. Starch is composed of two components having different molecular weights: about 20 to 30% straight-chain amylose (molecular weight about 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (molecular weight about 300,000 to 2,000,000). It also contains traces of lipids, phosphoric add and cations. While amylose forms long intertwined chains of about 300 to 1,200 glucose molecules because of the 1,4 bonding, the amylopectin chain branches through 1,6 bonds after an average of 25 glucose units, giving a branch-like structure with about 1,500 to 12,000 glucose molecules. Starch derivatives that can be obtained by polymer-like reactions of starch are also suitable, along with pure starch, for producing water-soluble envelopes in the context of the present invention. For example, such chemically modified starches comprise products of esterifications or etherifications, in which hydroxyl hydrogen atoms are substituted. However, starches in which the hydroxyl groups are replaced by functional groups not bound through an oxygen atom can also be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethylstarch (CMS), starch esters and starch ethers, as well as amino starches.
[0200] Pure cellulose has the empirical formula (C 6 H 10 O 5 ) n . Considered formally, it is a β-1,4-polyacetal of cellobiose, which is itself made up of two molecules of glucose. Suitable celluloses consist of about 500 to 5,000 glucose units, and accordingly have average molecular weights of 50,000 to 500,000. In the context of the present invention, cellulose derivatives that can be obtained from cellulose by polymer-like reactions are usable as disintegrants based on cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxyl hydrogen atoms are replaced. However, celluloses in which the hydroxyl groups are replaced by functional groups not bound through oxygen atoms can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethylcellulose (CMS), cellulose esters and ethers, and amino celluloses.
[0201] A further object of the present invention is a process for producing a fluid reservoir according to the invention, in which one brings a mixture of additives that are highly viscous or solid at T≦20° C., and fluids, to a liquid state by heating, mixes this flowable mixture with a porous polymer substrate, and then lets it cool.
[0202] In this way the accessible pore system of the polymer substrate can be fully charged if necessary and the pores can also be sealed preferably by cooling after charging.
[0203] A process for producing a fluid reservoir in which
a) one or more common fluids at temperatures of 20 to 22° C. are mixed by stirring with additive(s) having a flow point in the range of 20° C. to 100 C and then b) the mixture is heated to temperatures in the range of the flow point of the additive, preferably above the flow range, so that a flowable mixture results, and then c) while retaining the elevated temperature, other optional additives, especially the usual additives for laundry detergents, advantageously selected from the group of zeolites, bentonites, silicates, phosphates, urea and/or its derivatives, sulfates, carbonates, citrates, citric acid, acetates and/or salts of anionic surfactants are suspended in the mixture, with the mixture still flowable, and then d) the flowable mixture is mixed with a porous polymer substrate at temperatures of 25° to 50° C., and finally e) the resulting mixture is allowed to cool
is a preferred embodiment of the invention.
[0209] If the polymer is preheated to a temperature of 25°-150° C. before it is mixed with the flowable mixture, that is a preferred embodiment.
[0210] In a preferred embodiment the cooling of the mixture is accelerated by adding cold.
[0211] According to a preferred embodiment of the invention it is also possible to suspend the ingredients of an inclusion mixture according to the invention, comprising odorants in particular, and the porous particulate polymer substrate and optionally other additives in liquid carbon dioxide (CO 2 ), mixing them (further) there, and then removing the liquid carbon dioxide, by, for example, simply reducing the pressure in the system so that vaporization can occur. If the expansion of the carbon dioxide is intentionally slowed, particularly advantageous fluid reservoirs can be produced. It is advantageous to work with liquid carbon dioxide in a pressure range of 20 bar to 70 bar at 20° C. Carbon dioxide can likewise be used in other pressure ranges and temperature ranges as long as it is liquid under those conditions.
[0212] Laundry detergents or cleaners containing fluid reservoirs according to the invention, and likewise a cosmetic containing fluid reservoirs according to the invention are an extremely preferred subject of the present invention.
[0213] Use of the fluid reservoirs according to the invention, especially in the form of fragrance blocks and/or fragrance bags for odorizing rooms, vehicles, or closets is likewise a further preferred subject of the invention.
[0214] Use of the fluid reservoirs according to the invention for odorizing objects, preferably laundry detergents, washing machines and cleaning machines, dry laundry and packages is likewise a further preferred subject of the invention.
[0215] Use of the fluid reservoirs according to the invention for odorizing textiles during the washing or drying process, preferably done by machine, is likewise a further preferred subject of the invention.
[0216] Use of the fluid reservoirs according to the invention for direct manual treatment of objects, preferably for rubbing on the objects, especially in manual washing of objects, is likewise a further preferred subject of the invention.
[0217] For instance, fluid reservoirs that hold ingredients of manual dishwashing agents, selected, for example, from
(a) surfactants, such as alkane sulfonates, alkyl ether sulfates, alkyl polyglucosides and/or cocoamidopropyl-betaine, advantageously those suitable for wetting the material being washed and the dirt, removal of grease and other contaminants, (b) (organic) acids, such as citric acid, advantageously suitable for adjusting the pH and for influencing drainage, (c) hydrotropes, such as cumene sulfonate, advantageously suited to avoid phase separation, (d) fat replacers, such as fatty acid amides, advantageously suitable for replacing skin fat, (e) care ingredients, such as Aloe vera extracts, advantageously suitable for skin care, (f) fragrances (perfume), (g) dyes (h) substances with antibacterial action, such as sodium benzoate or sodium salicylate, advantageously suitable for reducing the microbial load. (l) preservatives.
[0227] For instance, fluid reservoirs may be preferred that contain ingredients of machine dishwashing agents, selected, for example, from the following:
[0228] phosphates, such as pentasodium triphosphate, phosphonates, citrates, such as sodium citrate, sodium polycarboxylates, sodium metasilicate, soda, sodium bicarbonate, sodium disilicate, active chlorine, sodium perborate, bleach activator, such as TAED, enzymes, such as proteases and amylases, (low-foam) nonionic surfactants, silver and glass protection, odorants.
[0229] For example, fluid reservoirs may be preferred which contain ingredients of textile detergents, for instance, selected from the following:
anionic surfactants, such as preferably alkylbenzenesulfonate and/or alkyl sulfate, nonionic surfactants such as preferably fatty alcohol polyglycol ether, alkyl polyglucoside and/or fatty acid glucamide, builders, such as preferably zeolite, polycarboxylate and/or sodium citrate, alkalies, such as preferably sodium carbonate, alcohols such as preferably ethanol and/or glycerol, bleaching agents such as preferably sodium perborate and/or sodium percarbonate, corrosion inhibitors such as preferably sodium silicate, stabilizers, such as preferably phosphonates, foam inhibitors such as preferably soaps, silicone oils and/or paraffins, enzymes such as preferably proteases, amylases, cellulases, and/or lipases, antiredeposition agents such as preferably carboxymethylcellulose, discoloration inhibitors such as preferably polyvinylpyrrolidone derivatives, adjusting agents such as preferably sodium sulfate, odorants, optical brighteners, such as preferably stilbene derivatives and/or biphenyl derivatives, and water.
[0231] For example, fluid reservoirs may be preferred which contain ingredients of all-purpose cleaners, selected, for instance, from the following:
surfactants, such as alkane sulfonates, alkylbenzenesulfonates, alkyl polyglucosides, fatty alcohol polyglycol ether sulfates, fatty alcohol polyglycol ethers, builders such as trisodium citrate, the sodium salt of nitrilotriacetic acid, sodium phosphonate, pentasodium triphosphate, solvents and hydrotropes (solubilizers), such as ethanol, propylene glycol ether, sodium toluene or cumene sulfonate, odorants, colorants, or preservatives. Acidic all-purpose cleaners contain acids, such as preferably acetic acid, citric or maleic acid. All-purpose cleaners adjusted to be (weakly) alkaline contain alkalies, such as preferably sodium hydroxide or soda [sodium carbonate].
[0233] Use of the fluid reservoir according to the invention as toilet blocks is likewise another preferred subject of the invention. A toilet block according to the invention, for hanging in the toilet bowl or flush tank, for instance, can release small amounts of acids, surfactant and/or fragrance and thus slow the deposition of contaminants.
[0234] A further subject of the invention is a product such as preferably a household sponge, rag or towel, with which at least one surface of the product is filled with firmly attached fluid reservoirs. For example, it is advantageous to have a scouring sponge having its scouring side occupied by the fluid reservoirs. When used manually, fluid is released from the reservoir due to the mechanical stress, so that, if the fluid is perfume, a pleasant odor is produced.
[0235] As was discussed previously, a fluid reservoir that contains at least one, preferably two or more substances typically contained in laundry detergents or cleaners is a preferred embodiment of the invention. Furthermore, a fluid reservoir according to the invention that contains a laundry detergent or cleaner is a highly preferred subject of the present invention. In the following, therefore, ingredients of laundry detergents or cleaning agents that can advantageously be contained in the fluid reservoir or which can be contained in a laundry detergent or cleaner that contains fluid reservoirs according to the invention are described in more detail.
[0236] These ingredients include builders. Builders include, in particular, zeolites, silicates, carbonates, organic cobuilders and, if there are no ecological prejudices against their use, also the phosphates.
[0237] The applicable finely crystalline synthetic zeolite that contains bound water is preferably Zeolite A and/or P. Zeolite MAP® (commercial product of the Crosfield company) is especially preferred as Zeolite P. However, Zeolite X is also usable, as are mixtures of A, X and/or P. A co-crystallizate of Zeolite X and Zeolite A (ca. 80% by weight Zeolite X) sold by CONDEA Augusta S. p. A as VEGOBOND AX® is commercially available and preferred for use in the context of the present invention. It can be described by the formula
[0000] nNa 2 O.(1-n)K 2 O.Al 2 O 3 .(2-2.5)SiO 2 .(3.5-5.5)H 2 O
[0000] The zeolite can also be as a powdering agent. Suitable zeolites have preferably have a mean particle size less than 10 μm (volume distribution; measuring method: Coulter Counter) and contain preferably 18 to 22% by weight, particularly 20 to 22% by weight bound water.
[0238] Suitable crystalline lamellar sodium silicates have the general formula NaMSi x O 2x+1 .H 2 O, in which means sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, and preferred values for x are 2, 3 or 4. Preferred crystalline lamellar silicates having the formula stated are those in which M stands for sodium and x takes on the value of 2 or 3. In particular, both β- and δ-sodium disilicate, Na 2 Si 2 O 5 .yH 2 O, are preferred.
[0239] Crystalline lamellar silicates having the general formula NaMSi x O 2x+1 .H 2 O, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, and y stands for a number from 0 to 33, can also be used particularly preferably. The crystalline lamellar silicates having the formula NaMSi x O 2x+1 .yH 2 O are, for example, sold by Clarian GmbH (Germany) under the trade name Na-SKS. Examples of these silicates include Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O (magadite), Na-SKS-3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O, makatite).
[0240] Crystalline lamellar silicates having the formula NaMSi x O 2x+1 .yH 2 O, in which x stands for 2, are also particularly suitable. The particularly suitable ones of these are Na-SKS-5 (α-Na 2 Si 2 O 5 ), Na-SKS-7 (β-Na 2 Si 2 O 5 , natrosilite), Na-SKS-9 (NaHSi 2 O 5 .H 2 O), Na-SKS-10 (NaHSi 2 O 5 .3H 2 O, kanemite), Na-SKS-11 (t-Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 (δ-Na 2 Si 2 O 5 ).
[0241] Amorphous sodium silicates having a Na 2 O:SiO 2 ratio of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and particularly 1:2 to 1:2.6 which have delayed dissolution and exhibit secondary washing properties are also usable. The delay of dissolution compared with the usual sodium silicates can be accomplished in various ways, such as by surface treatment, compounding, compacting/compressing or by overdrying. In the context of this invention the term “amorphous” is understood to include “X-ray amorphous”. This means that the silicates do not give sharp X-ray reflections in X-ray diffraction experiments, such as are typical of crystalline substances. Instead, they always exhibit one or more maxima of the scattered X-radiation indicating a range of several degrees for the angle of diffraction. However, if the silicate articles give diffuse or even sharp diffraction maxima in electron diffraction experiments, that can lead to very good or even particularly good builder characteristics. That can be interpreted to mean that the products have microcrystalline regions of the magnitude of 10 to a few hundred nm, with values up to a maximum of 50 nm and particularly up to a maximum of 20 nm preferred. Such so-called X-ray amorphous silicates likewise exhibit delayed dissolution in comparison with the usual water glasses. Compressed/compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
[0242] In the context of the present invention it can be preferable for this/these silicate(s), preferably alkali silicates, especially preferably crystalline or amorphous alkali disilicates, to be contained in laundry detergents or cleaners in proportions of 10 to 60% by weight, preferably 15 to 50% by weight, and especially 20 to 40% by weight, based in each case on the weight of the laundry detergent or cleaner.
[0243] Obviously it is also possible to use the generally known phosphates as builder substances, as long as it is not necessary to avoid such use for ecological reasons. That is particularly the case for use of agents according to the invention as washing agents for dishwashing machines. Among the multitude of commercially available phosphates, the alkali metal phosphates are the most important for the laundry detergent and cleaner industry, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).
[0244] Alkali metal phosphate is the summary designation for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish metaphosphoric acids, (HPO 3 ) n , and orthohosphoric acid, H 3 PO 4 , along with representatives of higher molecular weight. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposition on machine parts or lime incrustations in cloth, and also contribute to the cleaning power.
[0245] Examples of suitable phosphates are sodium dihydrogen phosphate, NaH 2 PO 4 , in the form of the dihydrate (density 1.91 g/cm 3 , melting point 60° C.) or in the form of the monohydrate (density 2.04 g/cm 3 ); disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , which can be used anhydrous or with 2 moles of H 2 O (density 2.066 g/cm 3 , water loss at 95° C.), 7 moles (density 1.68 g/cm 3 , melting point 48° C. with loss of 5 H 2 O) and 12 moles of water (density 1.52 g/cm 3 , melting point 35° C. with loss of 5 H 2 O), but particularly trisodium phosphate (tertiary sodium phosphate) Na 3 PO 4 , which can be used as the dodecahydrate, as the decahydrate (equivalent to 19-20% P 2 O 5 ) or in the anhydrous form (equivalent to 39-40% P 2 O 5 ).
[0246] Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is another preferred phosphate. Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 is also preferred. It exists in the anhydrous form (density 2.534 g/cm 3 , melting point 988°, also reported as 880°) and as the decahydrate (density 1.815-1.836 g/cm 3 , melting point 94° with loss of water). The corresponding potassium salt, potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 is also preferred.
[0247] The industrially important pentasodium triphosphate, Na 5 P 3 O 10 , is a non-hygroscopic colorless water-soluble salt that is anhydrous or crystallizes with 6 H 2 O. It has the general formula Na—[P(O)ONa)—O] n —Na with n=3. The corresponding potassium salt, pentapotassium triphosphate (K 5 P 3 O 10 ) (potassium tripolyphosphate) is commercially available as, for example, a 50% by weight solution (>23% P 2 O 5 , 25% K 2 O). The potassium polyphosphates are widely used in the detergent or cleaning agent industry. Sodium potassium tripolyphosphates also exist. They are likewise usable in the context of the present invention. They are produced, for example, if sodium trimetaphosphate is hydrolyzed with KOH:
[0000] (NaPO 3 ) 3 +2KOH→Na 3 K 2 P 3 O 10 +H 2 O
[0248] They can be used according to the invention exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of them. Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate, or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate, or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate are also usable according to the invention.
[0249] If phosphates are used as washing or cleaning active substances in laundry detergents or cleaners in the context of the present invention, the preferred agents contain this/these phosphate(s), preferably alkali metal phosphates, especially preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) in proportions of 5 to 80% by weight, preferably 15 to 75% by weight, and especially 20 to 70% by weight, based in each case on the weight of the laundry detergent or cleaner.
[0250] It is preferable to use potassium tripolyphosphate and sodium tripolyphosphate, in particular, in a weight ratio of more than 1:1, preferably more than 2:1, preferably more than 5:1, especially preferably more than 10:1 and particularly more than 20:1. It is particularly preferable to use potassium tripolyphosphate alone without admixtures of other phosphates.
[0251] Alkali carriers are other builders. Alkali carriers include, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, the alkali silicate and alkali metasilicates mentioned, and mixtures of those substances. In the context of the present invention it is preferred to use the alkali carbonates, especially sodium carbonate, sodium bicarbonate, or sodium sesquicarbonate. A builder system comprising a mixture of tripolyphosphate and sodium carbonate is particularly preferred. A builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is likewise particularly preferred.
[0252] The alkali metal hydroxides are used in low proportions if at all because of their poor chemical compatibility with the other ingredients of laundry detergents and cleaners, in comparison with other builders. They are preferably used in proportions of less than 10% by weight, preferably less than 6% by weight, especially preferably below 4% by weight, and particularly below 2% by weight, based in each case on the total weight of the laundry detergent or cleaner. Agents that contain less than 0.5%, based on their total weight, and especially no alkali metal hydroxides, are particularly preferred.
[0253] It can be especially preferable to use carbonate(s) and/or bicarbonate(s), preferably alkali carbonates, especially preferably sodium carbonate, in proportions of 2 to 50% by weight, preferably 5 to 40% by weight, and particularly 7.5 to 30% by weight, based in each case on the weight of the laundry detergent or cleaner. Agents that contain less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight, and particularly less than 9% by weight, based in each case on the weight of the cleaner, of carbonate(s) and/or bicarbonate(s), preferably alkali carbonate(s), especially preferably sodium carbonate, can be particularly preferred.
[0254] Polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates must be mentioned as organic cobuilders. These classes of materials are described in the following.
[0255] Examples of usable organic builders are the polycarboxylic acids, which can be used as their sodium salts. Here ‘polycarboxylic acids’ means those carboxylic acids that bear more than one acid function. Examples of those include citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, and nitrilotriacetic acid (NTA) as long as their use in not objectionable for ecologic reasons, and mixtures of them. Preferred salts are the salts of the polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, and mixtures of those.
[0256] The acids can also be used as such. The acids, aside from their builder action, typically also have the property of an acidifying component and so also serve to adjust a lower and milder pH of the laundry detergent or cleaner. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and arbitrary mixtures of them must be named.
[0257] Polymeric polycarboxylates are further suitable as builders. They include, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for instance, those with relative molecular weights of 500 to 70,000 g/mol.
[0258] The molecular weights stated for polymeric polycarboxylates are, in the sense of this document, weight-average molecular weights, M w , of the particular acid form. They are basically determined by means of gel permeation chromatography (GPC) using a UV detector. The measurement is made versus an external polyacrylic acid standard, which gives realistic molecular weights because of its structural relation with the polymers being examined. These figures clearly diverge from the molecular weight data found when polystyrenesulfonic acids are used as standards. The molecular weights measured with polystyrenesulfonic acids are generally distinctly higher than those reported in this document.
[0259] Polyacrylates preferably having molecular weights of 2,000 to 20,000 are especially suitable polymers. Again, the short-chain polyacrylates of this group, having molecular weights of 2,000 to 10,000 are preferred, and those with molecular weights of 3,000 to 5,000 are particularly preferred of this group because of their superior solubility.
[0260] Copolymeric polycarboxylates are further suitable, especially those that are copolymers of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. The copolymers of acrylic acid with maleic acid that contain 50 to 90% by weight acrylic acid and 50 to 10% by weight maleic acid have proven particularly suitable. Their relative molecular weights, based on the free acids, are generally 2,000 to 70,000 g/mol, preferably 20,000 to 50,000 g/mol, preferably 20,000 to 50,000 g/mol, and particularly 30,000 to 40,000 g/mol.
[0261] The (co)polymeric polycarboxylates can be used either as the powder or as the aqueous solution. Laundry detergents or cleaners contain preferably 0.5 to 20% by weight optionally (co)polymeric polycarboxylates, and especially 3 to 10% by weight.
[0262] The polymers can also contain allylsulfonic acids, such as allyloxybenzensulfonic acid and methallylsulfonic acid as monomers to improve the water solubility.
[0263] Biodegradable polymers made up of more than two different monomer units are particularly preferred, such as those that contain as monomers salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives, or which contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
[0264] Other preferred copolymers are those that contain as monomers preferably acrolein and acrylic acid/acrylic acid salts or acrolein and vinyl acetate.
[0265] Likewise, polymeric aminodicarboxylic acids, their salts, or their precursors must be mentioned as other preferred builder substances. Polyaspartic acids or their salts are especially preferred.
[0266] Polyacetals, which can be obtained by reaction of dialdehydes with polyol carboxylic acids having 5 to 7 C atoms and at least 3 hydroxyl groups are other suitable builder substances. Preferred polyacetals are obtained from dialdehydes such as glyoxylate, glutaraldehyde and terephthaldehyde or mixtures of them and from polyol carboxylic acids such as gluconic acid and/or gluconoheptanoic acid.
[0267] Dextrins, such as oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches, are other suitable organic builder substances. The hydrolysis can be done by the usual processes, such as acid-catalyzed or enzyme-catalyzed processes. They are preferably hydrolysis products with mean molecular weights in the range of 400 to 500,000 g/mol. A polysaccharide having a dextrose equivalent (DE) in the range of 0.5 to 40, and especially 2 to 30, is preferred. DE is a useful measure of the reducing action of a polysaccharide in comparison with dextrose, which has a DE of 100.
[0268] Both maltodextrins with a DE between 3 and 20; and dry glucose syrups with DEs between 20 and 37 are usable, as are the so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2,000 to 30,000 g/mol.
[0269] The oxidized derivatives of such dextrins are products of their reaction with oxidizing agents which are able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function.
[0270] Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate are other suitable cobuilders. It is preferable to use ethylenediamine-N,N′-disuccinate (EDDS) in the form of its sodium or magnesium salt. Glycerol disuccinate and glycerol trisuccinate are also preferred in this respect. Suitable proportions for use in formulations containing zeolite and/or silicate can, for example, be 3 to 15% by weight.
[0271] Examples of other usable organic cobuilders are acetylated hydroxycarboxylic acids or their salts, which can optionally be in the lactone form and which have at least 4 carbon atoms and at least one hydroxyl group as well as not more than two acid groups.
[0272] Furthermore, all the compounds that can form complexes with alkaline earth cations can be used as builders.
[0273] The group of surfactants includes the nonionic, anionic, cationic and amphoteric surfactants.
[0274] All the nonionic surfactants known to those skilled in the art can be used as the nonionic surfactants. Low-foaming nonionic surfactants can be used as preferred nonionic surfactants, for instance. It is particularly preferable for the laundry detergent or cleaner to contain nonionic surfactants from the group of alkoxylated alcohols. It is preferable to use as nonionic surfactants alkoxylated, advantageously ethoxylated, particularly primary alcohols having preferably 8 to 18 C atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol. The alcohol group can be linear or, preferably, methyl-branched in the 2 position, or it can contain a mixture of linear and methyl-branched groups, such as those that commonly occur in oxoalcohol groups. In particular, though, alcohol ethoxylates having linear groups of alcohols of natural origin having 12 to 18 C atoms, such as those from coco, palm, tallow, or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9-11 alcohols having 7 EO, C 13-15 alcohols having 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols having 3 EO, 5 EO or 7 EO, and mixtures of those, such as mixtures of C 12-14 alcohols with 3 EO and C 12-18 alcohol with 5 EO. The degrees of ethoxylation stated are statistical averages, which can be an integer or fraction for a particular product. Preferred alcohol ethoxylates exhibit a narrowed homolog distribution (narrow-range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols having more than 12 EO can also be used. Examples of those are tallow alcohols having 14 EO, 25 EO, 30 EO or 40 EO.
[0275] One can also use alkyl glycosides of the general formula RO(G) x , in which R is a primary straight-chain or methyl-branched aliphatic group, especially one methyl-branched in the 2 position, having 8 to 22, preferably 12 to 18 C atoms, and G is the symbol for a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization, x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10. It is preferable for x to be 1.2 to 1.4.
[0276] Another class of preferably usable nonionic surfactants that can be used either as the only nonionic surfactant or in combination with other nonionic surfactants, is that of the alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to4 carbon atoms in the alky chains.
[0277] Nonionic surfactants of the amine oxide type, such as N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide; and the fatty acid alkanolamides, can also be suitable. The proportion of these nonionic surfactants preferably does not exceed that of the ethoxylated fatty alcohols, and is particularly not more than half of that.
[0278] Polyhydroxyfatty acid amides having the formula
[0000]
[0279] in which R stands for an aliphatic acyl group having 6 to 22 carbon atoms, R 1 stands for hydrogen, or an alkyl or hydroxyalkyl group with 1 to 4 carbon atoms, and [Z] stands for a linear or branched polyhydroxyalkyl group with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups are also preferred surfactants. The poyhydroxyfatty acid amides are known substances that can normally be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine, then subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
[0280] The group of polyhydroxyfatty acid amides also includes compounds of the formula
[0000]
[0000] in which the R stands for a linear or branched alkyl or alkenyl group having 7 to 12 carbon atoms, R 1 stands for a linear, branched or cyclic alkyl group or an aryl group having 2 to 18 carbon atoms and R 2 stands for a linear, branched or cyclic alkyl group or an aryl group or an oxyalkyl group having 1 to 8 carbon atoms, with C 14 -alkyl or phenyl groups preferred, and [Z] stands for a linear polyhydroxyalkyl group, the alkyl chain of which is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of these groups.
[0281] [Z] is preferably obtained by reductive amination of a reducing sugar, such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can, for example, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as the catalyst.
[0282] Surfactants containing one or more tallow alcohols having 20 to 30 EO in combination with a silicone antifoam can be used with particular preference.
[0283] Nonionic surfactants of the group of the alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and especially from the group of EO-AO-0EO nonionic surfactants are likewise used with special preference.
[0284] Nonionic surfactants having melting points above room temperature are particularly preferred. Nonionic surfactant(s) having (a) melting point(s) above 20° C., preferably above 25° C., especially preferably between 25 and 60° C., and particularly between 26.6 and 43.3° C. is/are particularly preferred.
[0285] Low-foaming nonionic surfactants that can be solid or highly viscous at room temperature, having softening or melting points in the stated temperature range, are suitable nonionic surfactants. If nonionic surfactants that are highly viscous at room temperature are used, it is preferable for them to have a viscosity above 20 Pa·s, preferably above 35 Pa·s, and particularly above 40 Pa·s. Surfactants having a waxy consistency at room temperature are also preferred.
[0286] Surfactants used preferably, that are solid are room temperature, are derived from the groups of alkoxylated nonionic surfactants, especially the ethoxylated primary alcohols and mixtures of these surfactants having more complex structure, such as polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) nonionic surfactants). Such ((PO/EO/PO) nonionic surfactants are further distinguished by good foam control.
[0287] In a preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant obtained from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 C atoms with preferably at least 12 moles, especially preferably at least 15 moles, and particularly at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol.
[0288] A particularly preferred nonionic surfactant that is solid at room temperature is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol, and at least 12 moles, preferably at least 15 moles, and especially at least 20 moles of ethylene oxide. Of these, the so-called “narrow range ethoxylates” (see above) are especially preferred.
[0289] Ethoxylated nonionic surfactants obtained from C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 18-20 fatty alcohols and more than 12 moles, preferably more than 15 moles, and especially more than 20 moles of ethylene oxide per mole of alcohol are used with special preference.
[0290] It is preferable for the nonionic surfactant that is solid at room temperature also to have propylene oxide units in the molecule. Preferably such PO units make up as much as 25% by weight, especially preferably up to 20% by weight, and particularly up to 15% by weight of the total molecular weight of the nonionic surfactant. Especially preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols that also have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol portion of such nonionic surfactant molecules preferably amounts to more than 30% by weight, especially preferably more than 50% by weight, and particularly more than 70% by weight of the total molecular weights of such nonionic surfactants. Preferred agents are distinguished by containing ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule amount to as much as 25% by weight, preferably 20% by weight, and particularly 15% by weight of the total molecular weight of the nonionic surfactant:
[0291] Other nonionic surfactants that can be used with particular preference, having melting points above room temperature, contain 40 to 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend that contains 75% by weight of an inverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide, and 25% % by weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
[0292] Nonionic surfactants that can be used with special preference are, for example, obtainable from Olin Chemicals under the name Poly Tergent® SLF-18.
[0293] Surfactants having the formula
[0000] R 1 O[CH 2 CH(CH 3 )O] x [CH 2 CH 2 O] y CH 2 CH(OH)R 2 ,
[0000] in which R 1 stands for a linear or branched aliphatic hydrocarbon group having 4 to 18 carbon atoms, or mixtures of them, R 2 stands for a linear or branched hydrocarbon group having 2 to 26 carbon atoms, or mixtures of them, and x stands for values between 0.5 and 1.5, and y stands for a value of at least 15, are other specially preferred nonionic surfactants.
[0294] Other nonionic surfactants that can be used preferably are the end-group-capped poly(oxyalkylated) nonionic surfactants having the formula
[0000] R 1 O[CH 2 CH(R 3 )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2 ,
[0000] in which R 1 and R 2 stand for linear or branched, saturated or unsaturated aliphatic or aromatic hydrocarbon groups with 1 to 30 carbon atoms, R 3 stands for H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, or 2-methyl-2-butyl group, x stands for values between 1 and 30, and k and j stand for values between 1 and 12, preferably between 1 and 5. If x≧2, each R 3 on the preceding formula
[0000] R 1 O[CH 2 CH(R 3 )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2 ,
[0000] can be different. R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups having 6 to 22 carbon atoms, with groups having 8 to 18 C atoms being especially preferred. H, —CH 3 or —CH 2 CH 3 are especially preferred for the group R 3 . Especially preferred values of x are in the range of 1 to 20, preferably 6 to 15.
[0295] As described above, each R 3 in the preceding formula can be different if x≧2. In this way, the alkylene oxide unit in the square brackets can be varied. For example, if x stands for 3, the group R 3 can be selected to make up ethylene oxide (R 3 ═H) or propylene oxide (R 3 ═—CH 3 ) units. They can follow each other in any sequence, such as (EO )(PO )(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO )(PO), (PO)(PO)(EO) and (PO)(PO)(PO). Here the value of x was selected to be 3, and can be larger, with the the range of variation increasing with rising x values and, for example, a large number of (EO) groups combined with a small number of (PO) groups, or conversely.
[0296] Particularly preferred end-group-capped poly(oxyalkylated) alcohols of the preceding formula have values of k=1 and j=1, so that the preceding formula simplifies to
[0000] R 1 O[CH 2 CH(R 3 )O] x CH 2 CH(OH)CH 2 OR 2
[0000] In the latter formula, R 1 , R 2 , and R 3 are defined as above, and x stands for numbers from 1 to 30, preferably from 1 to 20 and particularly from 6 to 18. Surfactants in which the groups R 1 and R 2 have 9 to 14 C atoms, R 3 stands for H and x has values of 6 to 15 are particularly referred.
[0297] If one combines the latter statements, end-group-capped poly(oxyalkylated) nonionic surfactants having the formula
[0000] R 1 O[CH 2 CH(R 3 )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2 ,
[0000] in which R 1 and R 2 stand for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups having 1 to 30 carbon atoms, R 3 stands for H or for a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, or 2-methyl-2-butyl group, x stands for values between 1 and 30, and k and j stand for values between 1 and 12, preferably between 1 and 5 are preferred. Surfactants of the type
[0000] R 1 O[CH 2 CH(R 3 )O] x CH 2 CH(OH)CH 2 OR 2 ,
[0000] in which x stands for numbers from 1 to 30, preferably from 1 to 20 and particularly from 6 to 18, are particularly preferred.
[0298] Low-foaming nonionic surfactants having alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred in the context of the present invention. Of these, again, surfactants with EO-AO-EO-AO blocks are preferred, with one to ten EO or AO groups in each block being joined together before a block from the other group follows. Here, nonionic surfactants having the general formula
[0000]
[0000] are preferred, with R 1 standing for a straight or branched, saturated or singly or multiply unsaturated C 6-24 alkyl or alkenyl group; each group R 2 or R 3 , independently of each other, is selected from —CH 3 , —CH 2 —CH 3 , —CH 2 CH 2 —CH 3 , CH(CH 3 ) 2 , and the indices w, x, y and z, independently of each other, stand for integers from 1 to 6.
[0299] The preferred nonionic surfactants having the formula above can be produced from the corresponding alcohols, R 1 —OH and ethylene oxide or alkylene oxide. The group R 1 in the formula above can vary, depending on the source of the alcohol. If natural sources are used, the group R 1 has an even number of carbon atoms and is generally unbranched. The linear groups from alcohols of natural origin with 12 to 18 C atoms, such as from coconut, palm, tallow, or oleyl alcohol, are preferred. Examples of alcohols accessible from synthetic sources are the Guerbet alcohols or groups methyl-branched at the 2 position, or mixtures of linear and methyl-branched groups, such as usually occur in oxoalcohol groups. Independently of the manner of production of the alcohols used in the nonionic surfactants optionally contained in the agents, those nonionic surfactants are preferred in which R 1 in the formula above stands for an alkyl group having 6 to 24, preferably 8 to 20, especially preferably 9 to 15 and particularly 9 to 11 carbon atoms.
[0300] Butylene oxide, along with propylene oxide, is an alkylene oxide unit that can be contained in the preferred nonionic surfactants as an alternate to the ethylene oxide unit. However, even other alkylene oxides, in which R 2 or R 3 , independently of each other, are selected from —CH 2 CH 2 CH 3 or —CH(CH 3 ) 2 are suitable. Preferred nonionic surfactants are those of the formula above in which R 2 or R 3 stands for a group —CH 3 , w and x, independently of each other, stand for values of 3 or 4, and y and z, independently of each other; stand for values of 1 or 2.
[0301] In summary, those nonionic surfactants are particularly preferred that have a C 9-15 -alkyl group with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units. Those surfactants have the required low viscosity in aqueous solution and can be used with special preference according to the invention.
[0302] Other preferred nonionic surfactants are the end-group-capped poly(oxyalkylated) nonionic surfactants having the formula
[0000] R 1 O[CH 2 CH(R 3 )O] x CH 2 ,
[0000] in which R 1 stands for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups with 1 to 30 carbon atoms, R 2 stands for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups with 1 to 30 carbon atoms, preferably having between 1 and 5 hydroxyl groups and preferably further functionalized with an ether group, R 3 stands for H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl or 2-methyl-2-butyl group, and x stands for values between 1 and 40.
[0303] In a particularly preferred embodiment of the present application, R 3 in the general formula above stands for H. Of the resulting group of end-group-capped poly(oxyalkylated) nonionic surfactants of the formula
[0000] R 1 O[CH 2 CH 2 O] x R 2
[0000] those nonionic surfactants are particularly preferred in which R 1 stands for a linear or branched, saturated or unsaturated, aliphatic or aromatic having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms; R 2 stands for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups having 1 to 30-carbon atoms, preferably having between 1 and 5 hydroxyl groups, and x stands for values between 1 and 40.
[0304] In particular, those end-group-capped poly(oxyalkylated) nonionic surfactants are preferred that, according to the formula
[0000] R 1 O[CH 2 CH 2 O] x CH 2 CH(OH)R 2
[0000] have, aside from a group R 1 , which stands for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups with 1 to 30 carbon atoms, preferably with 4 to 20 carbon atoms, also have a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon group R 2 with 1 to 30 carbon atoms, which is adjacent to a monohydroxylated intermediate group —CH 2 CH(OH)—. In this formula, x stands for values between 1 and 90.
[0305] Nonionic surfactants having the general formula
[0000] R 1 O[CH 2 CH 2 O] x CH 2 CH(OH)R 2 ,
[0000] are especially preferred, in which there is, aside from a group R 1 , which stands for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups with 1 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, also a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon group R 2 with 1 to 30 carbon atoms, preferably 2 to 22 carbon atoms, which is adjacent to a monohydroxylated intermediate group —CH 2 CH(OH)— and in which x stands for values between 40 and 80, preferably for values between 40 and 60.
[0306] The corresponding end-group-capped poly(oxyalkylated) nonionic surfactants having the formula above can be obtained, for instance, by reacting a terminal epoxide having the formula R 2 CH(O)CH 2 with an ethoxylated alcohol having the formula R 1 O[CH 2 CH 2 O]— x-1 CH 2 CH 2 OH.
[0307] Especially preferred are those end-group-capped poly(oxyalkylated) nonionic surfactants having the formula
[0000] R 1 O[CH 2 CH 2 O] x [CH 2 CH(CH 3 )O] y CH 2 CH(OH)R 2 ,
[0000] in which R 1 and R 2 , independently of each other, stand for a linear or branched, saturated or singly or multiply unsaturated, hydrocarbon group having 2 to 26 carbon atoms, R 3 , independently of each other, is selected from —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 —CH 3 , or —CH(CH 3 ) 2 , but with —CH 3 preferred, and x and y, independently of each other, stand for values between 1 and 32, with nonionic surfactants in which the values of x are from 15 to 32 and the values of y are 0.5 and 1.5 quite particularly preferred.
[0308] Surfactants having the general formula
[0000]
[0000] in which R 1 and R 2 , independently of each other, stand for a linear or branched, saturated or multiply unsaturated, hydrocarbon group having 2 to 26 carbon atoms, R 3 , independently of each other, is selected from —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 —CH 3 , or CH(CH 3 ) 2 , but with —CH 3 preferred, and x and y independently of each other stand for values between 1 and 32, with nonionic surfactants having values of x of 15 to 32 and of y of 0.5 and 1.5 are quite particularly preferred.
[0309] The carbon chain lengths stated, as well as the degrees of ethoxylation or alkoxylation for the preceding nonionic surfactants are statistical averages, which can be integers or fractions for a particular product. Because of the production process, commercial products of the formulas stated generally are not made up of individual representatives, but of mixtures, so that there can be fractional numbers for both the carbon chain lengths and for the degrees of ethoxylation or alkoxylation.
[0310] Obviously, the nonionic surfactants named above can be used not only as individual substances but also as surfactant mixtures of two, three, four or more surfactants. Surfactant mixtures are not considered mixtures of nonionic surfactants which in their totality fall in one of the general formulas given above, but rather mixtures containing two, three, four or more nonionic surfactants that can be described by different ones of the general formulas presented above.
[0311] As anionic surfactants, those of the sulfonate and sulfate type are used. The preferred surfactants of the sulfonate type are C 9-13 -alkylbenzene-sulfonates, olefin sulfonates, i. e., mixtures of alkene and hydroxyalkane sulfonates, and disulfonates, such as are obtained, for example, from C 12-18 -monoolefins with terminal or internal double bonding by sulfonation with gaseous sulfur trioxide and subsequent acidic or alkaline hydrolysis of the sulfonation products. Alkane sulfonates, obtained from C 12-18 -alkanes, for instance, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, are also suitable. Esters of α-sulfofatty acids (ester sulfonates), such as the α-sulfonated methyl esters of hydrogenated coco, palm kernel or tallow fatty acids, are also suitable.
[0312] Sulfonated fatty acid glycerol esters are other suitable anionic surfactants. Fatty acid glycerol esters are understood to be the mono, di and tri-esters, and mixtures of them, such as are obtained on production by esterification of a monoglycerol with 1 to 3 moles of fatty acid, or transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfonated fatty acid glycerol esters are sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, such as caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
[0313] Preferred alk(en)yl sulfates are the alkali, and especially the sodium salts of the sulfuric acid hemiesters of the C 12 -C 18 fatty alcohols, for example, of coco fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or of the C 10 -C 20 oxoalcohols and the hemiesters of secondary alcohols having those chain lengths. Alk(en)yl sulfates of the specified chain lengths which comprise a synthetically produced straight chain petrochemically based alkyl group, which have degradative behavior similar to the adequate compounds based on fatty chemical raw materials are also preferred. The C 12 -C 16 -alkyl sulfates, C 12 -C 15 -alkyl sulfates, and C 14 -C 15 -alkyl sulfates are preferred from the viewpoint of detergent technology. 2,3-alkyl sulfates, which can be obtained from Shell Oil Company under the DAN® name are also suitable anionic surfactants.
[0314] The sulfuric acid hemiesters of straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide are also suitable, such as 2-methyl branched C 9-11 -alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12-18 fatty alcohols with 1 to 4 EO.
[0315] The salts of the alkyl sulfosuccinic acids are other suitable anionic surfactants. They are also called sulfosuccinates or sulfosuccinic acid esters, and are hemiesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and particularly ethoxylated fatty alcohols. Preferred sulfosuccinates comprise C 8-18 fatty alcohol groups or mixtures of them. Particularly preferred sulfosuccinates comprise a fatty alcohol group derived from ethoxylated fatty alcohols which are themselves considered nonionic surfactants. Again, sulfosuccinates, the fatty alcohol groups of which are derived from ethoxylated fatty alcohols with limited homolog distribution are particularly preferred. Likewise, it is also possible to use alk(en)ylsuccinic acids with preferably 8 to 18 carbon atoms, or their salts, in the alk(en)yl chain.
[0316] Soaps, in particular, can be considered as other anionic surfactants. Soaps of saturated fatty acids, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, as well as soap mixtures derived particularly from natural fatty acids, such as coco, palm kernel or tallow fatty acids, are suitable.
[0317] The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts, as well as soluble salts of organic bases such as mono-, di- or tri-ethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, and particularly the sodium salts.
[0318] The proportion of anionic surfactant in laundry detergents or cleaners can, for example, be in the range of 1-60% by weight, advantageously 5-40% by weight, and particularly 10-30% by weight.
[0319] Cationic surfactants and/or amphoteric surfactants can also be used in place of the specified surfactants or in combination with them.
[0320] Cationic compounds of the following formulas, for example, can be used as cationically active substances:
[0000]
[0000] in which each R 1 group is selected, independently of each other, from C 1-6 -alkyl, alkenyl or hydroxyalkyl groups; each R 2 group is selected, independently of each other, from C 8-28 -alkyl or alkenyl groups; R 3 ═R 1 or (CH 2 ) n T-R 2 ; R 4 ═R 1 or R 2 or (CH 2 ) n -T-R 2 ; T=—CH 2 —, —O—CO— or —CO—O—, and n is an integer from 0 to 5.
[0321] The proportion of cationic and/or amphoteric surfactants can preferably be less than 10% by weight, preferably less than 5% by weight, quite particularly preferably less than 2% by weight and particularly less than 1% by weight. It can also be preferable that no cationic or amphoteric surfactants are contained.
[0322] The group of polymers includes in particular the polymers with laundry detergent or cleaning action, such as the polymers that act as water softeners. In general, cationic, anionic and amphoteric polymers are usable along with nonionic polymers in laundry detergents or cleaners.
[0323] “Cationic polymers” in the sense of the present invention are polymers bearing a positive charge in the polymer molecule. That can be accomplished, for example, by (alkyl)-ammonium groups or other positively charged groups in the polymer chain. Particularly preferred cationic polymers are derived from the groups of quaternized cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts, and their copolymers with esters and amides of acrylic acid and methacrylic acid, copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino-acrylate and —methacrylate, vinylpyrrolidone-methylimidazolinium chloride copolymers, quaternized polyvinyl alcohols or the polymers with INCI names Polyquaternium 2, Polyquaternium 7, Polyquaternium 18 and Polyquaternium 27.
[0324] “Amphoteric polymers” in the sense of the present invention have also negatively charged groups or monomer units in the polymer chain, along with a positively charged group. These groups can, for example, be carboxylic acids, sulfonic acids, or phosphoric acids.
[0325] Preferred laundry detergents or cleaning agents are characterized by comprising a polymer having monomer units with the formula R 1 R 2 C═CR 3 R 4 , in which each group R 1 , R 2 , R 3 , R 4 , is selected, independently of each other, from hydrogen, derivatized hydroxyl group, C 1-30 linear or branched alkyl groups, aryl, aryl-substituted C 1-30 linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group having a positive charge in the pH sub-range of 2 to 11, or salts of them, provided that at least one group R 1 , R 2 , R 3 , R 4 is a heteroatomic organic group having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group with a positive charge.
[0326] In the context of the present invention, specially preferred cationic or amphoteric polymers contain as the monomer unit a compound having the general formula
[0000]
[0000] in which R 1 and R 4 independently of each other stand for H or for a linear or branched hydrocarbon group having 1 to 6 carbon atoms; R 2 and R 3 , independently of each other, stand for an alkyl, hydroxylalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has between 1 and 6 carbon atoms, and which is preferably a methyl group; x and y, independently of each other, stand for integers between 1 and 3. X − represents a counterion, preferably a counterion from the group of chloride, bromide, iodide, sulfate, bisulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate(tosylate), cumenesulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures of them.
[0327] Preferred R 1 and R 4 groups in the formula above are selected from —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH(CH 3 )—CH 3 , —CH 2 OH, —CH 2 CH 2 OH, —CH(OH)—CH 3 , CH 2 —CH 2 —CH 2 —OH, —CH 2 —CH(OH)—CH 3 , —CH(OH)—CH 2 —CH 3 and —CH 2 —CH 2 —O) n H.
[0328] Polymers having a cationic monomer unit of the general formula above in which R 1 and R 4 stand for H, R 2 and R 3 stand for methyl, and x and y are each 1 are quite specially preferred. The corresponding monomer unit having the formula
[0000]
[0000] is also known as DADMAC (diallyldimethylammonium chloride) if X=chloride.
[0329] Other specially preferred cationic or amphoteric polymers comprise a monomer unit having the general formula
[0000]
[0000] in which the R 1 , R 2 , R 3 , R 4 , and R 5 , independently of each other, stand for a linear or branched saturated or unsaturated alkyl or hydroxyalkyl group having 1 to 6 carbon atoms, preferably for a linear or branched alkyl group selected from —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH(CH 3 )—CH 3 , —CH 2 OH, —CH 2 CH 2 OH, —CH(OH)—CH 3 , —CH 2 —CH 2 —CH 2 —OH, —CH 2 —CH(OH)—CH 3 , —CH(OH)—CH 2 —CH 3 and —(CH 2 —CH 2 —O) n H and x stands for an integer between 1 and 6.
[0330] In the context of the present invention, those polymers having a cationic monomer unit of the general formula above in which R 1 stands for H and R 2 , R 3 , R 4 , and R 5 stand for methyl, and x stands for 3, are quite specially preferred. The corresponding monomer units having the formula
[0000]
[0000] are also called MAPTAC (methylacrylamidopropyl-trimethylammonium chloride) if X − =chloride.
[0331] Polymers that comprise as monomer units diallyldimethylammonium salts and/or acrylamidopropyltrimethylammonium salts are preferred according to the invention.
[0332] The amphoteric polymers mentioned previously have not only cationic groups but also anionic groups or monomer units. Such anionic monomer units are derived, for instance, from the group of linear or branched saturated or unsaturated carboxylates, the linear or branched, saturated or unsaturated phosphonates, the linear or branched, saturated or unsaturated sulfates, or the linear or branched, saturated or unsaturated sulfonates. Preferred monomer units are acrylic acid, (meth)acrylic acid, dimethylacrylic acid, ethylacrylic acid, cyanoacrylic acid, vinylacetic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, the allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acids or the allylphosphonic acids.
[0333] Preferred usable amphoteric polymers are derived from the groups of the alkylacrylamide/acrylic acid copolymers, the alkylacrylamide/methacrylic acid copolymers, the alkylacrylamide/methylmethacrylic acid copolymers, the alkylacrylamide/acrylic acid/alkyl-aminoalkyl(meth)acrylic acid copolymers, the alkylacrylamide/methacrylic acid/alkylamino(meth)acrylic acid copolymers, the alkylacrylamide/methylmethacrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, the acrylamide/alkylmethacrylate/alkylaminoethylmethacrylate/alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic polymers.
[0334] Preferred usable zwitterionic polymers are derived from the group of acrylamidoalkyltrialkylammonium chloride/acrylic acid copolymers and their alkali and ammonium salts, the acrylamidoalkyltrialkylammonium chloride/methacrylic acid copolymers and their alkali and ammonium salts, and the methacryloylethylbetaine/methacrylate copolymers.
[0335] Further preferred are amphoteric polymers that comprise, along with one or more anionic monomers, methacrylamido-trialkylammonium chloride and dimethyl(diallyl)ammonium chloride as cationic monomers.
[0336] Specially preferred amphoteric polymers are derived from the group of methacrylamido-alkyl-trialkylammonium chloride/dimethyl(diallyl)ammonium chloride/acrylic acid copolymers, the methacrylamidoalkyltrialkylammonium chloride/dimethyl(diallyl)ammonium chloride/methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride/dimethyl(diallyl)ammonium chloride/alkyl(meth)acrylic acid copolymers and their alkali and ammonium salts.
[0337] Amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride/dimethyl(diallyl)ammonium chloride/acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride/dimethyl(diallyl)ammoniurn chloride/acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride/dimethyl(diallyl)ammonium chloride/alkyl(meth)acrylic acid copolymers and their alkali and ammonium salts are especially preferred.
[0338] Laundry detergents or cleaners can comprise the previously named cationic and/or amphoteric polymers preferably in proportions between 0.01 and 10% by weight, based in each case on the total weight of the laundry detergent or cleaning agent. However, in the context of the present invention, those detergents or cleaning agents are preferred in which the proportion of cationic and/or amphoteric polymers is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4% by weight, especially preferably between 0.01 and 2% by weight, and particularly between 0.01 and 1% by weight, based in each case on the total weight of the machine dish-washing agent. Preferred agents can also be entirely free of cationic and/or amphoteric polymers.
[0339] Polymers that act as water softeners are, for example, the polymers that contain sulfonic acid groups. They can be used with special preference.
[0340] Copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are specially preferred as polymers containing sulfonic acid groups.
[0341] In the context of the present invention, unsaturated carboxylic acids of the formula
[0000] R 1 (R 2 )C═C(R 3 )COOH
[0000] are preferred, in which R 1 to R 3 are, independently of each other, a straight-chain or branched saturated alkyl group with 2 to 12 carbon atoms, a straight-chain or branched, singly or multiply unsaturated alkenyl group with 2 to 12 carbon atoms, an —NH 2 , —OH, or —COOH substituted alkyl or alkenyl group or or COOR 4 in which R 4 is a saturated or unsaturated, linear or branched hydrocarbon group with 1 to 12 carbon atoms.
[0342] Of the unsaturated carboxylic acids that can be described by the preceding formula, acrylic acid (R 1 ═R 2 ═R 3 ═H), methacrylic acid (R 1 ═R 2 ═H; R 3 ═CH 3 ) and/or maleic acid (R 1 ═COOH; R 2 ═R 3 ═H) are preferred.
[0343] Among the monomers containing sulfonic acid groups, those are preferred that have the formula
[0000] R 5 (R 6 )C═C(R 7 )—X—SO 3 H
[0000] in which R 5 to R 7 , independently of each other, stand for —H, —CH 3 , a straight-chain or branched saturated alkyl group with 2 to 12 carbon atoms, a straight-chain or branched, singly or multiply unsaturated alkenyl group with 2 to 12 carbon atoms, an —NH 2 , —OH, or —COOH substituted alkyl or alkenyl group or or COOR 4 in which R 4 is a saturated or unsaturated, linear or branched hydrocarbon group with 1 to 12 carbon atoms and X stands for an optionally present spacer group selected from —CH 2 ) n — with n=0 to 4, —COO—(CH 2 ) k — with k=1 to 6, —C(O)—NH—C(CH 3 ) 2 and —C(O)—NH—CH(CH 2 CH 3 )—.
[0344] Of these monomers, the preferred ones are those having the formulas
[0000] H 2 C═CH—X—SO 3 H
[0000] H 2 C═C(CH 3 )—X—SO 3 H
[0000] HO 3 S—X—(R 6 )C═C(R 7 )—X—SO 3 H
[0000] in which R 6 and R 7 independently of each other are selected from —H, —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 —CH 3 , or —CH(CH 3 ) 2 , and X stands for an optionally present spacer group selected from —(CH 2 ) n — with n=0 to 4, —COO—(CH 2 ) k — with k=1 to 6, —C(O)—NH—C(CH 3 ) 2 and —C(O)—NH—CH(CH 2 CH 3 )—.
[0345] Particularly preferred monomers comprising sulfonic acid groups include 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)-propane-sulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethyl methacrylamide and water-soluble salts of the acids named.
[0346] Other ionic or nonionic monomers that can be considered include in particular ethylenically unsaturated compounds. The proportion of these other ionic or nonionic monomers in the polymers used is preferably less than 20% by weight, based on the polymer. Polymers to be used especially preferably consist solely of monomers of the formula R 1 (R 2 )C═C(R 3 )COOH and monomers of the formula R 5 (R 6 )═C(R 7 )—X—SO 3 H.
[0347] In summary, copolymers of
i) unsaturated carboxylic acids having the formula R 1 (R 2 )C═C(R 3 )COOH, in which the R 1 to R 3 independently of each other stand for —H, —CH 3 , a straight or branched saturated alkyl group with 2 to 12 carbon atoms, a straight or branched, singly or multiply unsaturated alkenyl group with 2 to 12 carbon atoms, or an —NH 2 , —OH, or —COOH substituted alkyl or alkenyl group as described above or or COOR 4 in which R 4 is a saturated or unsaturated, linear or branched hydrocarbon group with 1 to 12 carbon atoms, ii) monomers comprising sulfonic acid groups, having the formula
[0000] R 5 (R 6 )C═C(R 7 )—X—SO 3 H
in which the R 5 to R 7 independently of each other stand for —H, —CH 3 , a straight or branched saturated alkyl group having 2 to 12 carbon atoms, a straight or branched, singly or multiply unsaturated alkenyl group having 2 to 12 carbon atoms, an —NH 2 , —OH, or —COON substituted alkyl or alkenyl group as defined above or or COOR 4 in which R 4 is a saturated or unsaturated, linear or branched hydrocarbon group with 1 to 12 carbon atoms and X stands for an optionally present spacer group selected from —(CH 2 ) n — with n=0 to 4, —COO—(CH 2 ) k — with k=1 to 6, —C(O)—NH—C(CH 3 ) 2 — and —C(O)—NH—CH(CH 2 CH 3 )— iii) and optionally other ionic or nonionic monomers are particularly preferred.
[0352] Other specially preferred copolymers comprise
i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid, and maleic acid, ii) one or more monomers containing sulfonic acid groups, having the formulas
[0000] H 2 C—CH—X—SO 3 H
[0000] H 2 C═C(CH 3 )—X—SO 3 H
[0000] HO 3 S—X—(R 6 )C═C(R 7 )—X—SO 3 H
in which R 6 and R 7 , independently of each other, are selected from —H, —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 CH 3 , and —CH(CH 3 ) 2 , and X stands for an optionally present spacer group selected from—(CH 2 ) n — with n=0 to 4, —COO—(CH 2 ) k — with k=1 to 6, —C(O)—NH—C(CH 3 ) 2 — and C(O)—NH—CH(CH 2 CH 3 )— iii) optionally other ionic or nonionic monomers.
[0357] The copolymers can comprise the monomers of groups i) and ii), and optionally iii), in varying proportions. All the representatives of group i) can be combined with all the representatives of group ii) and with all the representatives of group iii). Especially preferred polymers have certain structural units that will be described in the following.
[0358] For instance, copolymers comprising structural units of the formula
[0000] —[CH 2 —CHCOOH] m —[CH 2 —CHC(O)—Y—SO 3 H] p —
[0000] are preferred, in which m and p each stand for a real integer between 1 and 2000, and Y stands for a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon groups with 1 to 24 carbon atoms, with the preferred spacer groups being those in which Y stands for —O—(CH 2 ) n — with n=0 to 4, for —O—(C 6 H 4 )—, for —NH—C(CH 3 ) 2 —, or —NH—CH(CH 2 CH 3 )—.
[0359] These polymers are made by copolymerization of acrylic acid with an acrylic acid derivative comprising sulfonic acid groups. If one copolymerizes that sulfonic acid-comprising acrylic acid derivative with methacrylic acid, one gets a different polymer, the use of which is also preferred. The corresponding copolymers comprise structural units having the formula
[0000] —[CH 2 —C(CH 3 )COOH] m —[CH 2 —CHC(O)—Y—SO 3 H] p —
[0000] in which m and p each stand for a real integer between 1 and 2000 and Y stands for a spacer group that is selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon groups with 1 to 24 carbon atoms, with the preferred spacer groups being those in which Y stands for —O—(CH 2 ) n — with n=0 to 4, for —O—(C 6 H 4 )—, for —NH—C(CH 3 ) 2 —, or —NH—CH(CH 2 CH 3 )—.
[0360] Entirely analogously, acrylic acid and/or methacrylic acid can also be copolymerized with methacrylic acid derivatives that contain sulfonic acid groups, thus changing the structural units in the molecule. Thus one can get specially preferred copolymers having structural units of the formula
[0000] —[CH 2 —CHCOOH] m —[CH 2 —C(CH 3 )C(O)—Y—SO 3 H] p —
[0000] in which m and p each stand for a real integer between 1 and 2000 and Y stands for a spacer group that is selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon groups with 1 to 24 carbon atoms, with the preferred spacer groups being those in which Y stands for —O—(CH 2 ) n — with n=0 to 4, for —O—(C 6 H 4 )—, for —NH—C(CH 3 ) 2 —, or —NH—CH(CH 2 CH 3 )—. Copolymers are also preferred that have structural units of the formula
[0000] —[CH 2 —C(CH 3 )COOH] m —[CH 2 —C(CH 3 )C(O)—Y—SO 3 H] p —
[0000] in which m and p each stand for a real integer between 1 and 2000 and Y stands for a spacer group that is selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon groups with 1 to 24 carbon atoms, with the preferred spacer groups being those in which Y stands for —O—(CH 2 ) n — with n=0 to 4, for —O—(C 6 H 4 )—, for —NH—C(CH 3 ) 2 —, or —CH(CH 2 CH 3 )—.
[0361] Instead of, or in addition to, acrylic acid and/or methacrylic acid, maleic acid can also be used as a particularly preferred monomer of group 1). In this way, one arrives at copolymers preferred according to the invention which comprise structural units having the formula
[0000] —[HOOCCH—CHCOOH] m —[CH 2 —CHC(O)—Y—SO 3 H] p —
[0000] in which m and p each stand for a real integer between 1 and 2000 and Y stands for a spacer group that is selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon groups with 1 to 24 carbon atoms, with the preferred spacer groups being those in which Y stands for —O—(CH 2 ) n — with n=0 to 4, for —O—(C 6 H 4 )—, for —NH—C(CH 3 ) 2 —, or —NH—CH(CH 2 CH 3 )—. Copolymers are also preferred that have structural units of the formula
[0000] —[HOOCCH—CHCOOH] m —[CH 2 —C(CH 3 )C(O)O—Y—SO 3 H] p —
[0000] in which m and p each stand for a real integer between 1 and 2000 and Y stands for a spacer group that is selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon groups with 1 to 24 carbon atoms, with the preferred spacer groups being those in which Y stands for —O—(CH 2 ) n —with n=0 to 4, for —O—(C 6 H 4 )—, for —NH—C(CH 3 ) 2 —, or —CH(CH 2 CH 3 )—.
[0362] In summary, the copolymers preferred are those that comprise structural units having the formulas
[0000] —[CH 2 —CHCOOH] m —[CH 2 —CHC(O)—Y—SO 3 H] p —
[0000] —[CH 2 —C(CH 3 )COOH] m —[CH 2 —CHC(O)—Y—SO 3 H] p —
[0000] —[CH 2 —CHCOOH] m —[CH 2 —C(CH 3 )C(O)—Y—SO 3 H] p —
[0000] —[CH 2 —C(CH 3 )COOH] m —[CH 2 —C(CH 3 )C(O)—Y—SO 3 H] p —
[0000] —[HOOCCH—CHCOOH] m —[CH 2 —CHC(O)—Y—SO 3 H] p —
[0000] —[HOOCCH—CHCOOH] m —[CH 2 —C(CH 3 )C(O)O—Y—SO 3 H] p —
[0000] in which m and p each stand for a real integer between 1 and 2000 and Y stands for a spacer group that is selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon groups with 1 to 24 carbon atoms, with the preferred spacer groups being those in which Y stands for —O—(CH 2 ) n — with n=0 to 4, for —O—(C 6 H 4 )—, for —NH—C(CH 3 ) 2 —, or —NH—CH(CH 2 CH 3 )—.
[0363] The sulfonic acid groups in the polymers can be partially or entirely in the neutralized form. That is, the acidic hydrogen atom of the sulfonic acid group can, in some or all the sulfonic acid groups, be replaced by metal ions, preferably metal ions and particularly sodium ions. Use of partially of entirely neutralized copolymers comprising sulfonic acid groups is preferred according to the invention.
[0364] The monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95% by weight each of i) or ii) for copolymers that comprise only monomers of groups i) and ii); especially preferably 50 to 90% by weight monomer from group I) and 10 to 50% by weight of monomer from group ii), based on the polymer in each case.
[0365] Of the terpolymers, those comprising 20 to 85% by weight monomer from group i), 10 to 60% by weight monomer from group ii) and 5 to30% by weight from group iii) are especially preferred.
[0366] The molecular weights of the sulfo-copolymers preferably used according to the invention can be varied to adapt the properties of the polymer to the desired application. Preferred laundry detergents or cleaners are characterized by the copolymers having molecular weights of 2,000 to 200,000 g/mole, preferably 4,000 to 25,000 g/mole, and particularly 5,000 to 15,000 g/mole.
[0367] Bleaching agents are substances with washing or cleaning action that can be used with special preference. Of the compounds that produce H 2 O 2 in water and act as bleaching agents. sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Examples of other usable bleaching agents include peroxypyrophosphate, citrate perhydrate, and peracid salts or peracids such as perbenzoate, peroxophthalate, diperazelaic acid, phthaliminoperacid or diperdodecanedioic acid that provide H 2 O 2 . It is also possible to use bleaching agents of the group of organic bleaching agents. Typical organic bleaching agents are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaching agents are the peroxy acids, of which the alkyl peroxyacids and aryl peroxyacids must be mentioned in particular as examples. Preferred representatives that can be used are (a) peroxybenzoic acid and its ring-substituted derivatives such as alkylperoxybenzoic acids, as well as peroxy-α-naphthoic acid and magnesium mono-perphthalate; (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycapric acid, [phthaliminoperoxyhexanoic acid, (PAP)], o-carboxybenzamidoperoxycapric acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxcylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1,4-dioic acid, and N,N-terephthaloyl-di(6-aminopercapric acid).
[0368] Substances that release chlorine or bromine can also be used as bleaching agents. The suitable materials that release chlorine or bromine that can be considered include, for instance, heterocyclic N-bromamides and N-chloramides, such as trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and/or dichloroisocyanuric acid (DICA) and/or their salts with cations such as potassium and sodium. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
[0369] Laundry detergents or cleaners that contain 1 to 35% by weight, preferably 2,5 to 30% by weight, especially preferably 3.5 to 30% by weight and particularly 5 to 15% by weight bleaching agent, preferably sodium percarbonate, are preferred according to the invention.
[0370] The active oxygen content of the laundry detergent or cleaner is preferably between 0.4 and 10% by weight, especially preferably between 0.5 and 8% by weight, and particularly between 0.6 and 5% by weight, based in each case on the total weight of the laundry detergent or cleaner. Specially preferred agents have an active oxygen content greater than 0.3% by weight, preferably above 0.7% by weight, especially preferably above 0.8% by weight and particularly above 1.0% by weight.
[0371] Bleach activators are used in laundry detergents or cleaners, for example, to get good bleaching action in washing at temperatures of 60° C. and below. Compounds that yield aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, especially 2 to 4 C atoms and/or optionally substituted perbenzoic acid, under perhydrolysis conditions can be used as bleach activators. Substances bearing O-acyl and/or N-acyl groups of the specified number of C atoms and/or optionally substituted benzoyl groups are suitable. Multiply acylated alkylenediamines are preferred, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-1,4-dioohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or iso-nonanoyl-oxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated multifunctional alcohols, especially triacetin, ethylene glycol diacetate, isopropenyl acetate, 2,5-diacetoxy-2,5-dihydrofuran.
[0372] Other bleach activators used preferably in the context of the present invention are compounds from the group of cationic nitriles, especially cationic nitriles having the formula
[0000]
[0000] in which R 1 stands for —H, —CH 3 , a C 2-24 -alkyl or alkenyl group, a substituted C 2-24 -alkyl or alkenyl group having at least one substituent from the group —Cl, —Br, OH, —NH 2 , —CN, an alkyl or alkenylaryl group with a C 1-24 -alkyl group and at least one other substituent on the aromatic ring, or for a substituted alkyl or alkenylaryl group having at least one other substituent on the aromatic ring, R 2 and R 3 , independently of each other, are selected from —CH 2 —CN, —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH(CH 3 )—CH 3 , —CH 2 OH, —CH 2 —CH 2 —OH, —CH(OH)CH 3 , —CH 2 —CH 2 —CH 2 —OH, —CH 2 —CH(OH)—CH 3 , —CH(OH)—CH 2 CH 3 , —CH 2 CH 2 —O) n H with n=1, 2, 3, 4, 5 or 6, and X is an anion.
[0373] A cationic nitrile having the formula
[0000]
[0000] is specially preferred in which R 4 , R 5 and R 6 independently of each other are selected from —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 CH 3 , or —CH(CH 3 )_CH 3 , in which R 4 can also be —H and X is an anion, and preferably R 5 ═R 6 ═—CH 3 , and especially R 4 ═R 5 ═R 6 ═—CH 3 , and compounds of the formulas (CH 3 ) 3 N (+) CH 2 —CNX − , (CH 3 CH 2 ) 3 N (+) CH 2 —CNX − , (CH 3 CH 2 CH 2 ) 3 (+) CH 2 —CNX − , (CH 3 CH(CH 3 )) 3 N (+) CH 2 —CNX − , or (HO—CH 2 —CH 2 ) 3 N (+) CH 2 —CNX − are especially preferred, in which again, of the group of these substances, the cationic nitrile of the formula (CH 3 ) 3 N (+) CH 2 —CNX − , in which X − stands for an anion selected from the group of chloride, bromide, iodide, bisulfate, methosulfate, toluenesulfonate(tosylate) or xylenesulfonate is especially preferred.
[0374] Compounds which under perhydrolysis conditions yield aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, especially 2 to 4 carbon atoms, and/or atoms, especially 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acids, can also be used as bleach activators. Substances that bear O-acyl and/or N-acyl groups of the stated number of carbon atoms and/or optionally substituted benzoyl groups are suitable. The preferred compounds are multiply acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycourils, especially tetraacetylglycouril (TAGU), N-acyl imides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyloxybenzenesulfonate or iso-nonanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated multifunctional alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, N-methylmorpholinium-acetonitrile-methylsulfate (MMA) as well as acetylated sorbitol and mannitol or mixtures of them (SORMAN), acylated sugar derivatives, especially pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose, as well as acetylated, optionally N-alkylated glucamines and gluconolactones, and/or N-acylated lactams, such as N-benzoyl caprolactam. Hydrophilically substituted acylacetals and acyllactams are likewise used preferably. Combinations of conventional bleach activators can also be used.
[0375] To the extent that bleach activators other than the optional nitrilquats are to be used, it is preferable to use bleach activators from the group of multiply acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acyl imides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyloxybenzenesulfonate or iso-nonanoyloxybenzenesulfonate (n- or iso-NOBS), N-methylmorpholinium-acetonitrile-methylsulfate (MMA), preferably in proportions of up to 10% by weight, especially 0.1% by weight up to 8% by weight, particularly 2 to 8% by weight and especially preferably 2 to 6% by weight, based in each case on the total weight of the laundry detergent or cleaner containing the bleach activator.
[0376] So-called ‘bleach catalysts’ can also be used Instead of, or in addition to, the conventional bleach activators. These substances are transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salene complexes or carbonyl complexes that intensify bleaching. Complexes of Mn, Fe, Co, Ru, Mo, Ti, V and Cu with N-containing tripod ligands, and Co, Fe, Cu and Ru ammine complexes are also usable as bleach activators.
[0377] Bleach-intensifying transition metal complexes, especially those having Mn, Fe, Co, Cu, Mo, V, Ti and/or Ru as the central atom, preferably selected from the group of manganese and/or cobalt salts and/or complexes, especially preferably the cobalt(ammine) complexes, the cobalt(acetato) complexes, the cobalt(carbonyl) complexes, and the chlorides of cobalt or of manganese, of manganese sulfate, can optionally be used in the usual proportions, preferably in a proportion up to 5% by weight, especially from 0.0025% by weight to 1% by weight and especially preferably from 0.01% by weight to 0.25% by weight, based in each case on the total weight of the laundry detergent or cleaner containing the bleach activator. In special cases, though, even more bleach activator can be used.
[0378] Enzymes can be used to increase the washing or cleaning ability of laundry detergents or cleaners. Those include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and, preferably, mixtures of them. These enzymes are of natural origin in principle. Improved variants, based on the natural molecules, are available for use in laundry detergents and cleaners. They are preferably used appropriately. Laundry detergents or cleaners contain enzymes preferably in total proportions of 1·10 −6 to 5% by weight, based on the active protein. The protein concentration can be determined with known methods, such as the BCA procedure or the biuret procedure.
[0379] Of the proteases, those of the subtilisin type are preferred. Examples of those include the subtilisins BPN' and Carlsberg, Protease PB92, subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the subtilases, but not the enzymes thermitase, Proteinase K, and the proteases TW3 and TW7, which are no longer classified with the subtilisins in the narrower sense. Subtilisin Carlsberg, in the further-developed form, is available from Novozymes A/S, Bagsvrd, Denmark, under the trade name Alcalase®. Subtilisins 147 and 309 are offered as Esperase® or Savinase® by Novozymes. The variants listed under the designation BLAP® by Novozymes. The variants listed under the designation BLAP® are derived from the protease of Bacillus lentus DSM 5483.
[0380] Examples of other usable proteases are those available under the trade names Durazym®, Relase® , Everlase® , Nafizym, Natalase® , Kannase® and Ovozymes® from Novozymes; those available under the trade names Purafect®, Purafect®, OxP and Properase from Genencor; those available under the trade name of Protosol® from Advanced Biochemical Ltd., Thane, India; those available under the trade name Wuxi® from Wuxi Snyder Bioproducts Ltd., China; those available under the trade names Proleather® and Protease P® from Amano Pharmaceuticals, Ltd., Nagoya, Japan; and those available under the trade name Proteinase K-16 from Kao Corp., Tokyo, Japan.
[0381] Examples of amylases usable according to the invention include the α-amylases of Bacillus licheniformis, B. amyloliquefaciens or B. stearothermohilus, as well as the improvements on them for use in laundry detergents and cleaners. The enzyme from B. licheniformis is available from Novozymes as Termamyl®, and from Genencor as Purastar® ST. Further developments of these α-amylases are available from Novozymes as Duramyl® and Termamyl® ultra; from Genencor as Purastar® OxAm, and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®. The α-amylase from B. amyloliquefaciens is offered by Novozymes as BAN®, and variants derived from the α-amylase from B. stearothermophilus are offered as BSG® and Novamyl®, likewise from Novozymes.
[0382] The α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin-glucanotransferase (CGTase) from B. agaradherens (DSM 9948) are also recommended for this purpose.
[0383] The improvements of the α-amylase from Aspergillus niger and A. oryzae obtainable from Novozymes as Fungamyl® are also suitable. Amylase-LT® is another commercial product.
[0384] Lipases or cutinases are also usable according to the invention, especially because of their triglyceride-hydrolyzing activities, but also to generate peracids in situ from suitable precursors. These include, for example, the lipases originally available from Humicola lanuginosa ( Thermomyces lanuginosus ), or further-developed lipases, especially those with the amino acid replacement D96L. They are marketed by Novozymes, for example, under the trade names Lipolase®, Lipolase® Ultra, LipoPrime®, Lipozyme® and Lipex®. Cutinases originally isolated from Fusarium solani pisi and Humicola insolens are also usable, for example. Similarly usable lipases are available from Amano under the names Lipase CE. Similarly usable lipases are available from Amano under the names Lipase CE®, Lipase P®, Lipase B®, or Lipase CES®, Lipase AKG®, Bacillus sp. Lipase®, Lipase AP®, Lipase M-AP® and Lipase AML®. The lipases or cutinases from Genencor are also usable, for example. Their starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products that must be mentioned are the preparations M1 Lipase® and Lipomax® originally marketed by Gist-Brocades and the enzymes marketed by Meito Sangyko KK, Japan, as Lipase MY-30®, Lipase OF® and Lipase PL®, as well as the Genencor product Lumafast ®.
[0385] Enzymes classified as hemicellulases can also be used. They include, for example, mannanases, xanthanlyases, pectinlyases (=pectinases), pectin esterases, pectate lyases, xyloglucanases (=Xylanases), pullulanases and β-glucanases. Suitable mannanases are available, for example, as Gamanase® and Pectinex AR® from Novozymes, as Rohapec® B1L from AB Enzymes and as Pyrolase® from Diversa Corp., San Diego, Calif., USA. The β-glucanase obtained from B. subtilis is available as Cereflo® from Novozymes.
[0386] Oxidoreductases, such as oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, ligno-, glucose- or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching action. Denilite® 1 and 2 from Novozymes must be mentioned as suitable commercial products. It is advantageous to add additional preferably organic, especially preferably aromatic compounds that interact with the enzymes to strengthen the activity of the oxidoreductases in question (enhancers) or to assure electron flow when the redox potentials of the oxidizing enzymes and the dirt are greatly different (mediators).
[0387] The enzymes are, for example, either produced originally from microorganisms, such as those of the genera Bacillus, Streptomyces, Humicola or Pseudomonas, and/or are produced by suitable microorganisms by biotechnological processes that are themselves known, such as by transgenic expression hosts of the genera Bacillus or filamentous fungi.
[0388] The enzymes under consideration are preferably purified by processes that are themselves established, for example, by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, action of chemicals, deodorization or suitable combinations of those steps.
[0389] The enzymes can be used in any of the forms established at the state of the art. That includes, for instance, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly for agents in liquid or gel forms, solutions of the enzyme, advantageously as concentrated as possible, low in water and/or mixed with stabilizers.
[0390] Alternatively, the enzymes can be encapsulated for both the liquid and solid use forms, such as by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, such as those in which the enzyme is enclosed as in a solidified gel or in those of the core-shell, type in which the enzyme-containing core is coated with a protective layer that is impermeable to water, air and/or chemicals. Other additional active ingredients such as stabilizers, emulsifiers, pigments, bleaches or colorants can be applied in layered shells. Such capsules are applied by methods that are themselves known, such as by shaking or rolling granulation or in fluidized bed processes. Such granulations are advantageously low in dust and stable in storage because of the coating, for example, by application of polymeric film-formers.
[0391] It is further possible to formulate two or more enzymes together so that a single granulation has multiple enzyme activities.
[0392] A protein or an enzyme can be protected, particularly during storage, against damages such as inactivation, denaturation or decomposition due to physical influences, oxidation, or proteolytic hydrolysis. If the proteins and/or enzymes are obtained microbiologically, inhibition of proteolysis is especially preferred, particularly if the agent also contains proteases. Laundry detergents or cleaners can contain stabilizers for that purpose. Provision of such an agent is a preferred embodiment of the present invention.
[0393] Reversible protease inhibitors are one group of stabilizers. Benzamidine hydrochloride, borax, boric acids, boronic acids, or their salts or esters are often used, including in particular derivatives having aromatic groups, such as ortho-substituted, meta-substituted and para-substituted phenylboronic acids or their salts or esters. Ovomucoid and leupeptin, among others, must be mentioned as peptidic protease inhibitors. Formation of fusion proteins from proteases and peptide inhibitors is another option.
[0394] Other enzyme stabilizers include aminoalcohols such as mono-, di- and tri-ethanolamine and -propanolamine and mixtures of them, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of the acids named. End-group-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders can also stabilize a contained enzyme.
[0395] Lower aliphatic alcohols, but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other enzyme stabilizers that are often used. Calcium salts such as calcium acetate or calcium formate, and magnesium salts, are also used.
[0396] Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and/or polyamides stabilize enzyme preparations against physical influences or pH fluctuations, among other things. Polymers containing polyamine-N-oxides act as enzyme stabilizers. The linear C 8 -C 18 polyoxyalkylenes are other polymeric stabilizers. Alkyl polyglycosides can stabilize the enzymic components and can even increase their activity. Cross-linked nitrogenous compounds likewise act as enzyme stabilizers.
[0397] Reducing agents and antioxidants increase the stability of the enzymes against oxidative decomposition. Sodium sulfite is a sulfur-containing reducing agent, for example.
[0398] It is preferred to use combinations of stabilizers, for example, combinations of polyols, boric acid and/or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids, or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The action of peptide-aldehyde stabilizers is increased by the combination with boric acid and/or boric acid derivatives and polyols, and is further increased by the additional use of divalent cations such as calcium ions.
[0399] It is preferred to use one or more enzymes or enzyme preparations, preferably solid protease preparations and/or amylase preparations, in proportions of 0.1 to 5% by weight, preferably of 0.2 to 4.5% by weight, and particularly 0.4 to 4% by weight, based in each case on the total enzyme-containing agent.
[0400] It is possible to incorporation disintegrants, so-called ‘tablet explosives’, in these agents to make the breakup of solids easier, so as to shorten the disintegration times. According to Römpp (9 th Ed., Vol. 6, p. 4440) and Voigt, “ Lehrbuch der pharmazeutischen Technologie” [“Textbook of pharmaceutical technology ”] (6 th Ed., 1987, pages 182-184), ‘tablet explosives’ or disintegration accelerators are understood to be additives that provide for rapid disintegration of tablets in water or in gastric fluid and for release of pharmaceuticals in absorbable form.
[0401] These substances, which are called “explosive” agents because of their action, increase in volume on entry of water. On one hand, they increase their own volume (swelling). On the other hand, release of gases can produce a pressure that breaks the tablets into smaller particles. Carbonate/citric acid systems are disintegrants that have been known for a long time, and other organic acids can also be used. Examples of swelling disintegrants include synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as celluloses and starches and their derivatives, alginates, or casein derivatives.
[0402] Disintegrants can be used preferably in proportions of 0.5 to 10% by weight, preferably 3 to 7% by weight, and particularly 4 to 6% by weight, based in each case on the total weight of the agent containing the disintegrant.
[0403] Disintegrants based on cellulose are used as preferred disintegrants, so that preferred laundry detergents or cleaners contain such a cellulose-based disintegrant in proportions of 0.5 to 10% by weight, preferably 3 to 7% by weight, and particularly 4 to 6% by weight. Pure cellulose has the empirical composition (C 6 H 10 O 5 ) n . Considered formally, it is a β-1,4-polyacetal of cellobiose which is itself made up of two molecules of glucose. Suitable celluloses comprise about 500 to 5000 glucose units, and accordingly have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants usable in the context of the present invention also include cellulose derivatives that can be obtained from cellulose by polymer-like reactions. Such chemically modified celluloses include, for example, products of esterifications or etherifications, in which hydroxyl hydrogen atoms are substituted. However, celluloses in which the hydroxy groups are replaced by functional groups not bound through an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and amino celluloses. The cellulose derivatives named are preferably not used alone as cellulose-based disintegrants, but in mixtures with cellulose. The proportion of cellulose derivatives in these mixtures is preferably less than 50% by weight, especially preferably less than 20% by weight, based on the cellulose-based disintegrant. It is particularly preferable to use, as cellulose-based disintegrants, pure cellulose that is free of cellulose derivatives.
[0404] The cellulose used as a disintegrant additive is preferably not used in finely divided form, but converted into a coarser form before mixing into the premixes to be pressed, such as granulated or compacted. The particle sizes of such disintegrants are usually greater than 200 μm, preferably with at least 90% by weight between 300 and 1600 μm and particularly with at least 90% by weight between 400 and 1200 μm. The coarser cellulose-based disintegrants named above and described in more detail in the documents cited are used preferably in the context of the present invention. They are commercially available, for example, as Arbocel® TF-30-HG from the Rettenmaier company.
[0405] Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as an ingredient of those components. This microcrystalline cellulose is obtained by partial hydrolysis of cellulose under conditions such that only the amorphous regions of the cellulose (ca. 30% of the total cellulose) are attacked and completely dissolved while the crystalline regions (ca. 70%) remain undamaged. Subsequent disaggregation of the microfine cellulose resulting from the hydrolysis gives the microcrystalline celluloses, which have primary particle sizes of about 5 μm and which can, for instance, be compacted into granulations having an average particle size of 200 μm.
[0406] Preferred disintegrants, preferably a disintegrant based on cellulose, preferably in a granular, cogranular or compacted form, can be contained in agents that contain disintegrants in proportions of 0.5 to 10% by weight, preferably 3 to7% by weight, and particularly 4 to 6% by weight, based in each case on the total weight of the agent containing the disintegrant.
[0407] Effervescent systems that evolve gases can also be preferred tablet disintegrants according to the invention. The effervescent gas-evolving systems can consist of a single substance that releases gas on contact with water. Of these compounds, magnesium peroxide in particular must be named. It releases oxygen on contact with water. Usually, though, the gas-evolving effervescent system itself comprises at least two components which react with each other, forming gas. Although many systems are conceivable and feasible, releasing, for example nitrogen, oxygen or hydrogen, the effervescent gas-evolving system used in detergents or cleaning agents is chosen from both economic and ecological viewpoints. Preferred effervescent systems comprise alkali metal carbonate and/or bicarbonate, and an acidifying agent that is suitable to release carbon dioxide from the alkali metal salts in aqueous solution.
[0408] Of the alkali metal carbonates or bicarbonates, the sodium and potassium salts are definitely preferred over the other salts for reasons of cost. Obviously, it is not necessary to use the pure alkali metal carbonates or bicarbonates; rather, mixtures of different carbonates and bicarbonates can be preferred.
[0409] As an optional effervescent system, it is preferable to use 2 to 20% by weight, preferably 3 to 15% by weight, and particularly 5 to 10% by weight of an alkali metal carbonate or bicarbonate, and 1 to 15, preferably 2 to 12% by weight, and particularly 3 to 10% by weight of an acidifying agent, based in each case on the total weight of the agent.
[0410] For example, boric acid and alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used as acidifying agents that release carbon dioxide from the alkali salts in aqueous solution. To be sure, it is preferable to use organic acidifying agents, with citric acid a specially preferred acidifying agent. However, other solid mono-, oligo- and poly-carboxylic acids in particular can also be used. Of this group, again, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are preferred. Organic sulfonic acids such as amidosulfonic acid are also usable. Sokalan® DCS (BASF trademark), a mixture of succinic acid (up to 31% by weight), glutaric acid (up to 50% by weight) and adipic acid (up to 33% by weight) is commercially available and also preferably usable as an acidifying agent in the context of the present invention.
[0411] The preferred acidifying agents in the effervescent system are from the group of organic di- tri- and oligo-carboxylic acids or mixtures of them.
[0412] Preferred colorants, the selection of which presents no problem to those skilled in the art, have high storage stability and low sensitivity to the other ingredients of the agent or to light. They do not have any distinct substantivity for the substrates to be treated with the colorant-containing agent, such as textiles, glass, or ceramic or plastic tableware, so as not to stain them.
[0413] In selection of the colorant, one must take into consideration the fact that the colorants, in the case of laundry detergents, must not have excessive affinity to textile surfaces, particularly to plastic fibers, while in the case of cleaners one must avoid excessive affinity to glass, ceramic or plastic tableware. At the same time, in selection of suitable colorants, one must consider that colorants have different degrees of stability to oxidation. In general, water-insoluble colorants are more stable to oxidation than are water-soluble colorants. The concentration of the colorants in laundry detergents or cleaners varies, depending on their solubility and on their sensitivity to oxidation. For colorants with good water solubility, such as the Basacid® Green mentioned above, or Sandolan® Blue, also mentioned above, one typically chooses colorant concentrations in the range of a few hundredths to thousandths of one percent by weight. For the pigment colorants, which are specially preferred because of their brilliance, but are less water-soluble, such as the Pigmosol® colorants mentioned above, the suitable concentration of the colorant in laundry detergents or cleaners is, on the other hand, typically a few thousandths to ten-thousandths of one percent by weight.
[0414] Preferred colorants are those that can be oxidatively destroyed in the washing process, and mixtures of those with suitable blue colorants, the so-called bluing agents. It has proven advantageous to use colorants that are soluble in water or, at room temperature, in liquid organic substances. For instance, anionic colorants, such as anionic nitroso dyes are suitable. For instance, one possible colorant is Naphthol Green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020) which is available commercially for example, as Basacid® Green 970 from BASF, Ludwigshafen, or mixtures of it with suitable blue colorants. Other colorants used include Pigmosol® Blue 6900 (CI 74160), Pigmosol® Green 8730 (CI 74260), Basonyl® Red 545 FL (CI 45170), Sandolan® Rhodamin EB400 (CI 45100), Basacid® Yellow 094 (CI 47005), Sicovit® Patent Blue 85E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), Pigment Blue 15 (CI 74160), Supranol® Blue GLW (CAS 12219-32-8), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and/or Sandolan® Blue (CI Acid Blue 12219-26-0).
[0415] In addition to the preferably usable components described so far, the laundry detergents or cleaners can also contain other ingredients that further improve the application-technology and/or aesthetic properties of these agents. Preferred agents contain one or more substances from the groups of electrolytes, pH-adjusting substances, fluorescent substances, hydrotropes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, graying inhibitors, agents to prevent shrinkage, antiwrinkle agents, color transfer inhibitors, antimicrobially active substances, germicides, fungicides, antioxidants, antistatic agents, ironing aids, phobing and impregnating agents, antiswselling and antislip agents, and UV absorbers.
[0416] A large number of quite varied salts from the group of inorganic salts can be used as electrolytes. The alkali and alkaline earth metals are preferred cations, while the halides and sulfates are preferred anions. From the viewpoint of production technology, it is preferable to use NaCl or MgCl 2 in the laundry detergents or cleaners.
[0417] Use of pH-adjusting agents may be indicated to bring the pH of laundry detergents or cleaners to the desired range. All the well-known acids or bases can be used here as long as their use it not ruled out for applications technology or ecologic reasons, or for user protection. The proportion of this adjusting agent usually does not exceed 1% by weight of the total formulation.
[0418] Soaps, oils, fats, paraffins or silicone oils can be considered as foam inhibitors. They can optionally be applied to carrier materials. For example, inorganic salts such as carbonates or sulfates, cellulose derivatives, silicates, or mixtures of those materials are suitable carriers. In the context of the present invention, preferred laundry detergents or cleaners contain paraffins, preferably unbranched paraffins (n-paraffins) and/or silicones, preferably linear polymeric silicones, structured as (R 2 SiO) x , and called silicone oils. These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids with molecular weights between 1,000 and 150,000, and viscosities between 10 and 1,000,000 mPa·s.
[0419] Suitable antiredeposition agents, also called soil repellants, are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropyl-cellulose, with 15 to 30% by weight methoxyl groups and 1 to 15% by weight hydroxypropyl groups, based in each case on the nonionic cellulose ether, and the polymers of phthalic acid and/or terephthalic acid known at the state of the art, or their derivatives, especially polymers of ethylene terephthalate and/or polyethylene glycol terephthalate, or anionically and/or nonionically modified derivatives of them. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
[0420] Optical brighteners (so-called “white toners”) can be added to laundry detergents or cleaners to prevent graying and yellowing of the textiles treated. These substances adhere to the fibers and cause lightening and simulated bleaching by converting invisible ultraviolet radiation into longer-wave visible light, so that the ultraviolet light absorbed from sunlight is radiated off as a weak bluish fluorescence, which combines with the yellow tone of the grayed or yellowed laundry to give a pure white. Suitable compounds are derived, for example, from the substance classes of the 4,4′-diamino-2,2′-stilbenedisulfonic acids (flavonic acids), 4,4′-distyrylbiphenylenes, methylumbelliferone, coumarins, dihydroquinolines, 1,3-diarylpyrazolines, naphthalic acid imides, benzoxazole, benzisoxazol and benzimidazole systems, and pyrene derivatives with heterocyclic substituents.
[0421] Antiredeposition agents have the function of keeping dirt removed from the fibers separated in the liquor, thus preventing readsorption of the dirt. Water-soluble colloids, most of them organic, are suitable for that. Examples include the water-soluble salts of polymeric carboxylic acids, glue, gelatins, salts of ethersulfonic acids of starch or cellulose, or salts of acidic sulfuric acid esters of cellulose or starch. Polyamides having water-soluble acidic groups are also suitable for this purpose. Soluble starch preparations, and starch products other than those named above, such as degraded starch, aldehyde starches, etc., can also be used. Polyvinylpyrrolidone is also usable. Cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose, and mixtures of them can also be used as antiredeposition agents.
[0422] Synthetic anti-wrinkle agents can be used because textile surface structures, especially those of rayon, rayon staple fiber, cotton, and mixtures of them can tend to wrinkle because the individual fibers are sensitive to bending, kinking, pressing and crushing transverse to the fiber direction. They include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty acid alkylol ester, fatty acid alkylolamides or fatty alcohols, usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
[0423] Phobing and impregnating processes serve to provide the textiles with substances that prevent deposition of dirt or make it easier to wash out. Preferred phobing and impregnating agents include perfluorinated fatty acids, also in the form of their aluminum and zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol components or with polymerizable compounds coupled to perfluorinated acyl or sulfonyl groups. Antistatic agents can also be contained. The dirt-repelling finish with phobing and impregnating agents is often classified as an easy-care finish. Penetration of the impregnating agent in the form of solutions or emulsions of the active substances concerned can be made easier by addition of wetting agents, which reduce the surface tension. Water-repellent finishing of textile goods, tents, surfaces, leather, etc. is another area of application of phobing and impregnating agents. In this case, in contrast to making something water-tight, the pores of the cloth are not closed, so that the material remains able to breathe (hydrophobizing). The hydrophobizing agents used for hydrophobizing coat textiles, leather, paper, wood, etc., with a very thin layer of hydrophobic groups, such as long alkyl chains or siloxane groups. Suitable hydrophobizing agents include, for example, paraffins, waxes, metal soaps, etc. with additions of aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl groups, urea derivatives, fatty-acid-modified melamine resins, complex chromium salts, silicones, organotin compounds and glutardialdehyde as well as perfluorinated compounds. The hydrophobized materials do not feel greasy. Nevertheless, water droplets bead up on them, as they do on greased materials, without wetting them. Thus, silicone-impregnated textiles, for example, have a soft hand and repel water and dirt. Spots of ink, wine, fruit juices and the like are more easily removed.
[0424] Antimicrobially active substances can be used against microorganisms. Here one distinguishes between bacteriostats, bactericides, fungistats, and fungicides on the basis of their antimicrobial spectrum and their mechanism of action. Examples of important substances of these groups include benzalkonium chloride, alkylarylsulfonates, halophenols and phenylmercuric acetate. Use of these compounds can also be avoided entirely.
[0425] The laundry detergents or cleaners can contain antioxidants to prevent undesired changes to them or to the textiles treated due to the action of oxygen and other oxidative processes. This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
[0426] Additional use of antistatic agents gives better comfort for the wearer. Antistatic agents increase the surface conductivity, allowing charges to leak off better. External antistatic agents are usually substances with at least one hydrophilic molecular ligand. They provide a more or less hygroscopic film on the surface. These antistatic agents, usually surface-active, can be classified as nitrogenous (amines, amides, quaternary ammonium compounds), phosphor-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are likewise suitable as antistatic agents for textiles or as additives to laundry agents, in which case a softening effect is also produced.
[0427] Softening rinsers can be used for textile care and to improve the textile properties, such as a softer “hand” (softening) and reduced electrostatic charging (better wearer comfort). The active ingredients in softening rinsers are “esterquats”, quaternary ammonium compounds with two hydrophobic groups, such as distearyldimethylammonium chloride, but those are increasingly being replaced by quaternary ammonium compounds that have ester groups in their hydrophobic groups as intended cleavage sites for biodegradation.
[0428] Such “esterquats” with better biodegradability are available, for instance, by esterifying mixtures of methyldiethanolamine and/or triethanolamine with fatty acids and then quaternizing the reaction products with alkylating agents in the known manner. Dimethylolethyleneurea is also a suitable finishing agent.
[0429] Silicone derivatives can be used to improve ability to absorb water and rewettability of the treated textiles, and to make ironing of the treated textiles easier. These also improve the ability of laundry detergents or cleaners to rinse out, due their foam-inhibiting properties. Examples of preferred silicone derivatives include polydialkyl or alkylaryl siloxanes, in which the alkyl groups have one to five C atoms and are partially or completely fluorinated. Preferred silicones include polydimethylsiloxanes, which can optionally be derivatized and are then aminofunctional or quaternized, or have Si—OH, Si—H and/or Si—Cl bonds. Other preferred silicones include the polyalkeneoxide-modified polysiloxanes, i. e., polysiloxanes having polyethylene glycols, for instance, and the polyalkylene oxide-modified dimethylpolysiloxanes.
[0430] Finally, UV absorbers can also be used according to the invention. They adsorb to the treated textiles and improve the light resistance of the fibers. Compounds that have these desired properties are, for example, the compounds that act by non-radiative deactivation and derivatives of benzophenone with substituents in the 2 and/or 4 position. Substituted benzotriazoles, acrylates phenyl-substituted in the 3 position (cinnamic acid derivatives), optionally with cyano groups in the 2 position, salicylates, organic nickel complexes and natural material such as umbelliferone and the body's own urocanic acid are also suitable.
[0431] Because of their fiber-protecting action, protein hydrolyzates are other preferred active substances from the field of laundry detergents or cleaners in the context of the present invention. Protein hydrolyzates are mixtures of products obtained by acid, basic, or enzyme-catalyzed degradations of proteins. Protein hydrolyzates of both plant and animal origin can be used according to the invention. Examples of animal protein hydrolyzates include elastin, collagen, keratin, silk and milk protein hydrolyzates, which can also be in the form of salts. According to the invention, use of protein hydrolyzates of plant origin, such as soy, almond, rice, pea, potato and wheat protein hydrolyzate, is preferred. Even though it is preferable to use protein hydrolyzates as such, amino acid mixtures or individual amino acids such as arginine, lysine, histidine or pyroglutamic acid can optionally be used instead. It is likewise possible to use derivatives of the protein hydrolyzates, as in the form of their fatty acid condensation products.
[0432] The non-aqueous solvents that can be used according to the invention include, in particular, the organic solvents, of which only the most important can be listed here: alcohols (methanol, ethanol, propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, diethylene glycol), ethers and glycol ethers (diethyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran, mono, di, tri, polyethylene glycol ethers), ketones (acetone, butanone, cyclohexanone), esters (ethyl acetate, glycol esters), amides and other nitrogenous compounds (dimethylformamide, pyridine, N-methylpyrrolidone, acetonitrile), sulfur compounds (carbon disulfide, dimethylsulfoxide, sulfolan), nitro compounds (nitrobenzene), halohydrocarbons (dichloromethane, chloroform, tetrachloromethane, tri- and tetra-chloroethene, 1,2-dichloroethane, chlorofluorohydrocarbons), hydrocarbons (gasoline, petroleum ether, cyclohexane, methylcyclohexane, decalin, terpene solvents, benzene, toluene, xylenes). Alternatively, mixtures can for example be used instead of pure solvents, advantageously combining the solution properties of different solvents. One such solvent mixture that is especially preferred in the context of the present invention is, for instance, cleaner's naphtha, a mixture of different hydrocarbons suitable for chemical cleaning, preferably having more than 60% by weight of C12 to C14 hydrocarbons, especially preferably more than 80% by weight, and particularly more than 90% by weight, based in each case on the total weight of the mixture, preferably having a boiling point range of 81 to 110° C.
[0433] Other than where otherwise indicated, or where required to distinguish over the prior art, all numbers expressing quantities of ingredients herein are to be understood as modified in all instances by the term “about”. As used herein, the words “may” and “may be” are to be interpreted in an open-ended, non-restrictive manner. At minimum, “may” and “may be” are to be interpreted as definitively including, but not limited to, the composition, structure, or act recited.
[0434] As used herein, and in particular as used herein to define the elements of the claims that follow, the articles “a” and “an” are synonymous and used interchangeably with “at least one” or “one or more,” disclosing or encompassing both the singular and the plural, unless specifically defined herein otherwise. The conjunction “or” is used herein in both in the conjunctive and disjunctive sense, such that phrases or terms conjoined by “or” disclose or encompass each phrase or term alone as well as any combination so conjoined, unless specifically defined herein otherwise.
[0435] The description of a group or class of materials as suitable or preferred for a given purpose in connection with the invention implies that mixtures of any two or more of the members of the group or class are equally suitable or preferred; description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description, and does not necessarily preclude chemical interactions among the constituents of a mixture once mixed. Steps in any method disclosed or claimed need not be performed in the order recited, except as otherwise specifically disclosed or claimed or as needed to render such methods operative.
[0436] Changes in form and substitution of equivalents are contemplated as circumstances may suggest or render expedient. Although specific terms have been employed herein, such terms are intended in a descriptive sense and not for purposes of limitation.
EXAMPLE
[0437] A porous polymer carrier of cross-linked polypropylene was put into a Lödige mixer, combined with a melt of PEG (polyethylene glycol) 4000 and a perfume oil at 80° C., and mixed. The mixture solidified after about 1-2 minutes.
Resulting Composition of the Perfume Reservoir:
[0438]
[0000]
cross-linked polypropylene
48% by weight
PEG 4000
26% by weight
Perfume oil
26% by weight | Fluid reservoirs which are based on polymer substrates and are capable of storing large amounts of fluids. The storage is reliable and the reemergence from the liquid reservoir is readily controllable, for example, via the temperature or via mechanical actions, to achieve retardation of the fluid release. Also, processes for producing such fluid reservoirs and also their use, for example in washing or cleaning compositions. | 2 |
CROSS-REFERENCE TO A RELATED APPLICATION
This application is a continuation-in-part of application U.S. Ser. No. 10/313,497, filed Dec. 6, 2002, abandoned, which claims priority from U.S. Ser. No. 60/337,924, filed Dec. 6, 2001, now abandoned, the disclosure of each of which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
The subject invention pertains to the field of fertilizers, more particularly to the manufacture and use of slow-release fertilizers having essential elements necessary to promote growth on mineral stressed soils.
BACKGROUND OF THE INVENTION
On Oct. 12, 1999, the world population reached six billion (Wright, 1999). At the turn of the twenty-first century the estimated population was 6.1 billion. With such a dramatic increase in population, it is obvious that there is an ever increasing need to feed the world's population.
Because only 11% of the world's soils are fertile enough to be farmed without serious limitation, intense pressure is placed on using less fertile soils. Drought is a major problem for approximately 28% of the land; mineral stress is a problem for an additional 23%. Most soils affected by drought are alkaline, whereas most affected by mineral stress are acidic (Foth and Ellis, 1997).
While fertility of deficient soils can be improved utilizing fertilizers containing appropriate amounts of essential elements for plant growth, these fertilizers may not contain the essential elements required by humans. This is especially true for crops grown upon acidic soils such as: lateritic, heavily-leached soils found throughout much of the tropical world (Moffat, 2000); silica-sand soils of Africa and Florida (Tan, 1998); young igneous soils containing larger fragments of unreactive feldspars and quartz, found in Zimbabwe and Zambia (Paton, 1978); and moderately acidic soils such as those in southeastern United States and many other parts of the world (Foth and Ellis, 1997). Thus, there is a need for fertilizers that contain essential elements required by both plants and humans to provide human populations with good physical and mental health.
Attempts to prepare such fertilizers have met with mixed results. Commercially available fertilizers are usually formulated by blending a mixture of various chemical compounds, which are not necessarily compatible. For example, the 12-12-12 microelements fertilizer, used on many illitic clay-loam soils, is one of the best commercial fertilizers on the market today. It consists of a granulated mixture of ammonium nitrate, urea, ammonium sulfate, and sulfuric acid blended with granular monocalcium/dicalcium phosphate (GTSP), granular potassium chloride, and granulated micro and trace elements. These are all essential nutrients needed to sustain healthy plant life (Foth and Ellis, 1997). After blending, fertilizer chemicals such as ureas can displace the hydrate water contained in the monocalcium/dicalcium phosphate compounds (Whittaker et al., 1933) yielding a sticky or soupy mess. Further, microelements such as iron can be readily oxidized to the plus three state (Fe 3+ ) and react with phosphate anions (PO 4 − ) to form an insoluble, unavailable ferric phosphate.
Even after application, many micro and trace element granules are so widely spaced that many plants cannot get all essential elements required for growth. Furthermore, bacterial action can result in 30% or more of the nitrogen value being lost to the atmosphere as nitrogen and nitrous oxide gases (Foth and Ellis, 1997). Finally, summer rains can wash soluble salts into aquifers, streams and lakes. Therefore, improvements need to be made to reduce the rate of release of nitrogen compounds and other essential elements to the soil.
In the late seventies, a slow-release fertilizer was developed by acidulating a high-assay phosphatic clay slime with sulfuric acid, then adding the micro and trace elements followed by formaldehyde, potassium chloride, and urea. This product worked well as a fertilizer, but was somewhat expensive and too slow in releasing essential elements.
In the late eighties, another slow-release fertilizer was developed for use in regions abundant in chicken populations. The initial mixture contained: ground chicken bones; viscera; ground phosphate ore; and sulfuric acid in which chopped chicken feathers had been dissolved. Micro and trace essential elements, potassium chloride, and urea or ammonium nitrate were added. This product was an adequate fertilizer, but limited in its application.
Thus there is a continuing need for improvements to slow-release fertilizers containing essential elements.
All references cited herein are incorporated by reference in their entirety, to the extent not inconsistent with the explicit teachings set forth herein.
BRIEF SUMMARY OF THE INVENTION
The present invention relates to the improvement of slow-release fertilizers. This improvement utilizes dolomitic phosphatic clay slime to inhibit the precipitation of insoluble micro and trace essential elemental phosphates. In one specific embodiment, the improvement further utilizes an additive for breaking down the fertilizer granules. Additives useful for this embodiment include, without limitation, phosphogypsum, silica sand, natural gypsum, clay, fine coal dust, or combinations of any of the foregoing. Advantageously, the additive facilitates the removal of the trace essential elements from the fertilizer. The water contained in the slime disproportionates most of the monocalcium phosphate produced in the manufacture to the more insoluble dicalcium phosphate. In addition, it utilizes urea as a coordinating ligand to form complex chains with calcium and magnesium. The process is followed by heat for granulation. Therefore, there is no residual water post-granulation to create the sticky, soupy by-product resulting from the production of other urea containing fertilizers.
The resulting slow-release fertilizer contains all essential elements needed by plants and humans, with the exception of carbon, iodine (found in table salt), or the more toxic essential elements such as arsenic, lead, and cadmium (Stanitski et al., 2000).
Accordingly, the present invention provides an enhanced fertilizer.
The present invention also provides an enhanced slow-release fertilizer.
The present invention provides an enhanced slow-release fertilizer containing essential elements.
The present invention provides methods for making enhanced slow-release fertilizers containing essential elements for use in mineral stressed soils.
The present invention also provides methods for using dolomitic phosphate ores.
Further advantages of the present invention will become apparent by reference to the following detailed disclosure of the invention and appended drawings.
DETAILED DESCRIPTION OF THE INVENTION
Materials suitable as a base and fertilizer can be provided to prepare a fertilizer of the present invention. For example, four phosphate ore samples are useful for preparing slow-release fertilizers according to the present invention. Two of the ores are dolomitic and obtained from C.F. Industries' (CFI) Hardee County, FL mine—of the two, sample one contains 0.5% MgO, and sample two contains 2% MgO. These ores are hand-ground into two fractions—a minus 70 mesh (−212 micron) plus 140 mesh (+106 micron) and a minus 140 mesh (−106 micron). Sample three is an ore (phos rock) obtained from Texas Gulf Sulfur's (TGS) Polk County, FL mine and is generally used in manufacturing commercial fertilizers. Sample three is ground to a minus 35/60 Tyler mesh size (about −400+200 micron). Sample four is an igneous phosphate ore obtained from Zimbabwe Phosphate Industries Ltd.'s Dorowa mine in Harara, Zimbabwe. It analyzes at 35.5% P 2 O 5 ; 1.9% Fe 2 O 3 ; 48.1% CaO; 0.8% MgO; 0.6% K 2 O; 0.5% Na 2 O; and 2% CO 2 . It is ground to minus 140 mesh (−106 micron) size, generally used for making commercial granular triple super phosphate (GTSP) fertilizers. The use of finely ground ores in the manufacturing process reduces the reaction times.
According to the subject invention, four stages are used in the preparation and evaluation of slow-release fertilizers, the processing conditions of which are illustrated in Table 1. The first stage consists of measuring out a sufficient amount of 95.5% sulfuric acid (H 2 SO 4 ) to react with the phosphate ore, and combining it with water to yield a H 2 SO 4 concentration at about 40%-90%. (In experiment 23 C, 85.2% phosphoric acid was used.) The coarse fraction of ground ore in the CFI ores (samples one and two) and the commercial ore sizes in the TGS (sample three) and Dorowa ores (sample four) are added. The mixture is stirred with a glass rod during the reaction while the temperature rises to a maximum of around 110°-120° C.; when the reaction is complete, the temperature decreases. In approximately 20 minutes a partially dried mass is formed. At this stage, a portion of the phosphate ore has been converted to monocalcium phosphate (Ca H 2 PO 4 .H 2 O); gypsum (CaSO 4 .2H 2 O); and in the case of CFI and Dorowa ores, magnesium sulfate (MgSO 4 .6H 2 O) also forms.
At the second stage, micro and trace essential elements are dispersed in the slime (see Table 1). The partially dried mass is mixed with differing amounts of the CFI dolomitic phosphatic clay slime combination (approximately 5-20% solids, preferably 11%) and heated to around 80° C. for various times. The monocalcium phosphate disproportionates into dicalcium phosphate (CaHPO 4 .2H 2 O) and phosphoric acid. The phosphoric acid reacts with remaining unreacted phosphate ore until equilibrium is achieved. At equilibrium, a small amount of finely ground phosphate is added to neutralize the residual phosphoric acid. At this point, the clay (magnesium/calcium montmorillonite) platelets form a “house of cards” structure in which a variety of salts occupy the small compartments.
At the third stage, a mixture of urea (H 2 NCONH 2 ) and potassium chloride (KCl) is added to the partially dried compartmentalized mass (see Table 1). Urea reacts with the salts that occupy the small compartments to release water and forming thin slurries. The temperature is held to between about 80° to 90° C. until most of the water is removed by evaporation. The calcium and magnesium ions coordinate with one sulfate or hydrogen phosphate ion and two urea bidentate ligand molecules. The potassium ions bind between two montmorillonite platlets. The compartmentalized mass is dried further at about 110° C. as it is granulated by mechanical means. It is important not to exceed 110° C. during the final granulation. The final pH is approximately 7.0 due to the neutralizing effect of the urea. The composition of each experimental fertilizer is provided in Table II.
The fourth stage tests fertilizer resistance. Fertilizer size granules are placed in petri dishes and tested for physical and chemical breakdown as they are subjected to conditions similar to that during use such as rainfall (see Table III). Some samples disintegrate in just a few days while others still have some granular integrity at twenty weeks. A few samples were analyzed for type of phosphate by Thornton Laboratories, Inc., Tampa. These results and the stoichiometry of each fertilizer composition are shown in Table II.
Inspection of the data shown in the three tables indicates that a 10-13-10(10% N, 13% P 2 O 5 , 10% K 2 O) fertilizer composition is readily obtained (see Ex. 13) that contains over 12% calcium, 8% sulfur, almost 8% chlorine, 0.5% magnesium and the following essential elements: 1% Fe; 1% Zn; 0.03% Mn; 0.01% Cr; 0.01% Co; 0.01% B; 0.01% Mo; 0.001% Ni; 0.001% Sn; 0.001% V; and 0.001% Se. Most of the phosphate is in the available form. Some granules of this composition last over twenty weeks with daily wetting and drying cycles before completely disintegrating. Both granular single super phosphate (GSSP), see 23B, and granular triple super phosphate (GTSP) see 23C, experimental test samples had disintegrated extensively within a few hours.
Granules appear to require phosphatic clay slime, urea bidentate ligands, and some magnesium ions to have the longest survival time. The phosphatic clay slime prevents transition metal ions such as iron from precipitating as iron (III) phosphate. Experiment 23A has a strong red color indicating that without phosphatic clay slime being present, iron (III) phosphate does precipitate. Its solubility may be so low that it may not be available to plant life in the fertilizer. The significance of magnesium ions was unexpected. Smaller magnesium ions hold the urea ligand more tightly than does the calcium ion. This enables linkages to form between magnesium and calcium ions via the bidentate urea ligands, thereby forming chains throughout each compartment made by the clay slime montmorillonite platlets. Those having no urea (Ex. 12), little or no magnesium (Ex. 18) have short lifetimes, while those without clay slime form phosphate precipitates with some of the essential micro and trace elements (see Ex. 23A).
It is well known (Whittaker et al, 1933) that gypsum and urea react in water at 30° C. to form complexes. Since a maximum of four urea bidentate molecules can form a complex with calcium, the probable complex shape is cubic. However, when dried at 110° C. the ions appear to link together for form hexagonal complexes containing only one bidentate urea molecule and one bidentate hydrogen sulfate ion and/or one bidentate hydrogen phosphate ion as cross-linking ligands. The use of the smaller magnesium ion, also complexed with these ligands in the linkage, makes the chains stronger and more resistant to attack by water molecules.
During the hot acid attack, magnesium and calcium ions contained between the montmorillonite platlets are displaced by hydrogen ions. When potassium chloride is added, the potassium ions displace the hydrogen ions to form weak micaceous structures. There is some competition with a number of the minor and trace element ions; however, the potassium ions fit in better. Therefore, most of the essential elements are tied up in the compartmentalized structure as complex ions and are released at a lower rate.
One specific embodiment of the present invention is directed to incorporating at least additive to the fertilizer during its final granulation. The additive can be selected from any ground solid particle capable of breaking down the subject fertilizers. A preferred particle size for the additive is between about 100 micron and about 300 micron. The skilled artisan can select additive to target nutrient release during the growing season of the fertilized plant. Examples of suitable additives include, without limitation, phosphogypsum, natural gypsum, silica sand, clay, and coal dust. In one embodiment, the additives are combinations of any of the foregoing. The fineness of the additives affects the break down of the fertilizer granules. As the additives become more fine, the fertilizer granules will tend to break down quicker and to release the essential elements into the surrounding soil and plant roots.
The additives are incorporated into the fertilizers prepared according to the subject invention until the weight percent of the additives is about 2% to about 5%. In specific embodiments, the weight percent of the additives in the subject fertilizers is about 2%, about 2.1%, about 2.2%, about 2.3%, about 2.4%, about 2.5%, about 2.6%, about 2.7%, about 2.8%, about 2.9%, about 3%, about 3.1%, about 3.2%, about 3.3%, about 3.4%, about 3.5%, about 3.6%, about 3.7%, about 3.8%, about 3.9%, about 4%, about 4.1%, about 4.2%, about 4.3%, about 4.4%, about 4.5%, about 4.6%, about 4.7%, about 4.8%, about 4.9%, or about 5%. In one embodiment, the fertilizer is prepared from 0.5% MgO ore. In another embodiment, the fertilizer is prepared from 2.0% MgO ore. Advantageously, the additives can be incorporated into the fertilizers named in Tables I, II, and III in the weight percentages disclosed above.
In one embodiment, a high quality silica sand is the additive, and the sand is obtained from a silica deposit that yields products of at least 95% SiO 2 .
The additive enhanced fertilizers of the present invention may optionally be applied to the soil only once per growing season or applied multiple times. Optionally, the additive enhanced fertilizers can be applied to the leaves and stems of the plants.
As used in this specification and the appended claims, the singular forms “a”, “an”, and “the” include plural reference unless the context clearly dictates otherwise. Thus, for example, a reference to “a plant ” includes more than one such plant.
The terms “comprising”, “consisting of”, and “consisting essentially of” are defined according to their standard meaning and may be substituted for one another throughout the instant application in order to attach the specific meaning associated with each term.
The term “dolomitic phosphatic clay slime” also refers to montmorillonite clay slime. They may be substituted for another throughout the instant application.
The term “phosphogypsum” refers to gypsum (i.e., calcium sulfate) that is the by-product of phosphoric acid production.
The term “silica sand” is interchangeable with the term “industrial sand” and refers to high quality quartz (SiO 2 ). Silica sand is deposited by natural processes and exhibits a crystalline structure.
The term “natural gypsum” is interchangeable with the term “gypsum” and refers to naturally forming hydrated calcium sulfate [CaSO 4 .2(H 2 O)].
Following are examples which illustrate procedures for practicing the invention. These examples should not be construed as limiting. All percentages are by weight and all solvent mixture proportions are by volume unless otherwise noted.
EXAMPLE 1
In a preferred embodiment, the following steps are performed:
Step 1
40%-90% (preferably 70%) sulfuric acid (H 2 SO 4 ) is reacted with dolomitic phosphate to yield a mixture containing 34-41% H 2 SO 4 and 59-66% dolomitic phosphate. The mixture is heated at about 100°-130° C. for approximately 15-30 minutes to form water soluble monocalcium phosphate Ca(H 2 PO 4 ) 2 .H 2 O and CaSO 4 .2H 2 O
a) Ca 10 (CO 3 )(PO 4 ) 6 +7H 2 SO 4 →3Ca(H 2 PO 4 ) 2 .H 2 O+7CaSO 4 .2H 2 O+H 2 CO 3
b) CaCO 3 .MgCO 3 +2H 2 SO 4 →CaSO 4 .2H 2 O+MgSO 4 .7H 2 O+2CO 2 (as gas)
Step 2
Dolomitic phosphatic clay slime (approximately 5-20%, preferably 11% solids) is mixed with 0.05% Fe, 0.02% Zn, 0.001% Cu, 0.0002% Mn, 0.0002% Se, 0.0001% B, 0.0001% Cr, 0.0001% Co, and 0.0001% Mo and added to yield a mixture containing 35-55% (dolomitic phosphatic clay slime mixture) and 45-65% (monocalcium phosphate mixture). The mixture is heated for 30-90 minutes at about 70° C.-100° C. The water in the slime disproportionates the Ca(H 2 PO 4 ) 2 .H 2 O to CaHPO 4 .2H 2 O and phosphoric acid (H 3 PO 4 ). The H 3 PO 4 dissolves additional phosphate ore, and reacts with the dolomitic phosphatic clay slime binding the soluble essential elements to the clay platlets. In addition, the H 3 PO 4 reacts with aluminum at the periphery of the clay platlets linking them together.
Step 3
Enough finely divided dolomitic phosphate ore is added at about 70° C. to 100° C. to partially neutralize the H 3 PO 4 and bring the pH to about 3-6.
Step 4
Finally, KCl and urea are added to yield a mixture containing 2-12% KCl and 8-15% urea. Urea raises the pH and displaces hydrate water from biproduct gypsum (CaSO 4 .2H 2 O), dicalcium phosphate (CaHPO 4 .2H 2 O), and monocalcium phosphate (Ca(H 2 PO 4 ) 2 .H 2 O). Because urea is a bidentate amine ligand, it coordinates any free transition essential element ions, calcium ions, and magnesium ions binding them together. The mixture is heated to between 100°-120° C., thereby driving off the water and granulating the remaining mixture into hard granules for application. The resulting granules release the essential elements slowly as moisture is added. As a result, most of the essential elements remain in the soil and loss of essential elements to rain water runoff is thereby reduced.
EXAMPLE 2
Four rows were planted with ten plants of tomatoes per row. The tomato variety was Florida 47. The plants were spaced two feet apart, and each of the rows were spaced five feet apart.
Different fertilizers, including specific embodiments of the present invention, were applied to the soil surrounding the tomato plants and a top the tomato plants. The fertilizer was applied to completely surround the tomato plants.
One fertilizer was a 10-10-10 fertilizer with no added nutrients. A second fertilizer was prepared from 2.0% MgO ore. A third fertilizer was prepared from 0.5% MgO ore.
Tomato plants fertilized with the above were compared (average tomato yield per plant) to tomato plants fertilized with a 10-10-10 fertilizer prepared from 2.0% MgO ore and the additive phosphogypsum. The specific embodiments included a fertilizer prepared with a dolomite clay slime and a fertilizer prepared with a dolomite clay slime and phosphogypsum. Each plant was fertilized only at the time of planting; each plant was watered daily with a soker hose.
The tomatoes grew to a height of approximately two feet, regardless of the type of fertilizer. The tomato plants fertilized with the fertilizers of the invention were not attacked by insects nor did fungus grow at the juncture between the stem and the fruit. These tomatoes' diameters were approximately within the range of 3-4 inches. The yield is given in Table IV.
Inasmuch as the preceding disclosure presents the best mode devised by the inventor for practicing the invention and is intended to enable one skilled in the pertinent art to carry it out, it is apparent that methods incorporating modifications and variations will be obvious to those skilled in the art. As such, it should not be construed to be limited thereby but should include such aforementioned obvious variations and be limited only by the spirit and purview of this application.
TABLE I
Processing Conditions
Ex. No.
Type
Size
Amt
H 2 SO 4
Amt
Temp
Time
Type
VI-JP
Ore
μm
g
%*
g
° C.
min
clay**
3
CFI, 0.5
−212
18.0
95.5
7.2
120
20
P. clay slime
4
CFI, 0.5
−212
18.0
95.5
7.2
120
20
P. clay slime
5
CFI, 0.5
−212
18.0
95.5
7.2
120
20
P. clay slime
6
CFI, 0.5
−212
18.0
95.5
7.2
120
20
P. clay slime
7
CFI, 2.0
−212
18.0
95.5
7.2
120
20
P. clay slime
8
CFI, 0.5
−212
18.0
95.5
7.2
120
20
P. clay slime
9
CFI, 0.5
−212
18.0
95.5
7.2
120
20
P. clay slime
10
CFI, 0.5
−212
18.0
95.5
10.0
120
20
P. clay slime
11
CFI, 0.5
−212
18.0
95.5
14.0
120
20
P. clay slime
12
CFI, 0.5
−212
18.0
95.5
10.0
120
100
P. clay slime
13
CFI, 0.5
−212
18.0
95.5
11.0
120
20
P. clay slime
14
CFI, 2.0
−212
18.0
95.5
11.0
120
20
P. clay slime
15
CFI, 2.0
−212
18.0
95.5
11.0
120
20
P. clay slime
16
CFI, 2.0
−212
18.0
95.5
11.0
120
20
P. clay slime
17
CFI, 0.5
−212
18.0
95.5
11.0
120
20
P. clay slime
18
TGS
−420/+200
18.0
95.5
11.0
120
20
P. clay slime
19
DOR, ZIM
−106
18.0
95.5
11.0
120
20
P. clay slime
20
CFI, 0.5
−212
18.0
95.5
11.0
120
20
P. clay slime
21
CFI, 0.5
−212
18.0
95.5
11.0
120
20
P. clay slime
22
CFI, 0.5
−212
18.0
95.5
11.0
120
20
P. clay slime
23A
CFI, 2.0
−212
18.0
95.5
11.0
120
20
water
23B
CFI, 2.0
−212
18.0
95.5
11.0
120
20
water
23C
CFI, 2.0
−212
18.0
H 3 PO 4 ,
11.3
120
20
water
85.2%
Ex. No.
Amt
Temp
Time
Type
Amt
Temp
Time
Final Wt
VI-JP
g
° C.
min
urea/KCl
g/g
° C.
min
g
3
10
80
10
gran/gran
6.0/6.0
80/100
120
34.4
4
10
80
10
gran/gran
7.0/6.0
80/120
120
36.3
5
10
80
10
gran/gran
9.8/2.4
80/120
120
34.2
6
10
80
10
gran/gran
12.0/6.0
90/120
120
39.7
7
10
80
10
gran/gran
5.9/4.0
85/105
120
33.5
8
10
80
10
gran/gran
5.9/4.3
80/110
120
33.9
9
10
80
10
gran/gran
7.4/5.3
80/110
120
35.3
10
10
80
10
gran/gran
8.0/5.3
80/110
120
37.0
11
10
80
90
none/none
8.8/6.3
80/110
120
42.6
12
10
80
60
gran/gran
0/0
80/110
120
25.8
13
20
80
35
gran/gran
9.0/6.5
80/110
120
41.1
14
20
80
35
gran/gran
11.0/5.2
80/110
120
45.2
15
20
80
60
gran/gran
10.0/3.4
80/110
120
43.6
16
30
80
60
gran/gran
10.0/3.4
80/110
120
44.4
17
30
80
60
gran/gran
10.0/3.4
90/120
120
44.5
18
30
80
45
gran/gran
10.0/3.4
80/110
120
44.0
19
30
80
60
gran/gran
10.0/3.4
90/110
120
44.1
20
30
80
60
gran/gran
10.0/3.4
90/110
120
43.5
21
30
80
60
gran/gran
10.0/3.4
90/110
120
45.1
22
30
80
60
gran/gran
10.0/3.4
90/110
120
44.9
23A
10
80
60
gran/gran
10.0/3.4
90/110
120
39.2
23B
10
80
60
none
xxxxxxx
xxxxxx
xxxx
26.3
23C
10
80
60
none
xxxxxxx
xxxxxx
xxxx
26.1
*4.0 H 2 Og also added to H 2 SO 4
**Dolomitic-phosphate montmorillonite clay slime (11% solids) containing micro-elements Fe, Zn and trace elements Cu, Mn, Se, Cr, Mo, B, Sn, V, Si
TABLE II
PRODUCT COMPOSITION (%)
Ex. No.
Total
Water
Citrate
Avail
VI-JP
P 2 O 5
Sol P 2 O 5
Sol P 2 O 5
P 2 O 5
N2
K 2 O
Ca
S
Mg
Cl
03
14.4
1.3
6.5
7.8
8.1
11.2
6-8
6.4
0.5
8.0
04
15.2
0.5
7.0
7.6
9.1
10.8
6-8
6.4
0.5
7.6
05
14.6
0.8
7.9
8.7
14.1
4.1
6-8
6.4
0.5
3.0
06
13.9
0.6
5.8
6.4
14.0
9.7
6-8
6.4
0.5
7.0
07
~7
8.1
6.2
6-8
6.4
1.0
4.5
08
~7
8.1
6.3
6-8
6.4
0.5
4.5
09
~7
9.7
5.2
6-8
6.4
0.5
4.0
10
13.2
3.1
6.5
9.5
10.1
5.3
14
8.2
0.5
4.0
11
12.3
2.1
7.6
9.6
10
10
13
8.2
0.5
~8
12
2.0
0
0
19
13.0
0.5
<0.5%
13
13.3
1.7
11.5
13.1
10.2
10.0
17
8.2
0.5
7.7
14
13.1
10.2
6.1
8.2
1.0
~5
15
13.1
9.0
4.9
8.2
1.0
~4
16
13.1
11.3
5.2
17
8.0
1.0
4.0
17
13.1
11.3
5.2
17
8.0
0.5
4.0
18
13.1
11.3
5.2
17
8.0
0.5
4.0
19
13.1
11.3
5.2
17
8.0
0.5
4.0
20
13.1
11.3
5.2
17
8.0
0.5
4.0
21
13.1
11.3
5.2
17
8.0
0.5
4.0
22
13.1
11.3
5.2
17
8.0
0.5
4.0
23A
~14
11.3
5.2
17
8.0
0.5
4.0
23B
~19
0
0
27
~12
~7.5
0
23C
?
0
0
27
—
~7.5
0
TABLE III
DEGRATION OF FERTILIZER GRANULES*
Exp. No.
Granule
One
Two
Four
Six
Eight
Ten
Twelve
Sixteen
Twenty
VI-JP
Firmness
Week
Weeks
Weeks
Weeks
Weeks
Weeks
Weeks
Weeks
Weeks
Comments
03
Firm
Sl.d.
Sl.d.
Sl.d.
Mod.d.
Mod.d.
Mod.d.
Mod.d.
Ext.d.
Ext.d.
Contains
unreacted ore
04
Soft
Mod.d.
Mod.d.
Ext.d.
Com.d.
05
Soft
Mod.d.
Mod.d.
Com.d.
06
Soft
Mod.d.
Mod.d.
Com.d.
07
Firm
Mod.d.
Mod.d.
Mod.d.
Mod.d.
Mod.d.
Mod.d.
Mod.d.
Mod.d.
Mod.d.
Contains
unreacted ore
08
Soft
Mod.d.
Mod.d.
Mod.d.
Ext.d.
Com.d.
09
Firm
Mod.d.
Mod.d.
Mod.d.
Ext.d.
Ext.d.
Ext.d.
Ext.d.
Ext.d.
Ext.d.
Contains
unreacted ore
10
Firm
Ext.d.
Ext.d.
Ext.d.
Ext.d.
Ext.d.
Ext.d.
Com.d.
11
Soft
Mod.d.
Mod.d.
Mod.d.
Ext.d.
Ext.d.
Ext.d.
Com.d.
12
V. Soft
Ext.d.
Com.d.
13
Firm
Sl.d.
Sl.d.
Mod.d.
Mod.d.
Ext.d.
Ext.d.
Ext.d.
Ext.d.
Ext.d.
14
Firm
Ext.d.
Ext.d.
Com.d.
15
Firm
Ext.d.
Ext.d.
Com.d.
16
Firm
Ext.d.
Ext.d.
Com.d.
17
Firm
Ext.d.
Ext.d.
Ext.d.
Ext.d.
Ext.d.
Com.d.
18
Soft
Ext.d.
Ext.d.
Ext.d.
Ext.d.
Ext.d.
Ext.d.
19
Firm
Mod.d.
Mod.d.
Mod.d.
Mod.d.
Mod.d.
Mod.d.
20
Firm
Mod.d.
Ext.d.
Ext.d.
Ext.d.
Ext.d.
Ext.d.
21
Firm
Mod.d.
Ext.d.
Com.d.
22
Soft
Ext.d.
Ext.d.
Ext.d.
Ext.d.
Ext.d.
Ext.d.
23A
Firm
Sl.d.
Mod.d.
Mod.d.
Mod.d.
Mod.d.
Mod.d.
Mod.d.
23B
Soft
Com.d.
23C
Soft
Com.d.
TABLE IV
COMPARISON OF A 10-10-10 MICRO ELEMENTS FERTILIZER
WITH THREE DIFFERENT SLOW-RELEASE FERTILIZERS
Type Fertilizer
Average Yield Tomatos/Plant
Row 1B
Commercial Ferilizer
2.4
Row 3A
10-10-10 fertilizer prepared
4.0
with 2.0% MgO (VI-JP14)
Row 3B
10-10-10 fertilizer prepared
4.5
with 0.5% MgO and 13%
calcium (VI-JP13)
Row 4B
10-10-10 fertilizer prepared
7.2
with 2.0% MgO and 5%,
ground phosphogypsum added
during final granulation
REFERENCES
Foth, H. D. and B. G. Ellis (1997) Soil Fertility , (2 nd ed.) Lewis Publishers, New York, N.Y.
Moffat, A. S. (1999) “Engineering plants cope with metals,” Science 285:369-370.
Paton, T. R. (1978) The formation of Soil Material , George Allen and Unwin, Boston, Mass.
Stanitski, C. L., L. P. Eubanks, C. H. Middlecamp, and W. J. Stratton (2000), Chemistry in Context , (3 rd ed.), McGraw Hill, Boston.
Tan, K. H. (1998) Principles of Soil Chemistry , (3 rd ed.), Marcel Decker, Inc., New York, N.Y.
Whittaker, C. W., F. O. Lundstrom, and S. B. Hendricks (1933) “Reactions between Urea and Gypsum,” Industrial and Engineering Chemistry 25:1280-1282. Wright, R. (1999) “Milestone means worry as planet hits 6 billion,” Tampa Tribune, 18 July, World population hits 6 billion, Tampa Tribune, 12 October. | Several compositions of matter have been discovered that can be used in the manufacture of slow-release fertilizers that contain all of the essential elements needed by plants and humans. Slow-release fertilizers manufactured with these formulations can be used on mineral stressed soils to increase the quality and production of food crops grown on them. Additives, including phosphogypsum, silica sand, natural gypsum, clay, and coal dust, facilitate the timing of the release of the essential elements into the soil. | 2 |
BACKGROUND
[0001] 1. The Field of the Invention
[0002] This invention relates to ski lifts and in particular to informational displays available and presented to riders on a chair lift system.
[0003] 2. The Background Art
[0004] Riders of ski chair lifts may spend considerable time riding a lift up a mountain side to the beginning of a particular run or series of runs, before skiing down one or more of those runs to the bottom to repeat the exercise. While skiing, a skier does exercise and may maintain body warmth by virtue of that exercise. However, considerable time is spent in a virtually stationary position in the chair. Moreover, considerable time is spent waiting in line at some resorts. Thus, considerable time is spent idle.
[0005] Typically, users may have only limited time to review area maps posted on signs about a ski resort. Instead, a user or rider of a ski lift may typically have a folded map in a pocket. Folded maps are necessarily problematic. Removing bulky gloves to unfold a map and fold it up again is not highly effective, and can be very uncomfortable.
[0006] For example, high above the surface of the earth, ski chair lifts may sometimes be dozens of feet high in the air. Thus, riders are exposed to wind and cold. Removing gloves and mittens while riding a chair life is hardly recommended due to the cold weather.
[0007] Riding a lift a user or rider is provided only limited opportunity for movement and thus is exposed to full force of the prevailing climate, which is typically cold to support the necessary environment for a ski resort. Comfort may be improved by keeping protective clothing in place.
[0008] Meanwhile, riders have a limited time upon completing a run to review a larger area map posted on signage at the resort. Moreover, a user must go back into a line to wait for the next chair. Thus, it would be an advance if a user of a ski resort, a rider, a skier, could have access to a map, already printed, mounted right on the lift chair that a particular user is riding.
BRIEF SUMMARY OF THE INVENTION
[0009] In accordance with the foregoing, an apparatus and method in accordance with the invention provide a system of displays or panels that may be divided into an information region, and an advertising region. Typically, the information region occupies the largest and central portion of a panel. Meanwhile, the panel may be mounted to a safety bar that drops down in front of the riders upon seating themselves on the lift chair.
[0010] A display system is easily attached to the safety bar of a chair on a chair lift system at the beginning of a season. The display system includes brackets formed of rails holding clamp portions that may be fastened together to clamp the display system to a chair, such as to the safety bar across the lap of a rider. At the end of a season, the display system may be removed from each chair, the clamp portions removed, and the display systems stacked. In one simplified system, adjacent displays may be stacked back to back, and such adjacent pairs may be stacked with the displays in adjacent pairs positioned face-to-face. Thus, metal brackets on the backs need not scratch up the reading faces or surfaces. Meanwhile, the displays may be stored in minimal space, with great stability, while minimizing wear and damage.
[0011] Thus, an apparatus in accordance with the invention may include a system of brackets to secure a spine to the safety bar, and a panel to the spine. The panel may include informational regions and advertising regions to inform users concerning the resort, as well as other commercially available benefits, such as lessons, ski equipment, food, other products, or sponsored events or products. In certain embodiments, the visible panels may be subdivided physically as well as content-wise in order to be able to change out certain portions of a panel when that information become obsolete Likewise, when sponsored information receives a new sponsor, it may require new information or sponsor information.
[0012] In certain embodiments, a bracket may be easily removed in order that the system may be stored out of the weather during off season times. In particular, a bracket system may include a rail that receives fingers or clamps into a slide path or a way along the rail. Thus, the brackets, or at least the clamps if not the rails, may be readily removed in order to stack the panels together. Removable clamps may both stabilize them as a stacked array of panels, as well as reducing thickness, thus occupying considerably less space.
[0013] Thus, the larger dimensions in a direction parallel to the horizontal plane of a panel occupies considerable space. It is a saving of space to remove the clamps from a rail, which together form the bracket system. Thereby, the panels may be laid face to face or back to back in alternating pairs. The rails may be slightly offset in order to minimize the amount of space occupied by a set of stored panels. In due course, the systems may be reassembled. The brackets may be reassembled by sliding the clamps into the rails. With the attachment of a few fasteners, the panels may be reinstalled on the safety bars of the lift chairs of a ski lift.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The foregoing features of the present invention 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 typical embodiments of the invention and are, therefore, not to be considered limiting of its scope, the invention will be described with additional specificity and detail through use of the accompanying drawings in which:
[0015] FIG. 1 is a top, rear quarter perspective view of one embodiment of the apparatus in accordance with the invention;
[0016] FIG. 2 is a bottom rear quarter, perspective view of the apparatus of FIG. 1 ;
[0017] FIG. 3 is a perspective, exploded view of the apparatus of FIGS. 1-2 ;
[0018] FIG. 4A is a top plan view of the apparatus of FIGS. 1-3 ;
[0019] FIG. 4B is a top plan view of the one alternative embodiment of the apparatus of FIGS. 1-4A , having the panel portion subdivided into removable sub-portions;
[0020] FIG. 5A is a top plan view of the apparatus of FIGS. 1-4 , this one having a more rectangular shape for the main panel;
[0021] FIG. 5B is a top plan view of an alternative embodiment of the apparatus of
[0022] FIG. 5A , this corresponding to FIGS. 1-5A , but providing for both rectangular shaping of the main panel area, and also separable or removable portions of the panel;
[0023] FIGS. 6A-6D are bottom plan views of the apparatus of FIGS. 4A , 4 B, 5 A, and 5 B, respectively;
[0024] FIG. 7 is a front elevation view of the apparatus of FIGS. 4A and 5A ;
[0025] FIG. 8 is a rear elevation view of the apparatus of FIGS. 4 and 5 ;
[0026] FIGS. 9A and 9B are right end elevation view of the apparatus of FIGS. 4 and 5 , respectively;
[0027] FIGS. 10A and 10B are left end elevation views of the apparatus of FIGS. 4 and 5 , respectively;
[0028] FIG. 11 is a perspective view of one embodiment of a bracket in accordance with the invention, comprising a rail on which two independent clamps may slide toward one another to be secured to one another, clamping a safety bar from a lift chair therebetween;
[0029] FIG. 12 is a perspective view of an alternative embodiment of a bracket for use in the apparatus of FIGS. 1-10 , this particular bracket having an integrally, even homogeneously, formed clamp formed with the rail, and a second freely sliding clamp engaging the rail;
[0030] FIG. 13 is a perspective, exploded view of the bracket assembly of the apparatus of FIGS. 1-10 , and specifically the embodiment of FIG. 11 , also showing alternative embodiments of the cross section of the rail;
[0031] FIG. 14 is a partially cut away view of the joint region, for the apparatus of FIGS. 1-10 , and in particular, illustrates alternative mechanism for implementing an embodiment of FIGS. 1-10 and in particular the embodiment of FIGS. 4B and 5B wherein the panel is subdivided into different physical portions that are selectively attachable and removable in accordance with the invention; and
[0032] FIG. 15 is a perspective view of one embodiment of an apparatus in accordance with the invention, this embodiment including both the chair of a chair lift and its associated panel assembly in accordance with the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0033] It will be readily understood that the components of the present invention, as generally described and illustrated in the drawings herein, could be arranged and designed in a wide variety of different configurations. Thus, the following more detailed description of the embodiments of the system and method of the present invention, as represented in the drawings, is not intended to limit the scope of the invention, as claimed, but is merely representative of various embodiments of the invention. The illustrated embodiments of the invention will be best understood by reference to the drawings, wherein like parts are designated by like numerals throughout.
[0034] Referring to FIGS. 1-10 , an apparatus 10 or system 10 in accordance with the invention may include a display 12 or a panel 12 . The display 12 may be divided into regions 13 generally, including information regions 14 and advertising regions 16 . Each information region 14 may be designated for display of particular information. For example, the advertising region 16 may be devoted to advertising information. Meanwhile, the central region 14 may be designated for other, non-commercial information.
[0035] In one embodiment in an apparatus and method in accordance with the invention, the information region 14 may contain a map of a ski area. The map may be available to multiple riders sitting on a chair lift. In the illustrated embodiment, a user may view the information region 14 in order to determine a desirable area in which to ski. By providing a map in the information region 14 , a ski resort may thus improve traffic, better serve customers, and otherwise promote the satisfaction of users of the ski area.
[0036] In general, an apparatus 10 may be assembled as part of a ski lift chair. In certain embodiments, the apparatus 10 be considered to be both the display system 12 as well as the ski lift chair in its entirety. This may even include the towers. In other embodiments, the system 10 may include simply that portion thereof that will attach to a lift chair.
[0037] Nevertheless, in general, chair lift systems typically include towers provided with rollers across which a cable may pass. Chairs are suspended by hangers or columns from the cable. Typically an engine of some type will operate at one end of a loop formed of the cable, such as at the bottom or at the top of a ski run. The motor, driving a large sheave about which the cable passes in a closed loop, thus moves the cable along, drawing the lift chairs with the cable up the mountain and back down.
[0038] Typically, riders in a ski resort environment will ride the chair life from the bottom to the top. In some instances, maintenance personnel, safety personnel, and other staff may ride the chair lift down the mountain as well. In sight-seeing venues, riders may actually ride the lifts upward and downward on a regular basis.
[0039] An apparatus 10 or system 10 in accordance with the invention, may include a back bone 18 or spine 18 in addition to the display 12 . In order to maintain the information region 14 and advertising region 16 readable, to minimize distortion, to avoid random reflections of light therefrom, a spine 18 may increase the stiffness thereof.
[0040] As an engineering principle, a section modulus is increased in order to stiffen a material or a structure. Section modulus is increased when material is moved, placed, or otherwise located as far as possible from the neutral axiss. The neutral axis is the axis of zero stress and is typically near the center of a weighted cross-sectional area, as defined by engineering principles of radius of gyration of a cross section, and so forth. Thus, in one embodiment of an apparatus and method in accordance with the invention, a spine 18 may be formed to secure, fasten, bond, or otherwise attach or may be formed directly or integrally with the display 12 in order to provide increased stiffness thereof. The cross section may be rectangular, a box, a ‘T,’ and ‘L,’ a channel, or the like.
[0041] Stiffening the display 12 permits the maintenance of the desired shape. For example, in one embodiment, the display 12 may be substantially flat. In such an embodiment, any variation away from flatness tends to increase the chance of random reflections of light at multiple angles. Such random curvature may greatly interfere with the visibility or readability of materials due to random reflections of light making difficult the viewing of the display 12 from a single, selected angle chosen by a user.
[0042] The display 12 may be secured to a safety rail or safety bar of a chair lift by brackets 20 . Various embodiments of brackets 20 are contemplated in an apparatus 10 in accordance with the invention. Nevertheless, in one presently contemplated embodiment that has demonstrated many useful and valuable features, a bracket 20 may include a rail 22 or rail portion 22 and correspondingly fitted clamps 24 . In certain embodiments, the rail 22 may be formed with a portion of a clamp 24 as a homogeneously formed part thereof. In other embodiments, the clamps 24 may be completely separable from the rail 22 , and may be formed separately in a manufacturing process.
[0043] One advantage of a rail 22 having no clamps 24 integrally formed therewith is that the rail 22 may then be machined by a faster process, may be extruded, or may be otherwise manufactured in a simpler process. By contrast, inclusion of at least a portion of a clamp 24 as part of a rail 22 may involve more complex forming, molding, and the difficulties of release from such a mold.
[0044] The rail 22 and clamps 24 may be made of the same or different materials. Similarly, the rail 22 and clamps 24 may be provided in sizes and numbers to provide adequate securement by the brackets 20 of the display 12 to a chair apparatus of a chair lift.
[0045] In the illustrated embodiment, the clamps 24 may include apertures 25 . The apertures 25 may be formed, for example, into or through a portion of each rail 22 . Apertures 25 may thus receive fasteners.
[0046] In one embodiment, apertures 26 may also be formed in the spine 18 . The apertures 27 may receive securement mechanisms passing through the spine 18 , and into the apertures 25 of the brackets 20 . For example, the apertures 25 may be threaded to receive a machine screw. In this way, a counter-bore on the apertures 26 of the spine 18 may receive the head of a button-head, internal hex, or other machine screw. Thus, the spine 18 may present a substantially completely flat surface for receiving the display 12 secured thereto without projections extending therefrom.
[0047] In one embodiment of an apparatus and method in accordance with the invention, the apertures 26 in the spine 18 for receiving the fastening mechanisms of the brackets 20 may be clear holes, having no threads therein Likewise, at another location or several other locations, apertures 25 in the spine may be formed in order to secure the spine 18 to the panel 12 or display 12 . In such an embodiment, the apertures 28 in the panel 12 may receive the same fasteners that pass through the apertures 27 in the spine in order to secure together the spine 18 and the display 12 . Thus, the spine 18 and display 12 or panel 12 may form an assembly, which assembly may be assembled after the rails 22 have been assembled with the spine 18 . In this way, the apertures 26 of spine 18 be occluded or hidden ,typically, under the display 12 . The display 12 may typically be formed of a clear durable material having information printed, embossed, painted, laminated, or otherwise fixed on the underside thereof and thus protected from weather.
[0048] As a practical matter, the apertures 25 in the rails 22 and brackets 20 may be aligned with both the apertures 26 and the apertures 27 . In other words, the apertures 26 may be formed and placed to be identical to the apertures 27 , in order to assemble the brackets 20 , the spine 18 , and the display 12 with a single set of fasteners through a single set of apertures 26 , 27 . Nevertheless, manufacturing processes are sometimes best adapted to provide for sequential rather than simultaneous securement of several mechanisms to one another as described above.
[0049] For example, fasteners 30 pass through the spine 18 in the illustrated embodiment in order to secure the spine 18 to the brackets 20 . As illustrated here each of the fasteners 30 passes through the an aperture 26 in the spine 18 , and is threaded into an aperture 25 in a rail 22 of a bracket 20 . In contrast, each fastener 32 passes through a panel 12 and the apertures 28 therein, also passing through apertures 27 in the spine 18 . Typically, the fasteners 30 are threaded into the apertures 25 in the rails 22 . However, the fasteners 32 are typically formed to include both a screw or bolt portion and a nut portion in order to clamp the display 12 and the backbone 18 or spine 18 together therebetween.
[0050] Nevertheless, in certain embodiments, the fasteners 30 and 32 may be combined to use a single fastener 30 that passes through the display 12 , through the spine 18 , by way of apertures 28 in the panel 12 , the apertures 27 in the spine, which act in dual purpose as the apertures 26 as well. Thus, the fastener 30 ultimately threads into the apertures 25 in the rails 22 of the brackets 20 .
[0051] In general, a fastener 32 may be configured as a machine screw, having a counter sunk head, a cap head, or the like. Meanwhile, a nut 34 or keeper 34 may secure to the fastener 32 and tighten along the fastener 32 in order to clamp the display 12 or panel 12 securely against the spine 18 or backbone 18 . Nevertheless, in certain embodiments, the fasteners 32 may include rivets. In such an event, a keeper 34 may often be simply a washer to be held in place by the swelling of the rivet and opposite the head thereof. Meanwhile, other types of fasteners 32 may be used separately, or in combination with other fasteners described herein.
[0052] In certain embodiments of apparatus and methods in accordance with the invention, additional fasteners 36 may facilitate a selective separation and engagement of display 12 in which the information region 14 at the center of the display 12 is actually a physically separate piece from the advertising regions 16 . For example, in the example of a ski resort, a map of a ski resort is not likely to change repeatedly or frequently in a season or often over several years.
[0053] By contrast, advertisers may contract for a single season. Accordingly, the advertising regions 16 may benefit from being replaced by new advertising regions every season, or perhaps within a season. Accordingly, it may be beneficial to make the panel 12 or display 12 in such a way that the advertising regions 16 are removable and replaceable. In order to provide this interchangeability at disparate times between the information region 14 and the advertising regions 16 , fasteners 36 may be developed and installed to provide alignment in all three dimensions, or less, between the regions 14 and the regions 16 .
[0054] For example, in certain embodiments, alignment of straight edges may be sufficient to secure the alignment of the information region 14 and the advertisement region 16 against rotation or translation in any direction that may cross the line of demarcation therebetween. Nevertheless, if those edges are both flat, then they may slide vertically with respect to one another.
[0055] For example, in the plane of the display 12 , a certain amount of misalignment may occur in a direction along the line of interface between the information region 14 and the advertisement regions 16 . Similarly, alignment perpendicular to the plane of the display 12 may be slightly problematic, absent some mechanism to maintain alignment.
[0056] The fasteners 36 may provide one manner in which a bolt, with or without large washers, a clip, a clamp, or the like may be provided as fasteners 36 to enforce alignment. Likewise, a cross section may be made along the interface between the information region 14 and the advertisement region 16 in order to secure alignment in a direction perpendicular to the plane of the panel 12 .
[0057] Referring to FIGS. 11-13 , while continuing to refer generally to FIGS. 1-15 , an apparatus 10 in accordance with the invention may rely on a bracket 20 comprising a rail 22 supporting a clamp 24 . In certain embodiments, one of the clamps 24 may actually be formed into the rail 22 . In other embodiments, the rail 22 may be of a constant cross sectional area and shape, receiving therein two clamps 24 . One benefit to the latter configuration is that the apparatus 10 may be stowed during the off-season more readily.
[0058] For example, in the embodiment of FIG. 11 , the clamps 24 may be removed from the rails 22 . The resulting additional thickness of a rail 22 added to the spine 18 and the panel 12 is about an inch or less. If the rail 22 is formed with one of the brackets 24 as a monolithic and homogenous extension thereof, then the total thickness may be something closer to 3 inches. Moreover, the shape of a clamp 24 may render a stack of panels 12 quite unstable.
[0059] In contrast, the uniform dimension and the straight line or plane represented by the externally exposed surface of each of the rails 22 will tend to provide a stabilizing influence. For example, the apparatus 10 may be stowed with the clamps 24 completely removed from the rails 22 . In this way, the various instances of the apparatus 10 may be placed alternating face-to-face together, and then back-to-back together in alternating pairs throughout a stack. Each of the rails 22 may be offset compared to the adjacent rails 22 of the next display 12 in order. In this way, even the ribs or spine 18 may be offset in stacking. Thus, two of the apparatus 10 may be placed with rails facing, but offset, in such a way that the entire thickness of a stacked pair is only increased by ⅛th inch. This may provide almost double the number panels 12 stacked up in a given space. Storage and stowing are operational and space considerations.
[0060] The exploded view of FIG. 13 illustrates one manner in which a rail 22 may be configured, to have a base portion 38 into which the aperture 25 will be formed, such as by drilling. Meanwhile, along the length of the rail 22 , the cross sectional configuration provides a way 40 . A foot 42 or foot portion 42 of a clamp 24 may be set away from the main body of the clamp by a stem 44 . In certain embodiments, the material of the clamp 24 , including the stem 44 and its attached foot 42 may be forged, machined, cast, molded, or otherwise manufactured by a suitable method.
[0061] The foot 42 slides into and along the rail 22 in the way 40 . The way 40 may connect directly to a slot 46 formed in the top wall 54 of the rail 22 . Accordingly, the way 40 may be provided with a detent. The detent may be one of the fasteners 30 formed and sized to extend slightly into the way 40 . For example, at an appropriate point, one of the fasteners 30 may extend into the aperture 25 , and out into the way 40 . If such a location is artfully chosen, then the feet 42 of two opposing clamps 24 riding in that way may effectively bracket the detent (such as a fastener 30 ) in order to maintain their own position. An aperture 48 may be a completely clean aperture 48 lacking any threads. Meanwhile, a corresponding aperture 50 may be threaded into the corresponding opposite bracket clamp 24 . In certain embodiments, a fastener 52 , such as a machine screw or the like, may pass through the clear aperture 48 and thread into a threaded aperture 50 . Thus, the two opposing clamps sliding in the rail 22 may be drawn together.
[0062] If a detent 49 is provided, it may be a set screw in the side of a rail 22 , a welded or other button limiting movement, a fastener 30 may extend through the threaded aperture 25 and into the way 40 , to fit between the feet 42 of the two opposing clamps 24 . The fastener 52 may secure the two clamps 24 together. The detent 49 extending into the way 40 registers the two clamps 24 at fixed position along the rail 22 . In this way, the two clamps 24 may be registered at a position along the way 40 by the detent 49 . They are restrained to remain with the rail 22 by the top wall 54 wrapped around each of the feet 42 to secure it within the way 40 .
[0063] Referring to FIG. 13 , the way 40 may be formed to have any particularly useful cross section. For example, the base 38 may be made of a suitable thickness in order to provide sufficient purchase for a fastener 30 threaded into the aperture 25 . Meanwhile, the shape of the way 40 may provide for registration, clamping, easy sliding, or the like according to its shape. Some shapes contemplated may include a rectangle, a triangle, a trapezoid, a circle, or other suitable cross section.
[0064] In the event that one of the clamps 24 is integrally or homogeneously formed with the rail 22 , manufacturing costs will probably be comparably higher. If instead, the rail 22 is an extruded part, then substantially large lengths, even continuous lengths, of the rail 22 material may be extruded, and cut to length at a later time. Thus, the costs and manufacturing difficulty made be simplified by using a continuous rail 22 of a constant cross section.
[0065] Nevertheless, if a clamp 24 is formed integrally or homogeneously with a rail 22 , then that fixed clamp 24 may set the registration point against which the opposing clamp 24 will be drawn by a fastener 52 .
[0066] Referring to FIG. 14 , while continuing to refer generally to FIGS. 1-15 , a joint 60 may be formed at the interface between an information region 14 and an advertising region 16 of a display 12 or panel 12 . In the illustrated embodiment, various forms of registration elements 62 , 64 provide registration against the possibility of misalignment and surface roughness in a direction perpendicular to the plane of the display 12 or panel 12 .
[0067] For example, a male registration element 62 may be formed to be a simple corner, a corner extending out from a flat surface, a semicircle extending out from a flat surface, a semicircle, a trapezoid, a trapezoid extending out from a flat surface, or even a simple, flat, abutting joint 60 . Likewise, other shapes, such as a rectangular cross section having rounded edges for ease of installation may form the registration elements 62 , 64 .
[0068] In practice, the advertising region 16 may be provided with a detent, such as a ridge, boss, or the like extending slightly above the surface of the male registration element 62 . Similarity, a slight undercut for the corresponding mating registration element 64 may also include a detent, or simply grip the detent provided on the opposite piece. In this way, the advertising region 16 may actually snap to the information region 14 , or visa versa. Nevertheless, in certain embodiments, a pair of washers 66 or other fasteners may align the surfaces of the advertising region 16 and the information region 14 .
[0069] In the illustrated embodiment, one or more washers 66 , may be placed against the adjoining information region 14 and advertising region 16 about an aperture formed to receive a fastener 36 a. The fastener 36 a may thus pass through the aperture formed at the joint 60 in order to admit the fastener 36 and its keeper 34 , such as a nut. Accordingly, the washers 66 may be compressed together by the fastener 36 and its associated keeper 34 in order to maintain alignment in a direction perpendicular to the horizontal plane of the display 12 . Alternative embodiments of fasteners 36 are illustrated as a bolt 36 a, a clip 36 b, a rivet or plastic snap connector 36 c, a pop rivet 36 d, or the like. Each may fasten, contain, or both, the two regions 14 , 16 in alignment.
[0070] Other embodiments may rely on extensions of the spine 18 extending forward to the front edge of the panel 12 in order to maintain the alignment between adjacent regions 14 , 16 at their shared joint. The spine, for example, may extend coincident with the panel 12 in its entirety. The spine 18 , in such an embodiment, may be perforated with weight reduction apertures removing material in circles or other shapes in order to maintain maximum section modulus at minimum weight. Runners may extend the spine forward along the joint shared between two regions 14 , 16 . A narrow H-Beam may receive each region 14 , 16 at the joint.
[0071] Referring to FIG. 15 , while continuing to refer generally to FIGS. 1-15 , a chair 70 or a lift chair 70 may be suspended by a hanger 72 extending from a supporting cable 73 and extending down to support a yoke 74 . Typically, in order to accommodate riders loading, and standing on skis at the loading position, the front of a chair 70 must be completely clear. Thus, a rider standing in front of the chair 70 as the chair is brought around and behind the rider will strike close to the knees (back of the knees) of a rider. Thereupon, the rider sits down as the chair 70 sweeps forward.
[0072] Accordingly, the yoke 74 maintains the front of the chair 70 completely clear. Thus, no obstruction is present in front of the seat 76 nor in front of the back 78 , at least where the riders will be. Thus, the seat 76 and the seat back 78 will be clear.
[0073] However, having riders traveling by cable 73 many feet in the air above the surface of the mountain, can be dangerous. In order to keep riders in their seats, and protect against falls, a safety bar 80 may be configured, outwards, to pivot up or otherwise out of the way prior to riders seating themselves on the seat 76 of chair 70 . Upon sitting down on the seat 76 , and leaning against the back 78 , a rider may draw down on, or an attendant at the ski area may actuate, the safety bar. Thus the safety bar 80 may be dropped down, at the front, about a pivot 82 .
[0074] The safety bar 80 may be formed of a tubular material. Accordingly, each of the clamps 24 may be shaped to have a somewhat ‘V-shaped’ interior surface. Thus, the clamps 24 may be drawn together to secure the bracket 20 against a safety bar 80 , typically accommodating diameters of from about one inch to about 2 inches. Most safety bars 80 are circular in cross section, having a diameter of from about 1 to about 2 inches. Most have a one inch diameter, and others, common to the industry, typically have a diameter of up to one and three quarters inches. Thus, an apparatus 10 in accordance with the invention may be thought of as the assembly 10 attached to the chair 70 , and particularly to the safety bar 80 . Alternatively, one may think of the apparatus 10 as including both the chair 70 , and the entire assembly supporting the display 12 or panel 12 .
[0075] 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 which come within the meaning and range of equivalency of the claims are to be embraced within their scope. | A display system is easily attached to the safety bar of a chair on a chair lift system at the beginning of a season. The display system includes brackets formed of rails holding clamp portions that may be fastened together to clamp the display system to a chair, such as to the safety bar across the lap of a rider. At the end of a season, the display system may be removed from each chair, the clamp portions removed, and the display systems stacked. In one simplified system, adjacent displays may be stacked back to back, and such adjacent pairs may be stacked with the displays in adjacent pairs positioned face-to-face. Thus, metal brackets on the backs need not scratch up the reading faces or surfaces. Meanwhile, the displays may be stored in minimal space, with great stability, while minimizing wear and damage. | 1 |
RELATED APPLICATION
The present application is a divisional of U.S. patent application Ser. No. 11/126,853, filed May 10, 2005, which is a divisional of U.S. patent application Ser. No. 09/812,226, filed Mar. 19, 2001 entitled “Telecommunications Chassis, Module, and Bridging Repeater Circuitry,” the entirety of which are hereby incorporated by reference.
TECHNICAL FIELD
The present invention is directed to chassis for holding telecommunications modules, the modules themselves, and the repeater circuitry that may be contained within the modules. More specifically, the present invention is directed to a chassis and module with shielding and heat dissipation structures and to repeater circuitry for bridging applications.
BACKGROUND
A telecommunications chassis provides a mounting structure for telecommunications modules housing various types of circuitry. The telecommunications chassis must provide protection from externalities while also facilitating heat dissipation from the circuitry it contains. The chassis must also attempt to shield its interior from electromagnetic interference while limiting the amount of electromagnetic interference being emitted from the interior. For certain applications, such as providing uninterrupted service during maintenance, circuitry housed by the chassis may need to be moved from place to place. Thus, portability of the chassis for this type of application becomes important as well. As the data rate being handled by the circuitry within the chassis increases, the ability to shield and protect from externalities while dissipating heat becomes more difficult.
Similarly, with the telecommunications modules that may be housed by the chassis, the circuitry within the module must be protected from externalities within the chassis, the ability of the module to shield and protect the circuitry while dissipating heat becomes more difficult as the data rate being handled by the circuitry within the module increases.
Bridging repeater circuits, which may be housed by the modules and chassis previously discussed, must take a low-level electrical monitor signal from one device, such as a digital signal cross-connect, and recreate the electrical signal with the data and clock information intact and at a high level suitable for reception by another device. Bridging repeater circuits are useful where a device has failed or must otherwise be replaced but a break in service is to be avoided. The bridging repeater circuit bridges around the faulty device from one healthy device to a replacement device to establish signal transfer prior to the faulty device being disconnected. The bridging repeater circuit is generally housed by a portable structure which needs to provide protection from heat and interference so that it may be transported to the locations of faulty devices and successfully create the output signal. As the data rate increases, the repeater circuit's ability to recover the data and clock information from the low-level monitor signal to recreate the output signal becomes more difficult.
Therefore, there is a need for a chassis to provide protection to modules from externalities and interference while facilitating heat dissipation, even at high data rates and while being portable if necessary. There is also a need for a module to provide protection to circuits from externalities and interference while facilitating heat dissipation, even at high data rates. Additionally, there is a need for a bridging repeater circuit that can recover the data and clock portions from a low-level monitor signal to recreate a high-level output signal repeating the data and clock information, even at high data rates.
SUMMARY
The present invention includes various embodiments that facilitate telecommunications functions for electrical signals, including those with high data rates such as the STM-1 rate of 155.52 megabits per second (Mbps). A chassis and a module of the present invention provide heat dissipation and shielding structures that may be used for circuits operating at these high data rates. A repeater circuit of the present invention recovers data and clock information from low-level monitor signals to create an output signal with the data and clock information intact, even at these high data rates.
The present invention may be viewed as a telecommunications chassis. The chassis includes a shielding chamber having a first and second horizontal surface and a first and second vertical surface. The first and second vertical surfaces are disposed between the first and second horizontal surfaces, and the first and second horizontal surfaces and the first and second vertical surfaces are made of metal and are conductively connected. A vertical backplane has connectors for interfacing with repeater modules and is disposed between the first and second horizontal surfaces and the first and second vertical surfaces. The vertical backplane establishes contact with the first and second horizontal surfaces and the first and second vertical surfaces and has a ground conductor that is electrically connected to the connectors. An outer housing encompasses the shielding chamber and the vertical backplane and has an open side for receiving telecommunications modules. The outer housing has a first cover surface that is substantially parallel to but within a different spatial plane from the first horizontal surface and has a second cover surface that is substantially parallel to but within a different spatial plane from the vertical backplane. Spacing between the first cover surface and the first horizontal surface and spacing between the second cover surface and the vertical backplane form an airspace. A chassis ground conductor is also included and is electrically connected to the shielding chamber and the ground conductor of the vertical backplane.
The present invention may also be viewed as a telecommunications circuit module. The module includes a printed circuit board including circuitry. A metal backplate is substantially parallel to but within a different spatial plane from the printed circuit board. A metal shell has a frontplate, a top surface perpendicular to and extending from the frontplate, a bottom surface substantially parallel to the top surface and extending from a side of the frontplate away from the top surface, and a back surface perpendicular to the front plate and the top and bottom surfaces. The top surface, bottom surface, and back surface each has a folded edge that abuts the metal backplate to establish metal to metal contact. A metal jack holder extends perpendicularly from the printed circuit board and abuts the front plate, top surface, and bottom surface to establish metal to metal contact along a side away from the back surface. At least a portion of the circuitry is disposed between the frontplate and the backplate and between the metal jack holder and the back surface.
The present invention may be viewed as a repeater circuit. The repeater circuit includes an amplification portion that receives a first signal with data and clock information and increases the amplitude of the first signal to generate an amplified first signal. The amplification portion includes a current feedback amplifier stage and a voltage limiting amplifier stage. A transceiver portion receives the amplified first signal with increased amplitude, recovers the data and clock information from the received amplified first signal, and transmits a second signal with the data and clock information recovered from the first signal.
DESCRIPTION OF THE DRAWINGS
FIGS. 1A and 1B are front and back perspective views of an embodiment of the chassis of the present invention.
FIGS. 2A and 2B are perspective and right side views, respectively, of the sidewalls and front and rear trim pieces of the chassis.
FIGS. 3A and 3B are an exploded perspective view of inner components of the chassis and a perspective view of the chassis without outer coverings with the inner components being installed.
FIGS. 4A and 4B are a rear perspective view of the chassis without the outer coverings and an exploded perspective view of the rear cover piece and power supply, respectively.
FIGS. 5A , 5 B, and 5 C are a plan view of the uninstalled rear cover piece, power supply, and vertical backplane, a perspective of the rear cover piece and power supply showing ground wire connections, and a perspective with the top cover removed to show its ground wire connection.
FIG. 6 is a rear perspective view of the chassis without outer coverings showing ground wire connections and the rear cover piece installation.
FIGS. 7A , 7 B, and 7 C are an exploded perspective view of the chassis, an exploded detail view of the top outer covering fastener, and an exploded detail view of the bottom outer covering fastener, respectively.
FIGS. 8A and 8B are perspective views of an uninstalled door and hinge guide, respectively.
FIGS. 9A , 9 B, 9 C, and 9 D are a front perspective view, a rear perspective view, and exploded perspective views of an embodiment of the module of the present invention.
FIG. 9E is a perspective view of the chassis with a module partially inserted.
FIG. 10 is a plan view of the faceplate of the module.
FIG. 11 is a high-level block diagram showing the application of the bridging repeater circuit embodiment of the present invention to a network environment.
FIG. 12 is a block diagram of the circuitry of the bridging repeater circuit.
FIG. 13 is a block diagram of the input section of the bridging repeater circuit.
FIG. 14 is a circuit schematic of the input section.
FIG. 15 is a block-diagram of the power supply of the bridging repeater circuit.
FIG. 16 is a top layer view of the printed circuit board showing input signal paths.
FIG. 17 is an internal layer view of the printed circuit board showing the ground plane configuration of connector pins.
FIG. 18 is a cross-sectional view of the printed circuit board illustrating the six individual conductive layers separated by dielectrics.
DETAILED DESCRIPTION
Various embodiments of the present invention will be described in detail with reference to the drawings, wherein like reference numerals represent like parts and assemblies through the several views. Reference to various embodiments does not limit the scope of the invention, which is limited only by the scope of the claims attached hereto.
Embodiments of the present invention provide a chassis design that facilitates high-speed data rates of electrical signals through implementation of structures that provide heat dissipation and shielding. Embodiments also provide a module design that further facilitates high-speed data rates of electrical signals through implementation of additional structures that provide heat dissipation and shielding. Bridging repeater circuitry embodiments of the present invention also facilitate high-speed data rates of electrical signals by implementing structures that recover the data and clock portions of a low-level monitor signal through sufficient amplification and create a higher-level output signal repeating the data and clock portions.
FIGS. 1A and 1B illustrate an embodiment of the chassis of the present invention. The chassis 100 has a top cover 102 , a bottom cover 104 , and a rear cover 137 forming an outer housing 105 . Front trim piece 120 and rear trim piece 122 fit around the rear edges of the top cover 102 and bottom cover 104 , respectively. Front extensions 114 , 116 extend forward from the front trim piece 120 .
A door 108 is connected to the front extensions 114 , 116 through hinges 112 . The door 108 has a finger 110 that catches on the left front extension 114 to hold the door 108 closed. A rotatable handle 106 is connected to the chassis 100 through mount 107 . One or more covers 118 are mounted on the chassis 100 to isolate the interior of the chassis 100 when corresponding modules are not present.
The rear cover 137 has several rows of holes 138 for exhausting heat produced by the modules housed within the chassis 100 . The rear cover 137 also has a power socket 130 with electrical connections 132 for receiving AC power, such as 110V and/or 220V, from an external source. Typically, power socket 130 is internally fused and is switchable to receive either voltage. Rails 124 , 128 are mounted to the rear trim piece 122 and have feet 126 attached to them. The bottom cover 104 has a several rows of holes 136 for passing ambient air into the interior of the chassis 100 . The bottom cover 104 also has several feet 134 .
FIGS. 2A and 2B show sidewalls 140 , 148 of the chassis 100 . The sidewalls 140 , 148 are held in position by attachment to the front and rear trim pieces 120 , 122 . Several holes 150 are located at the top and the bottom of the left sidewall 148 . Similarly, several holes 142 are located at the top and bottom of the right sidewall 140 .
Ridges 152 are provided in the left sidewall 148 , and ridges 144 are provided in the right sidewall 140 . An inwardly recessed region 154 in the left sidewall 148 and inwardly recessed region 146 in the right sidewall 140 is created between the sets of ridges 152 and 144 . The inwardly recessed portions 154 , 146 are exposed between the top cover 102 and the bottom cover 104 , and the ridges 152 , 144 facilitate attachment of the top cover 102 and bottom cover 104 to the sidewalls 140 , 148 as discussed below. Handle mount holes 156 are provided in the recessed portions 154 , 146 to allow attachment of the handle mount 107 .
FIGS. 3A and 3B illustrate the assembly of the interior structures of the chassis 100 . A top horizontal surface 162 and a bottom horizontal surface 160 mount to a faceplate 158 and a vertical backplane 164 . Both the top and bottom horizontal surfaces 162 , 160 have several rows of ventilation holes 168 that allow air to pass up from the bottom of the chassis 100 through the installed modules and into the top of the chassis 100 where it is channeled between the top cover 102 and the top horizontal surface 162 and exhausted out the rear of the chassis 100 through holes 138 .
As can be seen the top and bottom horizontal surfaces 162 , 160 have curled edges 172 , 173 , 174 , and 175 that abut the faceplate 158 and the vertical backplane 164 . Each of these surfaces except the vertical backplane 164 is made of metal, such as cold rolled steel with a zinc chromate plating, such that metal-to-metal contact is established between them. The backplane 164 is typically printed circuit board material. Likewise, the sidewalls 140 , 148 are also made of metal, such as aluminum, and establish electrical continuity with the top and bottom horizontal surface 162 , 160 through metal brackets discussed below. A Faraday box, or shielding chamber, results which provides shielding for the modules housed by the chassis 100 . The grounding of the shielding chamber is discussed below. Similarly, an outer Faraday box results from the metal top and bottom covers 102 , 104 and the metal rear cover 137 whose grounding is also discussed below.
The vertical backplane has connectors 166 that allow the modules to be inserted into the chassis 100 and slidably engage connectors 166 to establish electrical connection. The vertical backplane connectors 166 typically provide DC power to the modules from a chassis power supply discussed below. The top and bottom horizontal surfaces 162 , 160 have slots 170 that receives fins on the module to guide it as it is inserted and to prevent lateral movement once it is installed. As best seen in FIG. 3B , the faceplate 158 has notches 176 that align with the slots 170 .
FIG. 4A shows the chassis 100 with the top cover 102 and the bottom cover 104 of the outer housing 105 removed. As shown the shielding chamber 101 is fully installed in the chassis 100 . The shielding chamber 101 is held in place by brackets 178 , 180 that mount to both the top horizontal surface 162 and the sidewalls 140 , 148 . As can be seen an airspace 103 is created by the placement of the shielding chamber 101 . The airspace 103 of this embodiment includes the area between the top horizontal surface 162 and the top cover 102 , the area between the rear cover 137 and the vertical backplane 164 , and the area between the bottom horizontal surface 160 and the bottom cover 104 .
The airspace 103 allows air to enter through the bottom cover 104 , rise through the shielding chamber 103 , return to the rear of the chassis 100 , and exit out the rear cover 137 . Air may also enter through the bottom cover 104 and rise directly between the vertical backplane 164 and the rear cover 137 and then exit from the chassis 100 . As shown in FIG. 4B , the chassis power supply 186 is mounted to the rear cover 137 , and the air rising up the vertical backplane 164 may assist in dissipating heat from the power supply 186 . Because the top cover 102 has no holes, any flames imposed on the interior of chassis 100 cannot escape from the top and are, therefore, adequately contained.
Also shown in FIG. 4B , the rear cover has an aperture 184 that is used to mount the power socket 130 . The power socket 130 has rear terminals 182 for electrical connection to the power supply 186 . Also, a portion of the holes 138 of the rear cover 137 lie directly behind the power supply 186 and allow it to radiate some heat directly out of the chassis 100 . Mounting the power supply 186 directly to the rear cover 137 also permits easy installation and maintenance of the power supply 186 because it can be accessed by simply removing the rear cover 137 and its electrical connections can be easily made while the rear cover 137 is removed.
FIGS. 5A , 5 B, and 5 C show the ground wire connections of the shielding chamber 101 , vertical backplane 164 , and outer housing 105 , and also shows the power connections of the power supply 186 . The power supply 186 typically receives AC power from the power socket 130 through wires 208 and 210 connected to jack 216 of the power supply 186 . The power supply 186 then typically outputs DC power through output jack 218 to the vertical backplane 164 through wires 212 and 214 where it is then distributed to each of the connectors 166 .
A ground tab 220 of the power supply 186 is electrically connected to the ground prong 207 of the power socket 130 through wire 206 . The ground tab 220 is electrically connected to a ground post 190 of the rear cover 137 through wire 204 . Ground wires are fixed to the ground post 190 and ground post 188 of the rear cover 137 through the fastening assembly 192 .
A ground conductor 164 ′ of the vertical backplane 164 that electrically connects the vertical backplane 164 to shielding pins of connectors 166 is also electrically connected to the ground post 190 through wire 196 . The right sidewall 140 is connected to the ground post 188 through wire 198 . The left sidewall 148 is connected to the ground post 188 through wire 202 . The top cover 102 is connected to the ground post 188 through wire 200 , and the bottom cover 104 is connected to the ground post 190 through wire 194 .
The top cover 102 and bottom cover 104 of the outer housing 105 have conductor tabs 102 ′ that extend from them for receiving connectors 201 of the ground wires 200 and 194 . The top cover 102 and bottom cover 104 may have a powder coat finish applied and the conductor tabs 102 ′ remain bare metal to establish electrical continuity with the ground wires 200 , 194 .
FIG. 6 shows the installation of the rear cover 137 and left and right rails 124 , 128 as well as the connections of the ground wires to the sidewalls 140 , 148 . Because the rear cover 137 is mounted to the rear trim piece 122 , the airspace 103 remains between the rear cover piece 137 and the vertical backplane 164 . The airspace 103 accommodates the power supply 186 .
The ground wire 198 extending from ground post 188 fastens to the right sidewall 140 through one of the holes 142 in the top of the sidewall 140 . Likewise, the ground wire 202 extending from ground post 188 fastens to the left sidewall 148 through one of the holes 150 in the top of the sidewall 148 . The ground wire 196 extending from ground post 190 fastens to a mounting hole 197 of the vertical backplane 164 that is also used to attach the vertical backplane 164 to the bottom horizontal surface 160 .
FIG. 7A shows an exploded view of the chassis 100 . As can be seen, the power supply 186 is placed within the airspace 103 , which is maintained by the spacing between the top cover 102 and top horizontal surface 162 , between the vertical backplane 164 and the rear cover 137 , and between the bottom cover 104 and the bottom horizontal surface 160 . A covering 109 may be placed over the faceplate 158 for aesthetics. The door 108 has a handle 108 ′ extending forwardly to facilitate opening and closing.
FIG. 7B shows a fastener for holding the top cover 102 onto the sidewall 140 . The ridges 144 of the sidewall 140 have a notched end 222 that receives a nut holder 224 and nut 226 that fits within the nut holder 224 . As shown in FIG. 7C , a nut holder 224 and nut 226 has been positioned by sliding it within the ridges 144 from the notched end 222 to an alignment dimple 230 . A screw passes through a hole in the bottom cover 104 to hold it in place. As shown, the top cover 102 and bottom cover 104 are both attached by four of these fasteners.
FIG. 8A shows the door 108 of the chassis 100 . The door 108 includes the handle 108 ′ which has the finger 110 extending from it. The finger 110 passes through a hole in the door 108 so that it may engage the front extension 114 . FIG. 8B shows a hinge guide 232 that mounts to the front extensions 114 , 116 . The hinge guide 232 has a hole 232 ′ for receiving a hinge shaft 112 ′ extending from hinge 112 that mounts the door 108 but allows it to open and close.
FIGS. 9A , 9 B, 9 C, and 9 D show an embodiment of the module of the present invention. The module 234 has a shell 235 that has a frontplate 236 , a top surface 250 , a bottom surface 262 , and a back surface 256 . The top surface 250 has several ventilation holes 252 , and the bottom surface 262 has ventilation holes 264 . The ventilation holes allow air to rise from the bottom of the chassis such as chassis 100 , up through the modules 234 installed in the chassis 100 , and into the top of the chassis 100 prior to being exhausted through the rear cover 137 . The shell 235 is typically made of metal, such as aluminum. The edge 266 of the top surface 250 is folded, as is the edge 268 of the bottom surface 262 . The edge 257 of the back surface 256 is also folded.
A metal backplate 254 that is typically made of aluminum mounts to the edges 266 , 268 , 257 of the shell 235 . The metal backplate 254 supports a printed circuit board 276 . Portions 255 of the metal backplate 254 extend beyond the perimeter of the printed circuit board 276 and provide a surface that can establish metal-to-metal contact with the folds of edges 266 , 268 , and 257 .
Connector jacks 274 pass signals between the circuitry on the printed circuit board 276 and external cable connectors (not shown). A metal jack holder 270 is mounted to the shell 235 and to a faceplate 238 . The metal jack holder 270 provides support for the connector jacks 274 with holes 272 that surround the cylindrical sleeve of the connector jacks 274 . The metal jack holder 270 also establishes metal-to-metal contact with the shell 235 and with the faceplate 238 . The faceplate 238 also establishes metal-to-metal contact with the backplate 254 and the front edges of the shell 235 .
The printed circuit board 276 is enclosed within the shell 235 , the backplate 254 , and the jack holder 270 which together form a Faraday box providing shielding for the circuitry on the printed circuit board 276 . A connector 260 is mounted to the printed circuit board 276 and is in electrical communication with the circuitry. Typically, the connector 260 provides DC power from the vertical backplane connector 166 to the circuitry. The back surface 256 of the shell 235 has an opening 258 that allows the connector 260 to pass through. Typically when maximizing shielding, the largest dimension of the opening is one-twentieth or less of the shortest wavelength of the signal to be handled by the circuitry.
The faceplate 238 has several holes for sending and receiving signals to and from coaxial cables. For a module 234 housing a repeater circuit, such as the bridging repeater circuit of the present invention, a monitor out port 242 , a signal out port 244 and a signal in port 246 are provided for each data channel. As shown, the module 234 houses two data channels. The faceplate may have a decal 278 attached to it to provide a visual indication of the purpose of each jack, light emitting diode (LED), switch, or other feature provided on the faceplate 238 .
The faceplate 238 generally has a fastener 240 for attachment to the chassis 100 . The metal backplate 254 has fins 248 located on the top and bottom edges. The fins 248 fit within the notch 176 of the chassis faceplate 158 and within the slot 170 of the top and bottom horizontal surfaces 162 , 160 shown in FIG. 3B .
FIG. 9E shows the chassis 100 with a module 234 being partially installed. The fins of the module 234 pass into the slots 170 of the top and bottom horizontal surfaces 162 , 160 and notch 176 of the chassis faceplate 158 . The module 234 slides into the opening in the chassis faceplate 158 and then continues to slide into the shielding chamber until the module connector 260 engages the vertical backplane connector 166 .
FIG. 10 is a closer view of the faceplate 238 of the module 234 . The faceplate 238 has the ports for monitor output 242 , signal output 244 , and signal input 246 . In addition, the faceplate may have a loss of signal (LOS) LED 282 that lights to indicate the signal through signal input port 246 is not adequately present. An LOS LED 280 may also be provided to indicate that the signal through signal output port 244 is not adequately present. Ports and LEDs for both a channel A and a channel B are shown.
FIG. 11 shows an exemplary network environment employing bridging repeater circuits of the present invention. A bridging repeater circuit 294 , which may be channel A or B of a module such as module 234 , is included as is a second bridging repeater circuit 292 which may be the other channel of the module. The bridging repeater circuits 292 , 294 are being used to bypass a faulty digital signal cross-connect circuit (DSX) 290 without disrupting the signal path between the healthy DSX 288 and the electrical to optical (E/O) multiplexer (mux) 298 . The bridging repeater circuits 292 , 294 may be housed in a module 234 for installation in portable chassis 100 , or they may be housed in a module suitable for installation in an existing chassis in the network environment such as a chassis with positions for the DSX devices.
Signal transmission through the portion of the network shown passes between several digital distribution frames (DDF) 284 that pass electrical signals to the mux 286 where they are multiplexed into an output line 285 . The mux 286 also receives multiplexed signals from a healthy DSX 288 through input line 287 and demultiplexes them for transfer to the several DDFs 284 . The healthy DSX 288 has output line 304 that feeds into the input of the faulty DSX 290 . The faulty DSX 290 has an output line 306 that feeds into the input of the healthy DSX 288 .
The faulty DSX 290 passes signals to the E/O mux 298 through line 289 and receives signals from the E/O mux 298 through line 291 . When the faulty DSX 290 needs to be temporarily or permanently replaced, a new DSX 296 is installed with a line 295 receiving signals from the E/O mux 298 that are the same as those signals received by the faulty DSX 290 through line 289 . The new DSX 296 is also installed with a line 297 sending signals to the E/O mux 298 . As discussed below, this line 297 duplicates the signal being provided over line 291 from the faulty DSX 290 to the E/O mux 298 .
The bridging repeater circuit 294 receives at its input the monitor signal output by the new DSX 296 through line 308 . The bridging repeater circuit 294 retransmits the data and clock information of the signal received from the new DSX 296 to the healthy DSX 288 through line 302 that connects to a make-before-break input jack of the healthy DSX 288 used for temporary connections. Because of this completed circuit through the bridging repeater circuit 294 , the line 306 connecting the output of faulty DSX 290 to the permanent input of healthy DSX 288 can be disconnected from the faulty DSX 290 and then redirected to the permanent output of new DSX 296 without breaking service in the channel.
The bridging repeater circuit 292 receives at its input the monitor signal output by the healthy DSX 288 through line 300 . The bridging repeater circuit 292 retransmits the data and clock information of the signal received from the healthy DSX 288 to the new DSX 296 through line 310 that connects to a make-before-break input jack of the new DSX 296 used for temporary connections. Because of this completed circuit through the bridging repeater circuit 292 , the line 304 connecting the input of faulty DSX 290 to the permanent output of healthy DSX 288 can be disconnected from the faulty DSX 290 and then redirected to the permanent input of new DSX 296 without breaking service in the channel. Once the healthy DSX 288 and the new DSX 296 have established communication in both channels through permanent connections, bridging repeater circuits 292 and 294 can be disconnected from both the healthy DSX 288 and the new DSX 296 .
FIG. 12 shows a block diagram of the circuitry 312 of the bridging repeater circuits 292 (channel A) and 294 (channel B). The bridging repeater circuit input is typically a 75 ohm SMB connector 314 , 316 for both channel A and channel B that receives the monitor signal at approximately 0.1 Volts (V). The input connectors are electrically connected to isolation transformers 318 , 320 for channels A and B, and the transformers have a turns ratio of 1:1. The isolation transformers 318 , 320 are electrically connected to the amplification portion of the input section that includes a current feed back operational amplifier 322 , 324 for each channel in series with a voltage limiting operational amplifier 326 , 328 for each channel.
The voltage limiting operational amplifier 326 , 328 of each channel feeds the amplified signal containing data and clock information, such as in a coded mark inversion (CMI) format, to an analog data input of the transceiver 330 , 332 of each channel. The transceiver 330 , 332 recovers the data and clock information from the signal and creates an output signal that repeats the data and clock information, also in CMI format. The transceiver output is connected to an additional isolation transformer 338 , 340 that passes the output signal to the output jack 350 , 352 , which may also be a 75 ohm SMB connector. The output signal may pass through a voltage divider network (not shown) prior to reaching the output jack 350 , 352 but the output signal is typically around 2 V.
The transceiver output is also connected to another isolation transformer 334 , 336 that passes the output signal to an additional voltage divider 342 , 344 that is connected to a monitor jack 346 , 348 , which may also be a 75 ohm SMB connector. The additional voltage divider 342 , 344 decreases the output signal received by the monitor jack 346 , 348 by about 27 dB.
A reference clock 354 , which is typically a 19.44 MHz oscillator, feeds a reference clock signal to the transceivers 330 , 332 . Rather than using a single oscillator, a separate oscillator for each transceiver 330 , 332 may also be employed. A low-voltage detector 356 may also be included to detect an under-voltage power supply condition. The low-voltage detector 356 feeds a detection signal to a programmable logic device (PLD) control 358 .
The PLD 358 also communicates with the transceivers 330 , 332 to determine whether the signals being received or output by the transceiver are of an adequate level. If the PLD 358 receives a detection signal from detector 356 indicating an improper supply voltage, the PLD 358 will trigger a major or minor alarm circuit 360 which is in communication with the backplane 364 . If the PLD 358 receives a transmit or receive signal from the transceiver 330 , 332 , it triggers a user LED 362 for channel A or B corresponding to transmit or receive to provide an indication of the loss of signal.
FIG. 13 shows the input channel and some of the transceiver components in more detail for channel A. Two amplification stages are utilized to provide a sufficient Gain-Bandwidth product to increase the 0.1 V monitor signal to 0.5 V peak-to-peak before it is delivered to the transceiver 330 . At relatively high data rates for electrical signals, such as 155.52 Mbps for STM-1 transmission, the bandwidth of the amplification portion must also be relatively large so as to include the highest frequency for that data rate. The current feedback operational amplifier, such as the Burr-Brown OPA658, is configured to produce a significant portion of the overall gain.
A voltage divider network is included with the current feedback amplifier 322 to provide a source for the voltage limiting amplifier 326 . The output of the voltage divider has a gain of about 8 dB over the monitor signal. The Burr-Brown OPA658 has a sufficient gain bandwidth product to provide the 8 dB of gain through the voltage divider while maintaining a frequency response suitable for a 155.52 MHz signal, as might be received for a 155.52 Mbps data rate.
The voltage limiting amplifier 326 , such as the Burr-Brown OPA689, also produces a significant portion of the overall gain. A voltage divider circuit is included with the voltage limiting amplifier 326 to provide a source for the transceiver 330 . The output of the voltage divider has a gain of about 8 dB over the signal received from the current limiting amplifier 322 . The Burr-Brown OPA689 has a sufficient gain bandwidth product to provide the 8 dB of gain through the voltage divider while maintaining a frequency response suitable for a 155.52 MHz signal.
The voltage limiting amplifier 326 has the additional task of limiting the voltage received by the transceiver 330 . The transceiver 330 has an input sensitivity range, and the voltage limiting amplifier 326 provides an output through the voltage divider that is guaranteed to be within a designated range, even if the monitor signal has an amplitude greater than anticipated. For the AMCC model S3031B STM-1 transceiver, which is a fully integrated CMI encoding transmitter and CMI decoding receiver, the input sensitivity is from 110 milli-volts (mV) to 1.3 V. Thus, it is desirable to constrain the output of the voltage divider of the voltage limiting operational amplifier 326 to fit within this range, and a 0.5 V peak-to-peak voltage is suitable. This limit is set-up using a voltage divider discussed in more detail below.
The transceiver 330 has an analog data input leading to a data/clock recovery circuit 336 . The transceiver also has a loss of signal input feeding a LOS circuit 334 . The LOS circuit 334 receives the input signal from the voltage limiting amplifier stage 326 after it has passed through an additional voltage divider network that reduces the signal to about 0.170 volts to set the floor for adequate signal strength. If the signal at the analog data input drops below the 0.170 V reference, the LOS out line passing to the PLD 358 is activated.
FIG. 14 shows the input circuit in more detail. A decoupling capacitor 382 and power supply filtering capacitors 382 ′ are included as is a ferrite bead 380 to reduce electromagnetic emissions from the power supply. The current feedback operational amplifier is configured with a 402 ohm feedback resistor 384 and a 178 ohm resistor 318 tied to ground and the inverting input to produce a gain of 3.26=(1+402/178). The voltage divider 386 of the current feedback stage includes a 22.1 ohm resistor 388 and a 75 ohm resistor 390 that cut the gain to 2.52=[3.26*75/(22.1+75)].
The voltage limiting operational amplifier 326 also has power supply filtering capacitors 396 and a ferrite bead 398 . The voltage limiting amplifier 326 is configured with a feedback resistor 392 of 604 ohms and a 150 ohm resistor 394 tied to ground and the inverting input to produce a gain of 5.03=(1+604/150). The voltage divider 408 of the limiting amplifier stage includes a 22.1 ohm resistor 410 and another 22.1 ohm resistor 412 to cut the gain to 2.52=[5.03*22.1/(22.1+22.1)]. The signal passes through another decoupling capacitor 396 ′ prior to entering the analog data input of the transceiver 330 .
The low voltage limiting function of the voltage limiting operational amplifier 326 is configured by an 18.22 kilo-ohm resistor 400 tied to the −5 V power supply and a 1 kilo-ohm resistor 402 tied to ground. A low voltage reference input of the operational amplifier 326 is tied between the resistor 400 and resistor 402 to set the low voltage limit to −0.26 V=[−5V*1000/(1000+18,220)].
The high voltage limiting function of the voltage limiting operational amplifier 326 is configured by an 18.22 kilo-ohm resistor 404 tied to the +5 V power supply and a 1 kilo-ohm resistor 406 tied to ground. A high voltage reference input of the operational amplifier 326 is tied between the resistor 404 and resistor 406 to set the high voltage limit to +0.26 V=[+5V*1000/(1000+18,220)].
FIG. 15 shows a block diagram of the power supply 368 of the bridging repeater circuit. −48V is received from a pin of the backplane connector 364 and it delivered through a 0.5 amp fuse 370 to a DC/DC converter 372 , such as model LW005A. This DC/DC converter converts the −48 V to +5 V and supplies the +5 volt to the appropriate circuitry including the amplifiers 322 , 326 and transceiver 330 . This DC/DC converter 372 also provides +5 V to a second DC/DC converter 374 , such as model HPR1000. This DC/DC converter converts the +5 V to −5 V and supplies the −5 V to the appropriate circuitry.
The +5 V supply is also connected to a reset control device 376 , such as model DS1810. The reset control 376 sends a reset signal to the transceiver 330 during power-up and during low voltage conditions. If the +5 V dips below a threshold, such as 4.75 V, then the reset control 376 holds the reset line low until the voltage rises above the threshold and for an additional 150 milliseconds thereafter to reset both the transmitter and receiver portions of transceiver 330 .
The +5V and −5 V supplies are also connected to the under-voltage detector 356 that connects to the PLD 358 . The under-voltage detector, such as model ICL7665S, triggers an output signal when the received voltage dips below 4.45 V to indicate to the PLD 358 that the voltage is beyond the acceptable range.
FIG. 16 shows a top layer 414 of the printed circuit board, such as printed circuit board 279 of FIG. 9C , for supporting the bridging repeater circuitry 312 . The printed circuit board 279 has signal traces that lead from the input jack area 416 to the output jack area 436 of channel A. A signal trace 418 carries the signal from the input jack area 436 to the isolation transformer area 420 . A signal trace 422 carries the signal from the isolation transformer area 420 to the first amplifier area 424 . A signal trace 426 carries the signal from the first amplifier area 424 to the second amplifier area 428 . A signal trace 430 carries the signal from the second amplifier area 428 to the transceiver area 431 to complete the input circuit.
As shown, the signal trace 422 between the transformer area 420 and first amplifier area 424 and signal trace 426 between the first amplifier area 424 and the second amplifier area 428 are individually linear. Furthermore, both of these traces 422 , and 428 are linear with respect to one another.
A signal trace 432 carries the signal from the transceiver area 431 to the second isolation transformer area 433 . A signal trace 434 carries the signal from the second isolation transformer area 433 to the output jack area 436 to complete the output circuit.
As can be seen the signal traces from input area 416 to output area 436 all lie within the top layer and are therefore disposed within a single spatial plane. Furthermore, the signal traces leading from the input area 416 to output area 436 have a constant width. No test vias or other trace deformations are present to disrupt the constant signal trace width. Placing the signals within the single spatial plane and maintaining the trace width from input to output improves the noise rejection of the bridging repeater circuit.
For maximizing signal integrity, the length of each continuous piece of signal trace should be maintained at 0.25 inches or below, especially for high data rates such as STM-1. Furthermore, potential interference sources such as the crystal oscillator 354 located in oscillator area 417 should be positioned closely to the transceiver portion 431 to minimize the length of the oscillator trace 419 . For maximizing signal integrity, the length of the oscillator trace 419 should be maintained at 0.8 inches or less.
FIG. 17 shows another layer of the printed circuit board supporting the bridging repeater circuit. This ground layer 437 includes a continuous copper sheet 440 and shielding pin connections from the pin connector layout 438 . The continuous copper sheet 440 is tied to the shielding pins which may be tied to chassis ground, such as through the connector 166 that is tied to the ground wire 196 through the ground conductor 164 ′ in chassis 100 .
The pins that are for shielding purposes, including pins shown with connections to the ground plane 440 such as pin 453 , surround the pins that carry −48 V power and the −48 V return including pins 441 , 442 , 443 , 444 , 445 , 446 , 447 , and 448 as well as pins carrying alarm relays such as pins 449 , 450 , 451 , and 452 . These shielding pins such as pin 453 in conjunction with the continuous copper sheet 440 establish a ground plane that may permeate any gaps between the opening 258 and connector 260 in the back surface 256 of module 234 . As shown, 12 out of 55 pins carry power or alarm relays leaving 78% of the pins as shields.
FIG. 18 shows a cross-section of the printed circuit board 460 . The printed circuit board 460 has several layers including conduction layers and dielectric layers. A solder mask 462 is applied to the top-most layer 464 , and another solder mask 488 is applied to the bottom-most layer 486 . A first conductive layer is made of two individual layers, a first layer 466 of copper and a plating layer 464 made of tin.
Beneath the first layer of copper 466 lies a resin dielectric layer 468 . Then a second conductive layer 470 of copper is included. Beneath the conductive layer 470 lies a dielectric layer 472 . Beneath the dielectric layer 472 lies a third conductive layer 474 . Beneath the conductive layer 474 lies a dielectric layer 476 . Beneath the dielectric layer 476 lies a fourth conductive layer 478 . Beneath the fourth conductive layer 478 lies a dielectric layer 480 . Beneath the dielectric layer 480 lies a fifth conductive layer 482 . Beneath the conductive layer 482 lies a dielectric layer 484 . The sixth and bottom-most conductive layer lies beneath the dielectric layer 484 and includes two individual layers, a copper layer 486 and a plating layer 488 that includes the solder mask.
The dielectric layer 476 has the greatest thickness, such as 28 mils followed by the two outer-most dielectric layers 468 and 484 having a thickness such as 8 mils. The intermediate dielectric layers 472 and 480 have the least thickness, such as 5 mils. The dielectric constant for these layers is about 4.3. The outer-most copper layers 466 and 486 contain about 0.5 oz of copper. The other copper layers 470 , 474 , 478 , and 482 contain about 1 oz of copper.
The conductive and dielectric layers are arranged such that the signals are on the outer conductive layer 464 to eliminate vias that add capacitance. The power and chassis ground are layers 474 and 478 , respectively, and are separated by the thickest dielectric 476 to limit the chassis noise that is introduced into the power lines. Conductive layer 470 is copper ground plane establishing a logic ground. Conductive layer 482 is another logic ground layer, and layer 486 carries power supply bypass lines including lines to resistors, capacitors, etc.
While the invention has been particularly shown and described with reference to preferred embodiments thereof, it will be understood by those skilled in the art that various other changes in the form and details may be made therein without departing from the spirit and scope of the invention. | A telecommunications chassis, module, and repeater circuit for use with signals having data rates including STM-1 (155.52 megabits per second) are disclosed. The chassis provides structures for establishing shielding and heat dissipation for the circuitry modules it contains including an outer and an inner Faraday box with an integrated ventilation pattern for circulating air. The module provides its own structures for establishing shielding and heat dissipation including a Faraday box and a ventilation pattern. The repeater circuit provides the ability to bridge a data signal between a monitor jack of one device and a higher signal level input jack of another device through multiple amplification stages and circuit board structures. The telecommunications chassis, module, and repeater circuit can be used in conjunction. | 7 |
[0001] This application claims benefit of U.S. Provisional Application 61/525,650 filed Aug. 19, 2011.
FIELD OF INVENTION
[0002] The present invention relates to a hydrodynamic separator unit designed to separate solid matter from a surface water fluid stream flowing into and through the unit in both normal and abnormally high fluid flow conditions.
BACKGROUND
[0003] One example of a prior art hydrodynamic separator is shown in U.S. Pat. No. 5,788,848 patent. This patent shows a system comprising inner and an outer non-concentric cylinders, the inner cylinder including a screen portion (the screened separator). The debris containing stream is feed to the internal space within the inner cylindrical screened separator; the material contained therein is retained within and below the inner cylinder while the fluid flows from the inside of the inner screened cylinder to an annular space between the inner and outer cylinder and exits from the surrounding outer chamber.
[0004] U.S. Pat. No. 6,241,881 discloses a similar cylindrical waste separator which includes on its upper portion an inlet for loaded influent and an outlet for cleaned effluent. The separator comprises a cylindrical portion having a lower part incorporating a basket. The inflow stream containing solid matter flows in a rotary motion to the area inside the cylindrical portion above the basket. The solid matter of a size greater than that of the mesh openings in the basket are retained within the cylinder and in the basket at the lower end of the cylinder and the fluid with solid matter smaller than the mesh openings, referred to as cleaned effluent, passes outward through the basket and cylinder walls. Cleaned effluent entering the peripheral area surrounding the basket and cylinder then flows upwards into the outlet pipe.
[0005] These arrangement have the disadvantage of clogging as a result of retained waste material, such as plastic bags, bottles, leaves, etc, that can accumulate against the inner walls of the screen causing the swirling, inflowing stream to penetrate the only the upper portion of the screen which, in turn, causes the inflowing stream to flow only through the upper portion of the basket. Bulky waste obstructing the basket walls thus reduces the flow capacity of liquid passing through the basket and the efficiency of separation and the inflowing stream tends to bypass the separator and flow directly to the outlet through an overflow weir.
[0006] U.S. Pat. No. 6,641,720, shows a separator which has a plurality of protruding segments adjacent openings in the panel, with each segment extending from the face of the panel at a position upstream of respective openings so as to project into the fluid flow path to form a substantially closed face to the liquid flowing over the screen, the intent being to prevent blockage of the openings in the screen.
[0007] An alternative hydrodynamic separator for urban and industrial effluents, shown in EP Published application 2,181,748, incorporated herein in its entirety by reference, includes a tank having a centrally located cylindrical chamber, the cylindrical chamber having a tubular screen made of expanded or perforated metal within the space defined by the cylindrical chamber. In these separators, fluid flowing into the separator circulates in the tank in a space exterior to the cylindrical chamber. Waste is constrained in a cyclone-like vortex that forms in the tank but outside the screened cylinder and moves downwards to the bottom of the tank while cleaned fluid flows through the lateral surface of an expanded metal screen of the cylinder and exits from the bottom of the centrally located screened chamber.
[0008] The rotation of the effluent stream in the periphery helps avoid the deposition of waste or particles on the screen so that the screen remains unobstructed.
SUMMARY
[0009] A unit for separating particulate matter and solid waste, particularly large sized particles in a flowing stream of surface water includes a cylindrical filter structure onto which the effluent stream flows. The filter structure separates solid wastes of specific dimensions which cannot pass through the filter structure from the cleaned stream which flows through the filter to a downstream outlet chamber from which the effluent stream cleaned from the retained solid waste is discharged. Solid waste particles smaller in size than the apertures of the screen cylinder may also be captured through swirl concentration, vortex separation and particle sedimentation processes inherent under flow conditions. The filter structure consists of a screen, which is designed to be traversed by the flowing stream, an inlet chamber and an outlet chamber, which are both contained in a tank. Solid waste of large dimensions, which cannot pass through the filter structure, is collected at the bottom of the inlet chamber. The separator unit further includes structure on the top thereof designed to redirect excess fluid flow that exceeds the design capacity of the separator. This internal bypass structure is, comprised of a combination of additional filter structures and weirs, to filter and direct the bypass of very large flows that exceed the design capacity of the primary filter screen cylinder. This bypass structure provides screening treatment of the large bypass flows and baffling retention of floating solids.
BRIEF DESCRIPTION OF DRAWINGS
[0010] FIG. 1 is a vertical axial cross-section and
[0011] FIG. 2 is a horizontal cross-section showing the hydrodynamic separator described in EP 2,181,748.
[0012] FIG. 3 is a vertical axial cutaway view of a separator incorporating features of the invention.
[0013] FIG. 4 is an enlarged view of the portion of FIG. 3 enclosed by circle B of FIG. 3 .
[0014] FIG. 5 is a top view of the separator taken along line 5 - 5 of FIG. 3 .
[0015] FIG. 6 is a schematic drawing showing the left side of the bypass system as shown in FIG. 4 and the flow paths of fluid during a high flow situation through that left side.
[0016] FIG. 7 is a vertical, cutaway perspective view of the separator of FIG. 3 prior to placement of the overflow structure.
[0017] FIG. 8 is a top view of the separator taken along line 8 - 8 of FIG. 7 .
DETAILED DESCRIPTION
[0018] Described and shown herein is a hydrodynamic separator for separating solid matter from a stream of liquid surface water such as urban and industrial storm water runoff containing waste material. Such a structure is typically used to separate debris in an inflowing stream before a finer treatment process can be applied to the flowing stream. The separator 10 , shown in FIGS. 3-6 includes an upper extension 12 , referred to herein as the Quad Bypass Tower. This construction is an improvement over the prior art structures such as shown in FIGS. 1 and 2 .
[0019] Referring to FIG. 1 , baffle 333 comprises a solid walled, hollow cylinder mounted on top of a primary screen cylinder 332 , which can be an expanded, perforated, punched, slotted or otherwise made porous to provide a screen material. The elevation of the top of this cylinder is set so there is about 1 to 2-ft of freeboard above the expected water surface elevation of the flow over the bypass weir 344 that is in the separate diversion vault 340 . The diversion weir structure shown in FIGS. 1 and 2 incorporates an overflow weir plate 344 . Under normal flow conditions, this weir plate diverts flow into the tank 300 . However in case of high flows, a portion of the flow passes over the overflow weir 344 and is directly discharged to the discharge chamber 349 and then to the effluent drain 350 without being filtered.
[0020] The separator consists of a hydrodynamic volume limited by a tank provided with an inlet for a waste containing influent stream and an outlet for the effluent stream with large particles removed.
[0021] To achieve the separation, the separator is divided into an inlet chamber and an outlet chamber, by a screen designed to retain large particles which accumulate in front of the screen or at the bottom of the separator. Clearing of the screen is achieved through the circulating movement of the effluent stream inside the separator. Cleaned effluents flow through the screen and are discharged at the outlet, without cluttering the screen.
[0022] The expanded, perforated, punched or slotted screen has a smooth metal separation surface of, for example, stainless steel with openings there through. The surface of the screen is installed vertically inside the tank.
[0023] The stream of effluent flowing along the separation surface induces a circular motion in the stream and waste of larger size, i.e. heavy solids is carried towards the center in a circular motion to descend to the bottom of the separator below the screen. Solid waste particles of smaller size than the apertures of the screen cylinder can also be captured along with the larger particles through swirl concentration, vortex separation and sedimentation.
[0024] FIGS. 7 and 8 show a hydrodynamic separator 10 , similar to that shown in FIGS. 1 and 2 , prior to inclusion of the upper extension 12 and incorporating features of the invention. A primary difference over FIGS. 1 and 2 of the hydrodynamic separator of
[0025] FIGS. 7 and 8 is that the top of the solid walled cylindrical partition baffle 133 is configured for addition of the upper extension 12 (Quad Bypass Tower), shown in FIG. 3 and best shown in FIG. 4 . The upper extension 12 allows large flows to bypass the separation/screening chamber, such as illustrated in FIG. 6 , while still receiving screening and baffling treatment. In FIGS. 1 and 2 , high flows will bypass over a weir 344 that is located in a separate structure upstream of the separator 10 , and these bypass flows would receive no screening or baffling treatment. The Quad Bypass Tower 12 allows the hydrodynamic separator 10 to be placed directly in the pipeline alignment and directly in the flow path without the separate upstream weir structure that is required for proper operation of the prior art structure, which diverts high flow rates around the unit.
[0026] Large installations, such as municipal installations, require a separate structure for diversion of treatment flows. On the other hand, the Quad Bypass Tower 12 is appropriate for installation in areas with moderate to small flow and with defined size drainage areas. The Bypass Tower 12 allows such an installation to accommodate the projected flows from a 25, 50 or 100-yr storm event.
[0027] Referring to FIGS. 1 , 2 , 7 and 8 the separator consists of a cylindrical treatment tank 300 , 100 of circular cross section having a partition baffle 330 , 130 of cylindrical shape centrally mounted within the volume of the treatment tank 300 , 100 . The partition baffles 330 , 130 comprise a solid walled lower portion 334 , 134 , a separation screen 332 , 132 of a cylindrical shape on top of the lower portion, and a solid walled cylindrical partition baffle 333 , 133 on top of the separation screen 332 , 132 enclosing an inner channel 320 , 120 .
[0028] The assembly that is formed by the lower part 334 , 134 , the screen 332 , 132 , and the upper part 333 , 133 subdivides the treatment tank 300 , 100 into an external inlet chamber 310 , 110 , to receive loaded effluents, and an internal outlet chamber 320 , 120 , from which cleaned effluents are discharged. The internal chamber 320 , 120 is connected to the effluent drain through a pipe 321 , 121 which opens from the bottom of internal chamber 320 , 120 . The effluent drain pipe 321 , 121 also functions as an outlet siphon minimizing the sedimentation of very fine, suspended particles in the filtered liquids that flowed through the screen 332 , 132 from accumulating in this portion of the flow path.
[0029] The pipe 321 , 121 opens to the bottom part of a discharge chamber 349 , which is located below the input channel 341 , 141 through which flow is fed into the treatment tank 300 , 100 . The influent stream containing waste material flows successively through the influent drain 341 , 141 to the diversion weir box 340 , then tangentially to the tank 300 , 100 as indicated by the arrows in FIG. 2 . The influent stream then flows in a swirl inside the external chamber 310 , 110 following the rotational direction indicated by the two arrows F 301 . As a result of the rotational flow, the waste in the influent stream is washed from the outer surface of screen 332 , 132 . This allows the cleaned effluent to flow through the screen, leaving the macro-waste in the peripheral space outside the surface of the cylindrical screen, and the cleaned effluent subsequently drains through the internal chamber 320 , 120 , and is discharge through the effluent drain 321 , 121 .
[0030] The hydrodynamic separator is typically from about 0.3 to about 10 meters in diameter and from about 0.6 to 15 meters in height, respectively. The access hole 302 on the lid 301 of tank 300 provides access into the external cell 310 , and also to the exterior of screen 332 .
[0031] In the previous designs, such as in U.S. patent U.S. Pat. No. 6,241,881, the loaded influent stream flows to a space enclosed by the screen and is filtered by passing outward through the screen so that the removed solid material tends to fill the space interior of the cylindrical screen. In the current separator, the feed stream is fed to the outside of the screen and flow is around the outer surface of the screen with the inflowing stream passing through the screen to provide a filtered stream exiting from the space within the cylindrical screen.
[0032] Referring to FIGS. 3 , 4 and 6 , the following describes the screened, baffled and bypass flows in a unit that incorporates the Quad Bypass Tower exposed to high fluid flows. This enhancement enables the high fluid flows to bypass the main filter system while still being processed in a single manhole structure, making it more versatile than the currently available manhole units such as shown in FIGS. 1 and 2 or inside to outside flow separators such as shown in the prior art described above. The flows referred to below are best shown in the FIG. 6 . The hydraulic conditions of the screened flow through the Quad Bypass Tower are such that clogging is minimized.
[0033] The Quad Bypass Tower in a preferred embodiment comprises a first filtering structure screen 235 , preferably a metal screen, attached to a pedestal 202 on the top of the baffle 333 . Above the first filtering structure is a second filtering structure 240 , comprising, in a preferred embodiment, upwardly extending, spaced apart bars. In a further preferred embodiment these bars are arranged in a conical manner. Above the second filtering structure is a cylindrical vertical wall 222 , the cylindrical wall 222 functioning as a first weir so that excess fluid input flows over the top thereof. A cylindrical hanging baffle 224 with a diameter greater than the diameter of the cylindrical vertical wall 222 extends both above and below the top of cylindrical vertical wall 222 . The cylindrical hanging baffle 224 also functions as a weir with even greater excess input fluid flowing over the top thereof to accommodate extremely high bypass flow conditions. While the first filtering structure 235 and second filtering structure 240 are shown to be a metal screen and a bar screen, respectively, one skilled in the art will recognize that other alternative filtering structures can be utilized. The intent is to provide a filtering function to remove at least a portion of the waste material in an overflow situation while allowing the same or greater flow of a cleaned (i.e., less waste containing) stream through the filtering structures and into the centrally located outlet from the internal chamber 320 , 120 . For example, any combination of screens, meshes, bars or porous flow barriers can be used.
[0034] If a high flow situation occurs a first bypass flow 200 passes through the first filtering structure (a perforated, punched, slotted or expanded metal screen) 235 mounted on the pedestal 202 . It functions as a non-blocking screen, like the primary separation screen 132 in the lower cylinder described above.
[0035] As flow increases a second bypass flow 210 passes through the second filtering structure (a bar screen) 240 . The bar screen 240 can comprise vertically oriented spaced apart bars but in a preferred arrangement they are oriented, as shown in the figures, configured as a cone. The second bypass flow 210 is intended to handle the greater amount of fluid as influent flow rate increases. Because the bar screen has a tendency to cause waste material to be pinned against its surface, this pinning tendency is mitigated by placing the bars at an incline downward angle in a conical configuration. With this configuration the trapped material tends to slide downward off the bar surface.
[0036] As the flow further increases a third bypass flow 220 , which is not screened, is allowed to spill over the top 223 of the cylindrical vertical wall 222 (functioning as a weir) and into the center of the internal chamber 120 . However, some waste obstruction is provided by the cylindrical hanging baffle 224 which retains floatables and also functions as another weir.
[0037] If very high flows are encountered bypass flow 230 occurs. The flow proceeds unfiltered upward external of, and then over, the top of the cylindrical hanging baffle 224 and into the internal chamber 120 . Under this flow condition, the first, second and third bypass flows 200 , 210 , 220 are at maximum flow and all the flow goes into the center of the internal chamber 120 .
[0038] The separator 10 may also be configured to include a discharge pipe (not shown) through the wall of the unit with its inlet positioned at an elevation equal to the top of the hanging baffle. The inclusion of this additional discharge pipe is dictated by hydraulic conditions and is intended to discharge fluid only in the most severe flow conditions which are far in excess of the normal design capacity of the separator 10 .
[0039] The various components of the system are sized in relationship to each other to have an acceptable flow through the system without any internal flow obstruction. Referring to FIG. 4 (not drawn to be dimensionally accurate but to readily illustrate the features), the dimensions below are provided as examples of a first embodiment with a 24″ internal diameter inlet pipe, and are not intended as limitations on the scope of the disclosure.
Referring to FIG. 6:
[0040]
[0000]
d 0 = diameter (Φ) of Inlet Pipe 345,
24
in
d 1 = diameter (Φ) of screen cylinder 235,
20
in
d 2 = top diameter (Φ) of bar screen cylinder 240,
28
in.
d 3 = diameter (Φ) of cylindrical hanging baffle 224,
34
in.
h 1 = ,Height of screen cylinder 235,
8
in
h 2 = Height of bar screen cylinder 240,
8
in
h 3 = Height of cylindrical vertical wall 222,
20
in
h 4 = Plunge depth of cylindrical vertical wall 222
20
in
h 5 = Height of hanging baffle cylinder 224
20
in
Open area of perforated, punched, slotted or expanded
0.33%,
Screen (α)
Open area of Conical Bar Screen (β)
0.5%,
First Bypass Flowrate 200, (Q)
10.15
ft 3 /s
Circumferential Weir Length of cylindrical Overflow Weir 222 , (L=π·d 2 ) 7.33-ft,
q=1.385(ft3/s)/ft,=Q/L, (Unit Weir Flow)
D c =0.390-ft, (q 2 /g) 1/3 (Critical Depth at Circular Overflow Weir)=4.7-in
H m =0.586-ft, 3/2·D c , Minimum Hydraulic Head above Circular Weir=7.0-in
[0045] One skilled in the art, based on the teachings herein can readily adjust these dimensions based on greater or lesser normal flow conditions and excess flows as may be projected for a 25, 50 and 100 year storm event and typify one possible set of dimensions for the Quad Bypass system.
[0046] One skilled in the art will recognize that the disclosure set forth herein is not limited to the specific embodiments shown or described herein. It should be further recognized that the bypass system described herein is not limited to outside-to-inside flow hydrodynamic separators but can be readily adapted for addition to the inside-to-outside flow structures shown in the prior art, for example as described above. | A system for separating waste materials from a flowing stream of surface water comprises a vertical cylindrical vessel and a vertical structure within the cylindrical vessel. The vertical structure comprises stacked filtering elements and weirs sized to accommodate normal and increased fluid flow for abnormally high surface water flow conditions. The flowing stream containing waste material under normal flow conditions enters the vessel and passes through a filtering wall portion in a lower section of the vertical structure and exits through and effluent pipe. Under higher flow conditions the water flows through an overflow structure mounted on top of a lower cylindrical structure The over flow structure comprises one or more upwardly extending filtering structures and weirs sized to accommodate the excess flow conditions, filter at least a portion of the waste material from said excess flow and direct such excess flow to the effluent pipe. | 4 |
BACKGROUND OF THE INVENTION
The present invention relates to a flush bolt mechanism for latching the inactive one of a pair of swinging doors.
Flush bolt mechanisms are known in the prior art, as shown, for example, in U.S. Pat. Nos. 2,034,570 and 3,578,369. These references show devices that have served to meet, in part, the needs of industry, although they are not fully satisfactory to meet existing requirements. Not only is it necessary that the flush bolt mechanism function to bolt the closed inactive door when the other of a pair of swinging doors is closed, but it is also desirable that the flush bolt mechanism function in a most satisfactory manner so that (1) it has a long and trouble-free life; (2) it will prevent retraction of the bolt when the flush bolt mechanism is subjected to heat conditions which are likely to cause buckling of the doors; (3) it will allow retraction of the bolt when forces of a predetermined magnitude are applied to the inactive door but not when the flush bolt mechanism has been subjected to the foregoing heat conditions; (4) damage is prevented to its components, such as its latch bolt, its actuator cam or the like, where the doors may become damaged or warped during usage that prevents proper alignment of the latch bolt with the keeper; and/or (5) it requires a force applied to the active door when closing the latter of only a relatively small preselected magnitude to drive the latch bolt home into the keeper. These and other needs which will not be discussed here are not satisfactorily met by the prior art.
SUMMARY OF THE INVENTION
The present invention has overcome the inadequacies of the prior art and meets the needs of industry set forth above.
According to one form of the present invention a bolt mechanism is provided for use in conjunction with a pair of swinging doors, the bolt mechanism comprising a support member having a surface adapted to be mounted essentially flush with the free edge of the pair of swinging doors, a shaft support means extending from the support member on the side thereof opposite said surface, a first shaft slidably carried by the support means and including a latch bolt at one end thereof adapted to be extended beyond a horizontal edge of the door, a spring means normally biasing the first shaft to a retracted position, a cam pivotally carried by the support member on an axis parallel to the first shaft and extending beyond the surface thereof and adapted to be engaged by the other of the swinging doors, a cam follower engaged by the cam, said follower being pivotally carried by the support member on an axis parallel to the said surface and in a plane perpendicular to the first shaft and having a lever arm mounted for movement about the cam follower axis, a second shaft pivotally carried at one end by the distal end of the lever arm and carried at the other end by the first shaft so that linear movement can be imparted to the first shaft against the bias of the spring upon movement of the second shaft in response to pivoting of the cam when engaged by the other of the swinging doors.
The second shaft is carried by the first shaft by a slide connection, and an override spring means normally biases the second shaft to an extended position relative to the first shaft, the first-named spring means and the override spring means having spring characteristics so that the first-named spring means can be displaced axially by a lesser load than is required to displace the override spring means. By virtue of this arrangement, an axial force of a preselected magnitude can be applied axially against the latch bolt and in combination with the spring force of the first-named spring means will move the latch bolt to its retracted position against opposition of the override spring means. If desired, either the keeper or the latch bolt can then be provided with a beveled surface so that a force applied against the door from the inner side thereof will exert a component of force axially against the latch bolt resulting in it being moved to its retracted position when the force exerted on the door is of a sufficient magnitude.
The bolt mechanism also has a heat-responsive mechanism whereby when the bolt mechanism is subjected to a predetermined temperature for a time sufficient to melt an element of the heat-responsive mechanism, the bolt mechanism will then be locked in the extended position of the latch bolt to prevent the door from inadvertently opening because of buckling during a fire or other condition which exposes the doors to abnormally high temperatures.
Thus, it is an object of the present invention to provide an improved flush bolt mechanism which more readily meets the needs of industry than can be realized from the prior art devices.
Other objects of this invention will appear in the following description and appended claims, reference being had to the accompanying drawings forming a part of this specification wherein like reference characters designate corresponding parts in the several views.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a fragmentary vertical section taken through a door and door frame illustrating in elevation a flush bolt mechanism embodying the present invention;
FIG. 2 is a rear elevational view of the flush bolt mechanism illustrated in FIG. 1;
FIG. 3 is an elevational view similar to FIG. 1, but showing the flush bolt mechanism in its extended position;
FIG. 4 is an elevational view similar to FIG. 3, but showing the latch bolt moved to its retracted position against the spring forces of the override spring means;
FIG. 5 is a view similar to FIG. 3, but showing the heat-responsive mechanism in a position to lock the latch bolt in an extended position;
FIG. 6 is a fragmentary sectional view taken on the line 6--6 of FIG. 1;
FIG. 7 is a fragmentary sectional view taken on the line 7--7 of FIG. 6;
FIG. 8 is a fragmentary sectional view taken on the line 8--8 of FIG. 1;
FIG. 9 is a fragmentary sectional view of a modified form of the flush bolt mechanism wherein the latch bolt has a beveled terminal end to allow the latch bolt to be retracted in response to a preselected force exerted on the inner side of the door; and
FIG. 10 is another embodiment of the flush bolt mechanism wherein the keeper has a beveled surface of predetermined magnitude for exerting an axial force against the keeper when a force of a predetermined magnitude is applied against the inner surface of the door.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Before explaining the present invention in detail, it is to be understood that the invention is not limited in its application to the details of construction and arrangement of parts illustrated in the accompanying drawings, since the invention is capable of other embodiments and of being practiced or carried out in various ways. Also, it is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation.
Referring now to the drawings, the invention will be described in greater detail. The bolt mechanism 10 includes a support member 12 having a surface 14 adapted to be mounted essentially flush with the free edge of one of a pair of swinging doors 16. A shaft support means 18 extends from the support member on the side thereof opposite the surface 14, and a first shaft 20 is slidably carried by the support means 18 and includes a latch bolt 22 at one end thereof adapted to be extended beyond a horizontal edge 24 of the door 16. A spring means 26 normally biases the first shaft to the retracted position shown in FIG. 1. For this purpose, a spring retainer 28 is fixed to the first shaft 20 and the spring 26 is held in compression between the retainer 28 and the shaft support means 18. To permit adjustment of the latch bolt 22 so that when in its retracted position it will be substantially flush with the surface 24 and so that when extended it will extend properly into keeper 29, the first shaft is constructed in a two-piece assembly threadedly connected together as at 31 to allow the first shaft 20 to be extended or contracted when being installed so that it has the proper length. A guide bracket 30 is mounted on the upper end of the door 16 through which the latch bolt 22 passes and is guided therein. Normally, the front edge 32 of the latch bolt 22 has a flat surface which rides against a flat edge, not shown, in the bracket 30 so that after installation has been completed, the first shaft 20 cannot rotate in the bracket 30 so as to vary its length.
A cam 34 is pivotally carried by the support means 18 on a pin 37, FIG. 7, which provides an axis parallel to the first shaft 20. The cam 34 extends beyond the surface 14 and is adapted to be engaged by the other of the swinging doors (not shown). A cam follower 38 is pivotally mounted on the pin 40 carried by the shaft support means 18, and it can be seen that this arrangement provides an axis that is parallel to the surface 14 and is in a plane perpendicular to the first shaft 20. The cam follower has a lever arm 42 that can be moved around the axis of the pin 40. A second shaft 44 is pivotally carried at one end by the pin 46 carried in the end of the lever arm 42, and the other end of the second shaft 44 is carried by the first shaft 20 by the arm 48 which is fixed at one end for travel with the first shaft 20 and provides a sliding fit at the other end for the second shaft 44. An override spring means 50, which is in the form of a compression spring held in a state of compression between the pin 52 and the arm 48, is provided for normally holding the second shaft 44 in fixed relation with respect to the first shaft 20. A nut 54 is threadedly connected to the upper end of the second shaft 44 to retain the override spring means 50 in place, and by virtue of the threaded connection between the nut 54 and the second shaft 44, the second shaft 44 can be displaced axially a small amount relative to the first shaft 20 so as to pivot the lever arm 42 about its axis 40, and thereby to assure that when initial installation is made, the cam follower 38 will be in engagement with the cam 34.
The shaft support means 18 also carries a pin 56 which passes through a hole (not shown) in the arm 48 to assist in maintaining the arm 48 in proper orientation with respect to the support means 18.
To prevent the door 16 from inadvertently opening if cam 34 should pivot due to a buckling condition of the doors which may be caused by fire or the like, a heat-responsive mechanism 58 is provided which is mounted on the support member 18 and is responsive to ambient temperature of a selected magnitude to secure the first shaft 20 against movement from its extended to its retracted position. The heat-responsive mechanism 58 includes a pin 60 made of any of the well known fusible metals or alloys such as bismuth, lead and tin or of these three metals and cadmium or mercury which can be combined to fuse or melt at a predetermined temperature. When in its solid state, the pin 60 functions to hold the U-shaped resilient element 62 in a bowed, stressed condition, such as can be seen in FIG. 1, and when the pin has melted or fused, the resilient element 62 will be released to move to a position, such as is shown in FIG. 5, where it is in engagement with the shaft 20 to retain the latter in a fixed position. For mounting purposes, the upper ends of the resilient element 62 are secured by the screws 64 to the support means 18. The first shaft 20 has a plurality of notches or axially spaced shoulders 66 which are engaged by the lower end of the U-shaped resilient element 62 when the latter is released to hold the first shaft 20 in its extended position, which can be seen in FIG. 5.
When selecting the springs 50 and 26, suitable spring characteristics are required so that the forces required to move the shaft 20 to its retracted position are less than the forces of the spring 50 which serve to move the first shaft 20 to its extended position, as shown in FIG. 3, in response to the pivotal movement of the cam 34. Thus, under normal circumstances the first shaft 20 and the second shaft 44 will move upward and downward as a unit in response to pivotal movement of the cam 34 overcoming the spring forces of the spring 26 whenever the cam 34 is pivoted to the position shown in FIG. 3.
However, when forces of the preselected magnitude are exerted axially against the latch bolt 22, the spring 50 will yield, as shown in FIG. 4, to permit the latch bolt 22 to be moved to the position shown in FIG. 4. It will be recognized that this action can not occur when the heat-responsive mechanism 58 has been actuated and the U-shaped resilient element 62 is retainingly engaging the first shaft 20.
In some instances it may be desired that a force of a preselected magnitude acting against the door 16 to open it be sufficient to overcome the locking action of the latch bolt 22, and for this purpose a modified latch bolt 122, as shown in FIG. 9, may be used to provide a beveled terminal end 124 which is shaped so that when a force is applied at 126 to the door, the reactive component of force acting upon the latch bolt 122 will be sufficient to compress the spring 50 to the position shown in FIG. 4, thereby permitting the door to be moved to an open position.
Another modified form of this arrangement can be seen in FIG. 10 where the keeper 128 has a beveled surface 130 which serves to apply the same reactive vertical component of force against the latch bolt 22. | A flush bolt mechanism is disclosed for latching the inactive one of a pair of swinging doors, the mechanism functioning to latch the closed inactive door in response to closing of the other door. The latch mechanism includes a bolt that is driven home by cam and spring assemblies. A heat-responsive mechanism is provided for retaining the bolt in its extended position when the heat-responsive mechanism is subjected to a temperature and for a time sufficient to melt one of its components. A release mechanism may be provided for retracting the extended bolt in response to a force of preselected magnitude applied against the inside of the inactive door. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a reinforcing device for a door, and in particular to a reinforcing device for use on multi-sectional garage doors.
2. Discussion of the Prior Art
Multi-sectional or sliding garage doors conventionally include a plurality of elongated horizontal oriented sections of wood or metal which are hingedly interconnected. Rollers or wheels are provided on the sides of the door for slidably mounting the door in parallel arcuate tracks, so that the door can readily be moved between the open and closed positions. A pair of large helical springs bias the door toward the open position so that the user is not required to lift the entire weight of the door in order to open the door. The combination of the weight of the door and the upward spring tension on the sides thereof may cause sagging of the centre of the door, and possible cracking thereof.
While reinforced doors have been proposed in the past, the reinforcement proposed for such doors cannot be used on modern multi-sectional garage doors. Examples of such doors or reinforcement for doors are disclosed by Canadian Pat. Nos. 186,374, issued to J. Little on Sept. 3, 1918; 192,002, issued to M.C. Blest on Aug. 5, 1919; 214,943, issued to H. Kaler on Jan. 3, 1922 and 517,184, issued to J.F. McKee et al on Oct. 4, 1955, and U.S. Pat. No. 2,804,953, issued to A.M. Buehler on Dec. 5, 1955.
The object of the present invention is to overcome the deficiencies of the prior art by providing a relatively simple, yet effective device for reinforcing a multi-sectional door.
GENERAL DESCRIPTION OF THE INVENTION
Accordingly, the present invention relates to a reinforcing device for use on a multi-sectional door of the type including a plurality of horizontal panels interconnected at each end to adjacent panels by hinges, said device comprising bar means for extending between the bottom centre of at least the lowermost door panel and the upper outer corners thereof, whereby the load on the door centre is transferred to the sides of the door to prevent sagging thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be described in greater detail with reference to the accompanying drawings, which illustrate a preferred embodiment of the invention, and wherein:
FIG. 1 is an elevational view of the inside of a garage door and a reinforcing device in accordance with the present invention;
FIG. 2 is a front elevational view of the bottom centre portion of the device of FIG. 1 on a larger scale;
FIG. 3 is a front elevational view of a hinge and one end of the device of the present invention; and
FIG. 4 is a front elevational view of a hinge and one end of a second embodiment of the invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
Referring to the drawing, the preferred embodiment of the invention is intended for use on a multi-sectional garage door 1 of the type including a plurality of rectangular, horizontal panels 2 connected to each other by hinges 3 (two shown) along the length thereof. In this case, the expression "rectangular horizontal panels" is intended to mean rectangular panels, the longitudinal or major axes of which are located in horizontal planes. The bottom end 5 of the door is reinforced by a crossbar 6, which is usually an angle iron secured to the bottom door panel 2 by bolts 7, and the sides of the door are reinforced by strips 8, which carry the outermost hinges 9.
The reinforcing device of the present invention can be installed on new doors or be sold as a kit for installation on existing doors. The device is defined by three flat strips 11, 12 and 13 of metal, and a turnbuckle 14. As best shown in FIG. 2, the innermost end 16 of each strip 11 is connected to the bottom centre of the bottom panel 2 by removing the centre bolt 7, placing the flattened end 16 of the strips 11 in overlapping relationship over the bolt hole so that holes (not shown) in the strip are aligned with such bolt hole, and re-inserting the bolt. A hole (not shown) is provided in the outer end 17 of each strip 11 for receiving a bolt 19, which is also inserted through one of a plurality of axially aligned holes 20 in the inner end of the strip 12. The outer end 22 of the strip 12 is connected to the turnbuckle 14 using a small bolt, nut, and flat and lock washers (none shown), and the turnbuckle 14 is similarly connected to the inner end 23 of the outer strip 13.
As best shown in FIG. 3, a notch 25 is provided in the outer end 26 of the strip 13 to facilitate the connecting of the latter to an outer door hinge 3. In order to connect the strip 13 to the hinge 3, one bolt 28 normally holding the hinge 3 on the door is removed, the end 26 of the strip is placed on the hinge 3 with the notch 25 receiving one of the hinge flanges 29, and the bolt 28 is re-inserted through aligned holes (not shown) in the strip 13 and the hinge 3 into the door.
In the second embodiment of the invention (FIG. 4), the notch 25 can be omitted form the outer end 26 of the strip 13, and an L-shaped bracket or connector 30 is provided for connecting the end 26 of the strip 13 to the hinge 3. Both lower hinge bolts 28 are removed and re-inserted through a vertical arm 32 of the connector 30. The horizontal arm 33 of the connector 30 extends inwardly beneath the flange 29 of the hinge 3, and is connected to the outer end 26 of the strip 13 by a bolt 34, washers 35 (one shown) and a nut (not shown). This embodiment of the invention is actually intended for use when the notch 25 does not fit over the hinge flange 29.
Typical installation instructions for the device could read as follows:
1. Remove the top nut and bolt 28 from the bottom half of the hinge 3.
2. Place the outer end 26 of the strip 13 on the hinge 3 so that the holes in the hinge and in the strip 13 are aligned. If the notch 25 does not permit such alignment, remove the other nut and bolt 28 from the bottom half of the hinge, attach the outer end 26 of the strip 13 to the horizontal arm 33 of the connector 30 and connect the latter to the hinge using the hinge bolts 28.
3. Connect one end of the turnbuckle 14 to the inner, free end 23 of the strip 13 using the 1/4" bolt, nut, and flat and lock washers provided in the kit.
4. Connect the other end of the turnbuckle to the outer end 22 of the strip 12 using the 1/4" bolt, nut and flat and lock washers provided in the kit.
5. Repeat steps (1) and (4) on the other side of the door interior.
6. Fasten the inner ends 16 of strips 11 to the crossbar 6 using the middle door bolt 7. If a lag screw is used at the door centre, replace the lag screw with the longer lag screw provided in the kit. If not hole is present at the door centre, it will be necessary to drill a 3/8" or 11/64"× 1" deep pilot hole into the vertical arm of the crossbar 6.
7. With the turnbuckles 14 fully extended, connect the inner ends of the strips 12 to the outer end of the strips 11 using the bolts, nuts and lock washers provided in the kit.
8. Hand tighten the turnbuckles 14, and retighten all nuts and bolts.
9. Check the cement on the bottom of the door to determine whether the cement is level, and whether settling at the edges has occurred.
10. Raise the door and place a 2" block beneath the centre of the door. Lower the door onto the block and tighten the turnbuckle 14 until the door is straight. Remove the block.
11. Raise and lower the door three or four times. If the door is not flush with the floor, repeat step (10).
12. In severe cases, the above steps may have to be repeated after a delay of three to four weeks.
In some cases, it may be necessary to drill a hole through the lower end of the bottom panel 2 of the door to accommodate a bolt for connecting the two flat irons at the base of the door. The bolt would replace a central lag screw 7 on the door.
Another embodiment of the invention includes all of the elements of the device of FIGS. 1 to 3, with the exception of the notch 25 in the strip 13. With or without the notch 25, it has been found that the outer, top end of the strip 13 can be inserted beneath the bottom portion of the hinge, i.e. the bolts 28 can be removed, the strip 13 inserted beneath the bottom arm of the hinge, and the bolts 28 reinserted.
It will be appreciated that a reinforcing device of the type described above can be mounted on the lowermost horizontal door panel only, or alternatively similar devices can be mounted on a plurality of the horizontal panels. | Multi-sectional garage doors tend to bow downwardly in the middle because of the weight of the door. A simple solution to this problem is to provide a reinforcing device on the lowermost horizontal panel, the device including a pair of elongated bars for extending between the bottom center of the panel and the upper outer corners thereof, so that the load on the center of the door is transferred to the sides thereof to prevent sagging. The elongated bar is formed in sections interconnected end-to-end, one of the sections being a turnbuckle for adjusting the upward pull on the bottom of the door. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This invention is a continuation in part application and claims priority to U.S. patent application Ser. No. 14/644,281 that was filed on Mar. 11, 2015.
BACKGROUND
[0002] At various times during the life of a well it is desirable to treat the well. Such treatments include drilling, cementing, perforating, fracturing, gravel packing etc. These treatments generally involve pumping fluid with a number of agents typically solids, into the wellbore. For instance when pumping a drilling mud the drilling mud may be a weighted or non-weighted water-based gel. When weighted, the weighting material may be a particulate such as barite.
[0003] One of the functions of a drilling fluid is to seal the wellbore so that the fluid is not lost into highly permeable subterranean zones penetrated by the wellbore. This is accomplished by depositing filter cake solids from the drilling fluid over the surfaces of the wellbore then dehydrating the drilling fluid in order to allow the solids to bridge over the formation pores while not permanently plugging the pores.
[0004] When drilling a wellbore, the drilling fluid is continuously circulated down the interior of the drill pipe, through the drill bit and back to the surface in the annular area on the outside of the drill pipe. At various points the wellbore may need to be cased. In this event circulation of the drilling fluid ceases while the drill bit and drill pipe are removed from the well and casing is run into the well. With circulation stopped gelled and dehydrated drilling fluid and filter cake is deposited on the walls of the wellbore.
[0005] Once the casing has been run into the well typically cement is pumped through the interior of the casing, out the bottom of the casing, and back up the exterior sides of the casing. With cement in the area between the exterior of the casing and the wellbore cement may harden bonding the casing to the wellbore thereby sealing the annular area and preventing fluid communication axially along the exterior of the casing. Unfortunately, the gelled and dehydrated drilling fluid and filter cake tend to provide a barrier between the cement and the desired bonding surface, either the casing or the wellbore, thereby preventing the cement from bonding the casing to the wellbore. Additionally, the drilling fluid is comparatively expensive therefore operators prefer to attempt to retrieve the maximum amount of drilling fluid from the wellbore in an effort to reduce costs. In an attempt to remove the remnants of the drilling fluid from the wellbore prior to cementing a fluid flush a clear fluid pad may be pumped through the wellbore.
[0006] Although high fluid permeability is an important characteristic of a hydrocarbon-producing formation, the permeability on the well may be adversely affected by loss of treating fluid into the formation. For example, in a fracturing or fracing treatment it is desirable to control loss of the treating fluid into the formation to maintain a wedging effect and propagate the fracture through the entire formation to improve its permeability. However, there are limitations on the amount of treatment fluid that is able to be pumped downhole at a sufficient pressure. Without a sufficient amount of pressurized fluid the portion of the formation having higher permeability will most likely consume the major portion of the treatment fluid leaving the least permeable portion of the formation virtually untreated. Therefore, it is desired to control the loss of treating fluids to the highly permeable formations during such treatments.
[0007] The efficient treatment of the wellbore, at times, requires temporarily reducing permeability of a portion of the formation to increase the availability of treating fluids to the less permeable portion of the formation in order to create a relatively uniform permeability across the formation, the formation zone, or several formations. Several fluid loss agents have been developed for use in these treatments.
[0008] Prior fluid loss control agents included dissolvable or degradable materials such as polyglycolic acid and polylactic acid solids. Such materials have been used as diverting agents that are dispersed in the treating fluid to temporarily reduce the permeability of a portion of the formation or a zone of the well. After the treatment is completed the diverting agents then dissolve and flow out of the well once the well is put on production. Unfortunately, these types of diverting agents require relatively high temperatures in order to dissolve. For example, both polyglycolic acid and polylactic acid solids require weeks to reach 80% degradation when the fluid temperature is low temperature or less than 160° F.
[0009] Therefore, there is still a need for a low temperature diverting agent which can effectively and temporarily prevent fluid loss including during treatment operations and is capable of being removed from a low temperature well after treatment operations without leaving any residue in the wellbore or in the formation.
SUMMARY
[0010] In an embodiment of the invention isobutylene urea, methylene urea, or formaldehyde urea, well known as agricultural fertilizer, may be used as a diverting agent. Generally, very large amount of the diverting agent is loaded into the fluid system. Usually from between about 20% to about 50% by weight of the fluid system is the diverting agent. A viscosifier is added to carry the diverting agent into the formation. When these materials are used as a diverting agent they are able to flow into the formation zone of high fluid loss and restrict fluid flow through the formation zone. Then at least 80% of the material degrades over the next few days. As the temperature increases the rate of degradation increases and as the temperature decreases the rate of degradation decreases. However, it has been found that in the presence of a small amount of an organic acid catalyzing agent such as citric acid, acetic acid, or formic acid the rate of degradation at low temperatures, temperatures less than 160° F., is vastly increased. Typically, in the presence of an organic acid catalyzing agent, at least 80% of the material degrades within a few hours, typically 3 to 4 hours.
[0011] In practice, a well is identified where the temperature of the formation zones are less than 160° F. In such an instance the frac fluid is batch mixed in a slurry form on the surface with at least a viscosity enhancer that can be but is not restricted to guar gum and its derivatives, carboxymethylcellulose, cellulose derivatives, or polyacrylamide derivatives. Immediately prior, usually less than 10 minutes, to pumping the fluid into the wellbore an amount of the diverting material and acid catalyzing agent such as citric acid, acetic acid, or formic acid in either live or encapsulated form is mixed with the fluid. In some instances, such as when a greatly increased rate of degradation is desired, an inorganic acid, such as HCl, may be used as the catalyzing agent. Typically, the small amount of organic acid catalyzing agent is from about 5% to about 50% by weight of the diverting agent. The diverting material in solid form has a size particle distribution between 0.04 mm and 4.00 mm. As fluid is pumped into this formation zone of high permeability the diverting agent begins to seal off the fractures making them less and less permeable eventually causing the fluid to be diverted to a formation zone that was previously less permeable than the initial formation zone. The permeability of the second formation zone is then increased by the fracturing operation while at the same time being filled with diverting agent until the permeability of the second formation zone is reduced by the diverting agent so that the third formation zone is now the highest permeability of the zones to be treated. The fracturing operation is continued so that the third zone is fractured thereby increasing its permeability. After treating all three zones the permeability across each zone is relatively uniform. The process of treating the zones of the well may be repeated until the overall permeability of the desired zones in the well is increased. The diverting agent, in the presence of the catalyzing agent, begins to degrade such that 80% of the material has degraded within a few hours. Typically, the diverting agent that was initially placed will have degraded to the point where it can flow out of the well, once the well is put on production.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 is a wellbore having three zones with fractures.
[0013] FIG. 2 is a photo of the slotted disk prior to a fluid loss test.
[0014] FIG. 3 is a photo of the fluid less cell during a fluid loss test.
[0015] FIG. 4 is a photo of the slotted disk saturated with a diverting agent following a fluid loss test.
[0016] FIG. 5 is a graph of isobutylene-urea in the presence of various catalyzing agents at 140° F. over time.
[0017] FIG. 6 is a graph of isobutylene-urea in the presence of various catalyzing agents at 160° F. over time.
[0018] FIG. 7 is a graph of isobutylene-urea in the presence of various catalyzing agents at 180° F. over time.
[0019] FIG. 8 is a photo of a 0.1 inch slotted disk that has been removed from a test cell.
DETAILED DESCRIPTION
[0020] The description that follows includes exemplary apparatus, methods, techniques, or instruction sequences that embody techniques of the inventive subject matter. However, it is understood that the described embodiments may be practiced without these specific details.
[0021] FIG. 1 depicts a wellbore 10 having three formation zones 12 , 14 , and 16 where fractures 22 , 22 a, 24 , 24 a, 26 , and 26 a have been propagated into each of the three zones 12 , 14 , and 16 . Fracturing fluid is prevented from passing further down the wellbore 10 by bridge plug 30 . As diverting fluid, including a diverting agent and catalyzer, is pumped down the wellbore 10 as indicated by arrow 28 the diverting fluid will flow towards the path of least resistance, the most permeable of the three formation zones 12 , 14 , or 16 . If initially formation zone 14 is the most permeable zone the fracturing fluid will initially flow into the formation zone 14 via fractures 24 and 24 a . As the fluid continues to be pumped into formation zone 14 . The areas of permeability within the formation zone will begin to bridge due to the diverting agent being pumped in to the formation zone 14 .
[0022] The fluid may be a mixture of viscosified water with guar gum, guar derivatives, carboxymethylcellulose, cellulose derivatives, polyacrylamide polymers, copolymers derivatives or combinations thereof. In certain instances, a friction reducer may be included, preferably carboxymethylcellulose. When low temperature degradation is required, such as when the fluid that is being restricted by the diverting agent is less than 160° F., a catalyzing agent that facilitates the degradation, dissolution, erosion, etc of the diverting agent is added to the fracturing fluid prior to the fracturing fluid being pumped down hole. Preferably the catalyzing agent is added approximately in conjunction with the fracturing fluid entering the wellbore. The catalyzing agent is an organic or inorganic acid but is preferably citric acid or acetic acid added in an amount of between 5% and 50% percent of the total amount of the diverting agent.
[0023] From the surface it is very difficult to determine which the amount of fluid that is pumped into a particular formation zone and a predetermined amount of fluid is pumped into the wellbore 10 to fracture the three formation zones 12 , 14 , and 16 . Therefore if all of the fracturing fluid was pumped into formation zone 14 then formation zones 12 and 16 would not be treated or treated to a lesser extent than formation zone 14 . However, in this example as more diverting fluid is pumped in the most highly permeable formation zone 14 more diverting agent is also pumped into formation zone 14 . As the diverting agent is pumped into formation zone 14 the diverting agent will act to seal the fractures 24 and 24 a, including any newly propagated fractures thereby reducing the permeability of the formation zone 14 and causing the fracturing fluid that follows the diverting fluid to flow to next most highly permeable formation zone such as formation zone 16 where the process is repeated until all of the formation zones 12 , 14 , and 16 have been treated to increase the permeability of all of the formation zones 12 , 14 , and 16 .
[0024] Once all of the formation zones 12 , 14 , and 16 have been treated the formation zones are not initially permeable due to the diverting agent that has been forced into each zone. However, with the presence of the catalyzing agent the diverting agent begins to break down in a few hours. It is generally accepted that upon 80% of the diverting agent degrading, the diverting agent is then able to flow out of the well. Once the diverting has degraded and begins to move out of the fractures and the formation zones the now increased permeability of the formation zones is restored.
[0025] FIGS. 2, 3, and 4 depict a fluid loss control test. FIG. 2 depicts a slotted disk 100 having a 0.1 inch wide slot 102 through the slotted disk 100 .
[0026] FIG. 3 depicts the fluid loss cell 110 . The slotted disk 100 from FIG. 2 is placed in to bottom of the fluid loss cell 110 such that any fluid that exits the fluid loss cell 110 will have to have through the slot 102 and then to exit 112 at the bottom of the fluid loss cell 110 . The test is conducted by placing 410 ml of a fracturing fluid into the fluid loss cell. In this test the fluid was mixed in the ratios of 25 pounds of guar viscosifier per 1000 gallons of fluid, 1000 pounds of isobutylene urea per 1000 gallons of fluid, and 1000 pounds of 100 mesh sand per 1000 gallons of fluid. The fluid loss cell was then pressurized to 500 psi. After 30 minutes 55 ml of fluid was lost.
[0027] FIG. 4 is the slotted disk 100 after being removed from the fluid loss cell 110 . The slot 112 is sealed with diverting agent and sand.
[0028] FIG. 5 a graph of the degradation of isobutylene urea in various catalyzing agents at 140° F. over time. Line 190 is the plot of isobutylene urea when using a diverting agent load of 1% citric acid by weight of the total diverting material. The useful degradation amount is generally considered to be about 20% of the diverting agent remains after degradation. In the presence of 1% citric acid the isobutylene urea does not degrade to 20% or less. Line 192 is the plot of isobutylene urea in using a diverting agent load of 3% citric acid by weight of the total diverting material. In the presence of a diverting agent load of 3% citric acid by weight of the total diverting material the isobutylene urea degrades to about 20% remaining in about 9 days. Line 194 is the plot of isobutylene urea in using 5% citric acid. In the presence of a diverting agent load of 5% citric acid by weight of the total diverting material the isobutylene urea degrades to about 20% remaining in about 9 days. Line 196 is the plot of isobutylene urea in using a diverting agent load of 10% citric acid by weight of the total diverting material. In the presence of a diverting agent load of 10% citric acid by weight of the total diverting material the isobutylene urea degrades to about 20% remaining in about 4 days. Line 198 is the plot of isobutylene urea in using a diverting agent load of 15% citric acid by weight of the total diverting material. In the presence of 15% citric acid the isobutylene urea degrades to about 20% remaining in about 3 days. Line 199 is the plot of isobutylene urea in using a diverting agent load of 20% citric acid by weight of the total diverting material. In the presence of a diverting agent load of 20% citric acid by weight of the total diverting material the isobutylene urea degrades to about 20% remaining in about 16 hours.
[0029] FIG. 6 a graph of the degradation of isobutylene urea in various catalyzing agents at 160° F. over time. Line 200 is the plot of isobutylene urea in using a diverting agent load of 1% citric acid by weight of the total diverting material. In the presence of a diverting agent load of 1% citric acid by weight of the total diverting material the isobutylene urea degrades to about 20% remaining in about 9½ days. Line 202 is the plot of isobutylene urea in using a diverting agent load of 3% citric acid by weight of the total diverting material. In the presence of a diverting agent load of 3% citric acid by weight of the total diverting material the isobutylene urea degrades to about 20% remaining in about 4 days. Line 204 is the plot of isobutylene urea in using a diverting agent load of 5% citric acid by weight of the total diverting material. In the presence of a diverting agent load of 5% citric acid by weight of the total diverting material the isobutylene urea degrades to about 20% remaining in about 4 hours. Line 206 is the plot of isobutylene urea in using a diverting agent load of 5% encapsulated citric acid by weight of the total diverting material. In the presence of a diverting agent load of 5% encapsulated citric acid by weight of the total diverting material the isobutylene urea degrades to about 20% remaining in less than 4 hours.
[0030] FIG. 7 a graph of the degradation of isobutylene urea in various catalyzing agents at 180° F. over time. Line 220 is the plot of isobutylene urea in using a diverting agent load of 1% citric acid by weight of the total diverting material. In the presence of a diverting agent load of 1% citric acid by weight of the total diverting material the isobutylene urea degrades to about 20% remaining in about 6½ days. Line 222 is the plot of isobutylene urea in using a diverting agent load of 3% citric acid by weight of the total diverting material. In the presence of a diverting agent load of 3% citric acid by weight of the total diverting material the isobutylene urea degrades to about 20% remaining in about 1 day. Line 224 is the plot of isobutylene urea in using a diverting agent load of 5% citric acid by weight of the total diverting material. In the presence of a diverting agent load of 5% citric acid the isobutylene urea degrades to about 20% remaining in less than 4 hours. Line 226 is the plot of isobutylene urea in using a diverting agent load of 5% encapsulated citric acid by weight of the total diverting material. In the presence of a diverting agent load of 5% encapsulated citric acid by weight of the total diverting material the isobutylene urea degrades to about 20% remaining in less than 4 hours.
[0031] FIG. 8 is a 0.1 inch slotted disk 300 that was removed from a test cell after a fluid loss control test where fluid 302 consists essentially of 1.2 pounds per gallon of isobutylene urea, 0.2 pounds per gallon of a guar viscosifier, and 1 pound per gallon of 100 mesh proppant were mixed and then pressurized through the slotted disk 300 . The initial volume in the test cell was 410 ml and the fluid loss after 30 minutes was 72 ml.
[0032] While the embodiments are described with reference to various implementations and exploitations, it will be understood that these embodiments are illustrative and that the scope of the inventive subject matter is not limited to them. Many variations, modifications, additions and improvements are possible.
[0033] Plural instances may be provided for components, operations or structures described herein as a single instance. In general, structures and functionality presented as separate components in the exemplary configurations may be implemented as a combined structure or component. Similarly, structures and functionality presented as a single component may be implemented as separate components. These and other variations, modifications, additions, and improvements may fall within the scope of the inventive subject matter. | A treatment to temporarily block highly permeable areas in a wellbore having a temperature of less than 160° F. A diverting agent, a catalyzer, and a viscosifier are mixed together and pumped in the wellbore where the treatment flows in the most highly permeable areas. The diverting agent then begins to block those areas as the well is treated finally causing the fluid to divert to other now more highly permeable areas of the wellbore. After less than 48 hours the diverting agent degrades sufficiently to restore the permeablility of the wellbore. | 4 |
BACKGROUND OF THE INVENTION
1. Field of Invention
The present invention relates to a sliding-assistant unit, and more particularly to a sliding-assistant unit for a linear motion apparatus.
2. Description of the Related Art
A sliding-assistant unit is applied between a slider and a linear track of a linear motion apparatus to help the slider sliding along the linear track for transferring things and reducing noise and friction during the linear motion apparatus being operated.
A conventional sliding-assistant unit as shown in FIG. 1 of U.S. Pat. No. 6,729,760B2 is applied on a slider ( 2 ) to help the slider to move along a track ( 1 ). However, components of the conventional sliding-assistant unit are complicated. Additionally, each component of the conventional sliding-assistant unit is different to others, such that the assembling and manufacturing of the conventional sliding-assistant unit are difficult and complicated.
Another conventional sliding-assistant unit disclosed in US publication 2006/0072862 is mounted on a slider ( 20 ) and includes four U-shaped roller rings ( 30 ) to receive multiple rollers ( 51 ) inside with each roller ( 51 ) being partially exposed out to contact a track ( 10 ). Although components of the conventional sliding-assistant unit are much simplified, but each U-shaped roller ring ( 30 ) is assembled by two half shells as shown in FIGS. 3 to 5 . Thus, a seam will be formed between the two half shells and then causes non-smoothness of an inner surface of the roller ring ( 30 ). Consequently, friction between the roller ring ( 30 ) and the rollers ( 51 ) will be further increased due to non-smoothness of the inner surface of the roller ring ( 30 ).
To overcome the shortcomings, the present invention provides a sliding-assistant unit for a linear motion apparatus to mitigate or obviate the aforementioned problems.
SUMMARY OF THE INVENTION
The primary objective of the present invention is to provide a sliding-assistant unit for a linear motion apparatus, which has simplified structures and is formed as one unity.
A linear motion apparatus has a linear track, a slider and two sliding-assistant units for a linear motion apparatus. The sliding-assistant units for a linear motion apparatus are mounted between the track and the slider to enhance ease of movement between the track and the slider, and each sliding-assistant unit has two roller rings. The roller rings are elongated rectangular rings, are selectively mounted oppositely crossly around each other. Each roller ring is designed with reduced components to make manufacturing and assembling the sliding-assistant unit easier. Moreover, the roller ring is designed as one unity so no seam will be formed due to assembling two different pieces, such that ensures contact between the rollers and the roller ring smooth.
Other objectives, advantages and novel features of the invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a linear motion apparatus;
FIG. 2 is an exploded perspective view of the linear motion apparatus in FIG. 1 ;
FIG. 3 is a perspective view in partial section of the linear motion apparatus in FIG. 1 with a sliding-assistant unit for a linear motion apparatus in accordance with the present invention;
FIG. 4 is a perspective view in partial section of the linear motion apparatus in FIG. 1 ;
FIG. 5 is a front view in partial section of the linear motion apparatus in FIG. 1 ;
FIG. 6 is a perspective view of a sliding-assistant unit for a linear motion apparatus in FIG. 3 ;
FIG. 7A is an exploded perspective view of the sliding-assistant unit for a linear motion apparatus in FIG. 3 ;
FIG. 7B is a partial enlarged perspective view of the sliding-assistant unit for a linear motion apparatus in FIG. 3 ;
FIG. 8 is an enlarged partial front view in partial section of the linear motion apparatus in FIG. 1 ; and
FIG. 9 is another enlarged partial front view in partial section of the linear motion apparatus in FIG. 1 .
DETAILED DESCRIPTION OF THE INVENTION
With reference to FIGS. 1 to 3 , a linear motion apparatus comprises a linear track ( 50 ), a slider ( 1 ) and two sliding-assistant units ( 4 ) in accordance with the present invention.
With further reference to FIGS. 4 and 5 , the track ( 50 ) is elongated and has two ends, an inner segment, a middle segment, an outer segment, an inner track protrusion, an outer track protrusion, two inner guiding paths ( 51 ) and two outer guiding paths ( 52 ).
The inner track protrusion is formed on and protrudes oppositely away from the inner segment of the track ( 50 ) and forms two opposite inclined edges between the inner segment and the middle segment.
The outer track protrusion is formed on and protrudes oppositely away from the outer segment of the track ( 50 ) and forms two opposite inclined edges between the outer segment and the middle segment.
The inner guiding paths ( 51 ) are straight and are respectively formed on the inclined edges of the inner track protrusion between the ends of the track ( 50 ).
The outer guiding paths ( 52 ) are straight and are respectively formed on the inclined edges of the outer track protrusion between the ends of the track ( 50 ).
The slider ( 1 ) is mounted slidably on the track ( 50 ) and has a sliding body ( 10 ) and two end caps ( 20 ).
The sliding body ( 10 ) is mounted slidably around the inner track protrusion of the track ( 50 ) and has an inner surface, two ends, two sides and two clamping walls ( 11 ).
The inner surface of the sliding body ( 10 ) corresponds to the inner segment of the track ( 50 ).
The clamping walls ( 11 ) are respectively formed on and protrudes from the inner surface of the sliding body ( 10 ) at the sides between the ends, are parallel to each other and together clamp the track ( 50 ). Each clamping wall ( 11 ) has an inner surface, a path protrusion, a first mounting hole ( 14 ) and a second mounting hole ( 15 ).
The path protrusion of each clamping wall ( 11 ) is formed on and protrudes from the inner surface of the clamping wall ( 11 ) between the ends of the sliding body ( 10 ), correspondingly face towards the middle segment of the track ( 50 ), is inclined symmetrically in transverse cross-section to form an inner path ( 12 ) and an outer path ( 13 ) and may have a hooking groove ( 16 ).
The inner path ( 12 ) of the path protrusion of each clamping wall ( 11 ) corresponds to and is parallel with the corresponding inner guiding path ( 51 ).
The outer path ( 13 ) of the path protrusion of each clamping wall ( 11 ) corresponds to and is parallel with the corresponding outer guiding path ( 52 ).
The hooking groove ( 16 ) is formed in the path protrusion between to the inner path ( 12 ) and the outer path ( 13 ).
The first mounting hole ( 14 ) of each clamping wall ( 11 ) is round in cross-section, is formed longitudinally through the clamping wall ( 11 ) and corresponds to and is parallel with the outer path ( 13 ) and the corresponding outer guiding path ( 52 ).
The second mounting hole ( 15 ) of each clamping wall ( 11 ) is round in cross-section, is formed longitudinally through the clamping wall ( 11 ) and corresponds to and is parallel with the inner path ( 12 ) and the corresponding inner guiding path ( 51 ).
The end caps ( 20 ) are mounted respectively on the ends of the sliding body ( 10 ) and each end cap ( 20 ) has two mounting recesses ( 21 ).
Each mounting recess ( 21 ) is formed in the end cap ( 20 ), may be formed as two elongated slots that cross each other and corresponds to and aligns with the inner path ( 12 ), the outer path ( 13 ), the first mounting hole ( 14 ) and the second mounting hole ( 15 ) of the corresponding clamping wall ( 11 ) and the corresponding inner guiding path ( 51 ) and outer guiding path ( 52 ).
With further reference to FIGS. 6 , 7 A and 7 B, the sliding-assistant units ( 4 ) for a linear motion apparatus in accordance with the present invention is mounted between the track ( 50 ) and the slider ( 1 ) and each sliding-assistant unit ( 4 ) comprises two roller rings ( 40 ).
The roller rings ( 40 ) are selectively mounted oppositely crossly around each other and each roller ring ( 40 ) has a frame ( 41 ), a roller assembly ( 45 ), a head cover ( 42 ) and a side cover ( 43 ).
The frame ( 41 ) of each roller ring ( 40 ) is an elongated rectangular ring, is resilient and has an elongated hole, a sliding-assistance bar ( 410 ), a mounting bar ( 411 ), an exposing bridge ( 412 ), a mounting head ( 413 ), a roller groove ( 400 ), a gap ( 4130 ) and two limiting protrusions ( 4102 ).
The elongated hole is formed through the frame ( 41 ).
With further reference to FIG. 8 , the sliding-assistance bar ( 410 ) of one of the roller rings ( 40 ) corresponds to and is selectively mounted between the corresponding inner guiding path ( 51 ) and the corresponding inner path ( 12 ). The sliding-assistance bar ( 410 ) of the other roller ring ( 40 ) corresponds to and is selectively mounted between the corresponding outer guiding path ( 52 ) and the corresponding outer path ( 13 ). The sliding-assistance bar ( 410 ) has an inner side, an elongated opening ( 4100 ) and an optional hook protrusion ( 4101 ). The elongated opening ( 4100 ) is formed through the sliding-assistance bar ( 410 ). The hook protrusion ( 4101 ) is formed on and protrudes inwardly from the inner side of the sliding-assistance bar ( 410 ) and corresponds to and selectively engages the hooking groove ( 16 ) to further hold the sliding-assistance bar ( 410 ) in position.
The mounting bar ( 411 ) is parallel with the sliding-assistance bar ( 410 ) and corresponds to and is selectively mounted through one first mounting hole ( 14 ) or one second mounting hole ( 15 ).
The exposing bridge ( 412 ) connects between the sliding-assistance bar ( 410 ) and the mounting bar ( 411 ) and cooperates with the sliding-assistance bar ( 410 ) and the mounting bar ( 411 ) to form a U-shaped mount. The U-shaped mount has a width. The width corresponding to a thickness of the frame ( 41 ).
The mounting head ( 413 ) is parallel with the exposing bridge ( 412 ), protrudes from the sliding-assistance bar ( 410 ) and corresponds to the mounting bar ( 411 ) and has two opposite outside surfaces, a proximal end, a heading edge, two mounting recesses ( 4133 ) and a mounting slot ( 4131 ).
The mounting recesses ( 4133 ) are respectively formed in the opposite outside surfaces of the mounting head ( 413 ) adjacent to the heading edge.
The mounting slot ( 4131 ) is formed in the proximal end of the mounting head ( 413 ) from the heading edge.
The gap ( 4130 ) is formed between the mounting head ( 413 ) and the mounting bar ( 411 ). Therefore, an user can bend the mounting bar ( 411 ) outward to enlarge the gap ( 4130 ) first then mount the mounting bar ( 411 ) through the first hole ( 14 ) or the second hole ( 15 ) while assembling, also two frames ( 41 ) are able to be mounted around each other due to the gap ( 4130 ).
With further reference to FIG. 9 , the roller groove ( 400 ) is formed in and around the frame ( 41 ) and has an opening.
The limiting protrusions ( 4102 ) are oppositely formed in the sliding-assistance bar ( 410 ) to prevent the rollers ( 451 ) from falling off.
The roller assemblies ( 45 ) of the sliding-assistant unit ( 4 ) are respectively mounted in the roller grooves ( 400 ) of the frames ( 41 ) of the sliding-assistant unit ( 4 ) and each has a resilient belt ( 450 ) and multiple rollers ( 451 ).
The rollers ( 451 ) are cylinders, are parallelly mounted rollably in a column along the resilient belt ( 450 ), are mounted rollably in the roller groove ( 400 ) of the frame ( 41 ) and are partially exposed out from the roller groove ( 400 ) and the elongated opening in the sliding-assistance bar ( 410 ) to touch and roll between the inner guiding path ( 51 ) and the inner path ( 12 ) or the outer guiding path ( 52 ) and outer path ( 13 ) to reduce friction of movement between the slider ( 1 ) and the track ( 50 ).
The head cover ( 42 ) is mounted detachably on the mounting head ( 413 ) to prevent the roller assembly ( 45 ) from falling off, corresponds to and is selectively mounted in the U-shaped mount of the frame ( 41 ) and has an end, two tabs ( 420 ) and an engager ( 421 ).
The two tabs ( 420 ) are formed on and protrude from the head cover ( 42 ) and correspond to and selectively engage the mounting recesses ( 4133 ) to hold the head cover ( 42 ) on the mounting head ( 413 ).
The engager ( 421 ) is formed on and protrudes from the head cover ( 42 ) and corresponds to and selectively engages the mounting slot ( 4131 ) to hold the head cover ( 42 ) on the mounting head ( 413 ).
The side cover ( 43 ) is elongated, is mounted detachably on the mounting bar ( 411 ) to prevent the roller assembly ( 45 ) from falling off and has an inner surface, an outer surface, two outer side-edges, a receiving groove ( 430 ), an oil groove ( 431 ) and multiple oil holes ( 432 ).
The outer surface is flat and distances from an inner surface of one first mounting hole ( 14 ) or one second mounting hole ( 15 ) when the mounting bar ( 411 ) is mounted in the first mounting hole ( 14 ) or the second mounting hole ( 15 ) such that allows lubricant to be added into the first mounting hole ( 14 ) or the second mounting hole ( 15 ).
The outer side-edges are oppositely adjacent to the outer surface, are curved and selectively abut to and fit the inner surface of one first mounting hole ( 14 ) or one second mounting hole ( 15 ) so presses the side cover ( 43 ) securely on the mounting bar ( 411 ).
The receiving groove ( 430 ) is formed in the inner surface of the side cover ( 43 ) to receive the roller assembly ( 45 ) and has a bottom.
The oil groove ( 431 ) is formed in the bottom of the receiving groove ( 430 ).
The oil holes ( 432 ) are formed through the side cover ( 43 ) and communicate with the oil groove ( 431 ) to allow lubricant to be added on the roller assembly ( 45 ) when the mounting bar ( 411 ) is mounted in the first mounting hole ( 14 ) or the second mounting hole ( 15 ).
Consequently, components of the sliding-assistant unit ( 4 ) are much simplified such that manufacturing and assembling of the sliding-assistant unit ( 4 ) becomes much easier. In addition, because there is no seam that will be formed on surface of the roller groove ( 400 ), so contact between the roller groove ( 400 ) and the rollers ( 451 ) will be smooth. Even though the gap ( 4130 ) is formed on the frame ( 41 ) for assembling the sliding-assistant unit ( 4 ), but continuing surface of the roller groove ( 400 ) at the gap ( 4130 ) is kept flat after assembling so will not generate negative influence to the smoothness of the contact.
Even though numerous characteristics and advantages of the present invention have been set forth in the foregoing description, together with details of the structure and function of the invention, the disclosure is illustrative only. Changes may be made in detail, especially in matters of shape, size and arrangement of parts within the principles of the invention to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed. | A linear motion apparatus has a linear track, a slider and two sliding-assistant units for a linear motion apparatus. The sliding-assistant units for a linear motion apparatus is mounted between the track and the slider to enhance ease of movement between the track and the slider, and each sliding-assistant unit has two roller rings to receive rollers. The roller rings are elongated rectangular rings, are selectively mounted oppositely crossly around each other. Each roller ring is designed with reduced components to make manufacturing and assembling the sliding-assistant unit easier. Moreover, the roller ring is designed as one unity so no seam will be formed due to assembling two different pieces, such that ensures contact between the rollers and the roller ring smooth. | 5 |
This is a divisional application of U.S. patent application Ser. No. 07/471,514, filed Jan. 29, 1990, now U.S. Pat. No. 5,254,087.
FIELD OF THE INVENTION
This invention pertains to automated tourniquet apparatus for use in intravenous regional anesthesia of a limb for surgery. In particular, the invention pertains to apparatus having means for automatically controlling the introduction, retention and release of anesthetic fluid in a portion of the limb distal to a pressurizing cuff.
BACKGROUND OF THE INVENTION
This invention pertains to apparatus for automating the administration and management of intravenous regional anesthesia (IVRA) for both upper and lower limbs. IVRA is an alternative to general anesthesia for limb surgery. IVRA has proven to be a simple and useful technique for satisfactorily anesthetizing the upper limb and is potentially well suited for greatly expanded utilization in surgery of lower limbs and in outpatient settings. In these settings, which are rapidly increasing in number worldwide, there is a large and unmet need for a rapid, simple, safe, and reliable technique for establishing limb anesthesia. However, significant practical problems with the technology of IVRA in the prior art, considerable variations in skill involving the manual administration of IVRA, and lingering concerns over the potential toxicity of certain IVRA agents, particularly for lower limbs, have greatly limited the acceptance of this promising technique.
IVRA is an anesthetic technique which requires the use of surgical pneumatic tourniquet. Surgical pneumatic tourniquet systems are frequently used on the upper and lower limbs to help maintain a bloodless operative field by regulating the maximum pressure applied to the limb by an encircling cuff at a pressure sufficient to stop arterial blood flow past the cuff for the duration of a surgical procedure. During operations performed under IVRA, the pneumatic tourniquet serves an additional role of preventing local anesthetic agent introduced into the veins in the limb distal to the cuff from flowing proximally past the cuff and out of the limb into the circulatory system. An insufficient pressure in the tourniquet cuff soon after introduction of the local anesthetic agent into the limb may result in the anesthetic agent entering the circulatory system in a high concentration, which can cause serious adverse reactions such as cardiovascular collapse, respiratory depression, epileptic seizures or even death.
IVRA is typically administered as follows. Blood is first exsanguinated from the limb, often by wrapping the limb with an elastic bandage, beginning distally and wrapping tightly towards the heart; after exsanguination, a tourniquet cuff is applied proximal to the operative site and inflated to a predetermined cuff pressure. The elastic bandage is removed and an anesthetic agent such as lidocaine mixed with sterile saline is introduced into a vein in the limb through an intravenous cannula. The anesthetic fluid mixture remains in the veins in the limb as long as the tourniquet is inflated to a sufficient pressure. Premature release of the agent shortly after introduction, as well as leakage of the agent under the cuff during introduction or during surgery, are serious and recognized hazards associated with prior art devices used for IVRA.
Administration of IVRA may involve the use of a single-bladder or a dual-bladder tourniquet cuff. If a dual-bladder cuff has been chosen and applied to the limb of a patient, typically the proximal bladder of the cuff is first inflated, after limb exsanguination, to a pressure intended to prevent blood flow past the cuff both proximally and into the exsanguinated limb. The anesthetic fluid mixture is then introduced into a vein in the limb as described previously. After a period of time sufficient for the anesthetic fluid mixture to induce analgesia in the limb below the proximal bladder of the cuff, the distal bladder is inflated to a pressure intended to prevent the flow of fluid past the cuff both proximally and distally. The distal bladder of the cuff is thus inflated over anesthetized tissue, thereby resulting in greater comfort for the patient for a greater period of time, thus potentially extending both the duration of surgical procedures which can be performed under IVRA and the number of patients for whom IVRA will be tolerable.
Surgical tourniquet systems of the prior art typically include an inflatable cuff for applying to a limb and an automatic pressure regulator for regulating the inflation pressure in the cuff near a reference level selected by an operator or determined automatically. Some tourniquet systems in the prior art have been associated with a number of reported hazards and problems which are not specific to IVRA, such as unnecessarily high pressures applied by the cuff leading to nerve injury and tissue damage beneath the tourniquet cuff, and unexpectedly low pressures applied by the cuff leading to sudden blood flow into the surgical site, complication of surgery, passive congestion of the limb, and hemorrhagic nerve infiltration. Additionally, the cuffs of prior art systems have design limitations which make the cuffs difficult to apply consistently to limbs of different shapes and sizes. These design limitations of many prior art inflatable cuffs and tourniquet systems lead to clinical situations in which the maximum pressure actually applied by a prior art cuff to a limb is significantly different than the pressure in the inflatable bladder of the cuff and thus pressure indicated by the tourniquet pressure display.
There are also specific hazards associated with the use of prior art tourniquet systems for IVRA because the pressure of liquid anesthetic agents introduced into limb veins has generally not been monitored in the prior art, which has led to excessive pressures in the veins distal to the tourniquet cuff, thus causing anesthetic agent to flow past the cuff and into the general circulation. This can lead to an ineffective regional anesthesia in general, and even to cardiac arrest and death in reported cases.
A serious problem associated with the use of prior art tourniquet systems in relation to the delivery of anesthetic agents for IVRA is that in the prior art the maximum pressure applied by the tourniquet cuff to the limb is determined and adjusted independently of, and without knowledge of, the delivery pressure of the anesthetic agent. Moreover, the anesthetic agent is delivered in the prior art manually at a maximum pressure that is highly variable and dependent on the variations in operator technique. Most significantly, in the prior art, the pressure of liquid in the veins distal to the cuff is not a function of the maximum pressure applied by the tourniquet cuff. Consequently, it cannot be assured that the applied pressure is sufficiently greater than the venous pressure distal to the cuff so that no anesthetic agent will flow unexpectedly past the cuff and into the general circulation.
Another problem associated with prior art tourniquet systems is that no provision exists for automatically adjusting the pressure applied by the cuff such that bleeding arterial vessels can be observed in the surgical wound prior to completion of surgery, while the anesthetic fluid mixture is simultaneously retained in the veins of the limb distal to the cuff. Bleeding vessels can be observed only if the applied pressure is reduced sufficiently to permit arterial inflow; however, at the same time the applied pressure must be great enough to stop venous outflow and thereby maintain anesthesia. Prior art tourniquet systems do not provide any methods for reliably establishing and maintaining this condition.
For reasons of improved patient safety, there is a clinical need for wider tourniquet cuffs which appear to stop blood flow distal to such cuffs at lower inflation pressures than narrower cuffs. However, a significant problem with prior art cuffs in general, and with wide cuffs in particular, is that reliable and consistent sealing of the bladders is difficult due to the high forces generated internally because the forces on the sealed seams of bladders are generally proportional to the total internal area of the cuff multiplied by the inflation pressure.
A number of problems are associated specifically with prior art pneumatic cuffs used for IVRA. First, prior art cuffs have generally employed two bladders which can be inflated or deflated independently. Each bladder of an IVRA cuff must be narrower than a conventional tourniquet cuff in order that the IVRA cuff can fit on the patient's limb and not obstruct the desired surgical site. Second, prior art tourniquet cuffs commonly employ a flexible thermoplastic stiffener to constrain the inflation of the bladder and direct cuff inflation inwardly toward the encircled limb. The incorporation of stiffeners into prior art cuffs stabilizes the cuff bladders across the bladder width and thus reduces the tendency of cuffs to roll longitudinally down a limb when the bladders are pressurized. However, certain problems and hazards are associated with the use of prior art stiffeners. First, the incorporation of stiffeners into prior art tourniquet cuffs has tended to cause such cuffs to form a substantially cylindrical shape when applied to a limb, resulting in a poor shape match for limbs that are non-cylindrical in shape in the region underlying the encircling cuff. The use of stiffeners in prior art cuffs has also tended to cause the cuffs to be more difficult to apply by operating room staff in a snug and consistent manner. Also, the incorporation of stiffeners into prior art cuffs has added significantly to the costs of manufacture of such cuffs. Finally, the incorporation of stiffeners into prior art cuffs has created difficulties when the cuffs are cleaned or resterilized because certain resterilization processes apply heat to the cuffs, distorting the shape of stiffeners which are commonly formed of flexible thermoplastic material, thus detrimentally affecting the subsequent ability of the distorted cuff to conform smoothly to the encircled limb.
The present invention overcomes many of the hazards and problems associated with technology described in the prior art and significantly reduces variations in the quality and safety of IVRA associated with variable knowledge, skill and experience of operators. Thus the present invention facilitates the increased use of IVRA for anesthesia of both upper and lower limbs.
An object of the present invention is to provide tourniquet apparatus for intravenous regional anesthesia which automatically relates the maximum pressure applied to a limb by the tourniquet cuff to the maximum pressure of fluid in the veins in a portion of the limb distal to the cuff, so that the flow of fluid past the cuff proximally and into the circulatory system can be automatically regulated and stopped in a safe and reliable manner, as desired by an anesthetist or surgeon.
Another object of the present invention is to provide tourniquet apparatus having automatic means for estimation of the lowest pressure which can be applied by the cuff of the tourniquet apparatus to a limb in order to stop blood flow distal to the cuff, where the cuff has design and physical characteristics which are substantially different than those of a conventional blood pressure cuff, where the cuff is applied with an undetermined degree of snugness at any location along the limb between its proximal and distal end, and where there may be a substantial mismatch between the shape of the encircled limb and the shape of the encircling cuff.
A related object is to provide tourniquet apparatus having wider and safer cuffs for reducing the probability that blood will unexpectedly flow past the cuff distally, for reducing the probability that anesthetic fluid mixture will unexpectedly flow past the cuff proximally, for reducing the probability that clinical staff will make errors in applying the cuff to the correct location anatomically, and for increasing the tolerance of the patient to the cuff when pressurized so that more patients can take advantage of intravenous regional anesthesia.
Another object of the present invention is to provide means for more consistent and safer exsanguination of a portion of the limb distal to the tourniquet cuff prior to introduction of anesthetic agent into a vein in that limb portion, by automatically regulating the pressure in a pneumatic exsanguinating cuff distal to the tourniquet cuff for a period of time, and by automatically and sequentially inflating the tourniquet cuff proximal to the exsanguinating cuff when sufficient blood has been exsanguinated from the surrounded portion.
The applicant is aware of the following United States Patents which are more or less relevant to the subject matter of the applicant's invention.
______________________________________4,469,099 9/1984 McEwen 128/3274,479,494 10/1984 McEwen 128/3274,605,010 9/1986 McEwen 128/6864,770,175 9/1988 McEwen 128/3274,869,265 9/1989 McEwen 128/7744,321,929 3/1982 Lemelson 128/6304,635,635 1/1987 Robinette-Lehman 128/3274,781,189 11/1988 Vijil-Rosales 128/3274,168,063 9/1979 Rowland 273/54B3,164,152 1/1965 Vere Nicoll 128/874,667,672 5/1987 Romanowski 128/327______________________________________
The applicant is also aware of the following United States patent application which is more or less relevant to the subject matter of the applicant's invention. U.S. application Ser. No. 388,669; Title: Tourniquet for Regulating Applied Pressures; Art Unit: 335; Inventor: McEwen.
SUMMARY OF THE INVENTION
The invention is directed toward tourniquet apparatus for controlling the release of anesthetic fluid contained in a limb vein distal to a pressurized cuff, comprising: a pressurizing cuff for substantially encircling a limb and applying a varying pressure to an underlying vein in response to variations in a pressure control signal; applied venous pressure sensing means for producing an applied venous pressure signal representative of a pressure applied by the cuff to the underlying vein; venous fluid pressure estimation means for producing a venous fluid pressure signal representative of the pressure of fluid in the vein distal to the cuff; and pressure control means responsive to the venous fluid pressure signal and applied venous pressure signal for generating a pressure control signal to maintain a predetermined relationship between the applied venous pressure signal and the venous fluid pressure signal. The venous fluid pressure estimation means may be a signal representative of a predetermined constant reference pressure. Interval selection means may be included for determining a first time interval and a second time interval wherein the pressure control means generates a pressure control signal so that during the first time interval the pressure applied by the cuff to the underlying vein is greater than the minimum pressure which stops the flow of fluid in the vein past the cuff proximally, and during the second time interval the pressure applied by the cuff to the vein is less than the minimum pressure which stops the flow of fluid in the vein past the cuff proximally.
The invention is also directed to improved cuff apparatus for use in intravenous regional anesthesia comprising an occlusive band for applying pressure to a limb, and locating means on the band for locating the band on the limb at a predetermined distance from an anatomical reference site.
The invention is further directed to apparatus for estimating the minimum pressure which must be applied by a cuff to a limb in order to stop blood flow past the cuff, comprising: a pressurizing cuff responsive to cuff pressure control means for substantially encircling and applying pressure to a limb; distal flow sensing means for sensing the flow of blood past the pressurizing cuff; cuff pressure control means for controlling the pressure applied by the pressurizing cuff to the limb near a reference pressure; and flow detection means responsive to the distal flow sensing means for varying the reference pressure to estimate the lowest reference pressure at which no blood flow can be sensed past the pressurizing cuff. The pressurizing cuff may be a tourniquet cuff having design and construction characteristics substantially different than those of a cuff required for accurate estimation of blood pressure at the selected location by a noninvasive technique. Advantageously, occlusion pressure estimation means responsive to the lowest reference pressure at which no blood flow can be sensed past the pressurizing cuff may be included for producing an estimate of the lowest constant reference pressure at which no blood will flow past the pressurizing cuff over a time period that is suitably long for the performance of a surgical procedure.
The invention is also directed to automatic exsanguinating tourniquet apparatus to facilitate intravenous regional anesthesia comprising: occlusive cuff means for encircling a limb and applying a pressure to the encircled limb portion; exsanguinating cuff means for surrounding and applying a pressure to a portion of the limb distal to the occlusive cuff means; first reference pressure means for producing a first pressure signal representative of a pressure to be applied by the exsanguinating cuff means to displace blood from the portion of the limb surrounded by the exsanguinating cuff means; second reference pressure means for producing a second pressure signal representative of a pressure to be applied by the occlusive cuff means to occlude blood flow distal to the occlusive cuff means; and automatic pressure regulating means for regulating pressure applied by the exsanguinating means near a pressure indicated by the first pressure signal for a first period of time, and for regulating a pressure applied by the occlusive means near a pressure indicated by the second pressure signal for a second period of time suitably long for the performance of a surgical procedure.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram of the preferred embodiment.
FIG. 2 is a pictorial representation of the application to a limb of the cuffs of the preferred embodiment in FIG. 1.
FIG. 3 is a cut-away view of the inflatable tourniquet cuff of the preferred embodiment.
FIG. 4 is a sectional view taken along line 4-4 of FIG. 3.
FIG. 5 is a pictorial representation of the application to a limb of the dual-bladder cuff of the preferred embodiment.
FIG. 6 is a plan view of the dual-bladder cuff shown in FIG. 5.
FIG. 7 is a sectional view taken along line 7--7 of FIG. 6.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The embodiment illustrated is not intended to be exhaustive or to limit the invention to the precise form disclosed. It is chosen and described in order to explain the principles of the invention and its application and practical use, and thereby enable others skilled in the art to utilize the invention.
Referring to FIG. 1, an inflatable tourniquet cuff 2, which has locating strip 4 for positioning cuff 2 relative to an anatomical landmark, is applied to limb 6. Cuff 2 is connected by tubing 8 to pressure transducer 10 (Spectramed 072911-000-583, Spectramed Inc., Oxnard, Calif.), and then by tubing 12 to valves 14 (EVO-3-12 V, Clippard Instrument Laboratory, Cincinnati, Ohio). Valves 14 allow tubing 12 to be connected to tubing 16 and pressure source 18 which provides a source of gas at a regulated pressure between zero and 500 mmHg. This arrangement provides a means of inflating cuff 2 to apply a distribution of pressures varying from zero to some maximum level to the tissues and blood vessels of limb 6 beneath cuff 2, with the specific pressure distribution dependent upon cuff design and application technique. Valves 14 are controlled by an applied pressure control signal generated by microcomputer 20. Pressure transducer 10 generates an inflation pressure signal which indicates the pressure of gas in cuff 2 and which is processed by signal conditioner 22, digitized by analog to digital converter (ADC) 24, and communicated to microcomputer 20. Limb pressure sensor 26, such as the biomedical pressure transducer described by McEwen in U.S. Pat. No. 4,869,265, is placed underneath cuff 2 at a location such that the maximum pressure applied by cuff 2 to limb 6 is transduced. Limb pressure sensor 26 generates an applied pressure signal which is indicative of that maximum pressure. The applied pressure signal is processed by signal conditioner 28, digitized by ADC 24, and communicated to microcomputer 20. Photoplethysmographic flow sensor 30 is placed on a portion of limb 6 distal to cuff 2 in order to sense blood flow in limb 6. Sensor 30 generates a blood flow signal which is processed by signal conditioner 32, digitized by ADC 24, and communicated to microcomputer 20. Cannula 34 is inserted in a vein in limb 6 distal to cuff 2 and is connected by tubing 36 to pressure transducer 38 to allow estimation of the venous fluid pressure; pressure transducer 38 generates a venous fluid pressure signal which is processed by signal conditioner 40, digitized by ADC 24, and communicated to microcomputer 20. Cannula 42 is inserted in a vein in limb 6 distal to cuff 2 and is connected by tubing 44 to pressure transducer 46; pressure transducer 46 is connected by tubing 48 to anesthetic container 50 which holds a fluid anesthetic such as lidocaine mixed with a sterile saline solution; anesthetic container 50 is typically a sterile saline bag in which the fluid anesthetic has been previously introduced with a syringe. The mixture of fluid anesthetic and sterile saline is delivered by delivery module 52; delivery module 52 applies a pressure to anesthetic container 50 and thereby forces the mixture from anesthetic container 50 into the vein through cannula 42. Delivery module 52 is connected by tubing 54 and valves 56 to pressure source 18. Valves 56, which control the delivery pressure of the anesthetic fluid mixture, are responsive to the delivery pressure control signal. Pressure transducer 46 generates a delivery pressure signal representative of the anesthetic fluid mixture pressure which is processed by signal conditioner 84, digitized by ADC 24, and communicated to microcomputer 20.
FIG. 2 shows exsanguinating cuff 62 applied to limb 6. Referring to FIG. 1, exsanguinating cuff 62, such as the Jobst-Jet Air Splint (Jobst Institute Inc., Toledo, Ohio) of a size appropriate for the portion of limb 6 to be exsanguinated, is connected through tubing 64 to pressure transducer 66; pressure transducer 66 is connected through tubing 68 and valves 70 to pressure source 18. This arrangement provides exsanguinating cuff 62 with a means of inflation. Valves 70 are operated by an exsanguinating control signal from microcomputer 20 in order to vary the pressure in exsanguinating cuff 62. This produces a variation in the distribution of pressures applied by exsanguinating cuff 62 to limb 6. Pressure transducer 66 generates an exsanguinating pressure signal which is processed by signal conditioner 72, digitized by ADC 24, and communicated to microcomputer 20. Doppler blood flow sensor 74 positioned under exsanguinating cuff 62 over an artery in limb 6 generates a residual blood signal which is processed by signal conditioner 76, digitized by ADC 24, and communicated to microcomputer 20.
The user communicates with the system by means of user panel 78. Switches 80 on user panel 78 are used to input information and commands from the user to microcomputer 20, and microcomputer 20 reports pressures, system status, and alarms to the user by audio/visual display 82.
In operation, the user instructs microcomputer 20 by means of user panel 78 to automatically estimate the lowest reference pressure at which no blood flow can be sensed past cuff 2 by photoplethysmographic blood flow sensor 30. This is accomplished by varying the reference pressure which causes the maximum pressure applied by cuff 2 to vary accordingly, and by monitoring the resulting variations in blood flow distal to cuff 2 as follows. Microcomputer 20 produces an applied pressure control signal which activates valves 14 to inflate cuff 2, thereby causing the maximum pressure applied to limb 6 by cuff 2 to increase as indicated by the applied pressure signal produced by sensor 26. While the reference pressure is being increased, microcomputer 20 detects the lowest applied pressure at which the flow signal falls below a predetermined threshold near zero. This value of the applied pressure is an estimate of lowest reference pressure which stops blood flow past cuff 2. Microcomputer 20 then acts to increase the applied pressure to 20 mmHg above this lowest reference pressure, after which an applied pressure control signal is generated to deflate cuff 2, thereby decreasing the applied pressure. While cuff 2 is being deflated, microcomputer 20 monitors the blood flow signal from sensor 30 and detects the applied pressure at which the flow signal exceeds the predetermined threshold. This value of the applied pressure is an estimate of the highest reference pressure at which blood flow past cuff 2 can be sensed. Microcomputer 20 then calculates the mean of the highest reference pressure and lowest reference pressure thus obtained and adds 75 mmHg to this mean value, thereby producing an estimate of the lowest constant reference pressure at which no blood will flow past cuff 2 over a time period which is suitably long for the performance of a surgical procedure. Once the lowest constant reference pressure has been estimated, blood flow sensor 30 is removed if clinically desired. For unusual clinical situations in which a blood flow signal cannot be detected by microcomputer 20, provision is made for an estimate of the lowest constant reference pressure to be entered manually by the user through user panel 78.
Following the estimation of the lowest constant reference pressure, the user instructs microcomputer 20 with switches 80 on user panel 78 to exsanguinate the portion of limb 6 surrounded by exsanguinating cuff 62. This is accomplished as follows. Microcomputer 20 generates an exsanguinating control signal which activates valves 70 and thus causes exsanguinating cuff 62 to inflate to a predetermined inflation pressure of approximately 100 mmHg. The pressure applied to limb 6 by exsanguinating cuff 62 is regulated at a constant level by microcomputer 20 using pressure transducer 66 and valves 70. Microcomputer 20 monitors the residual blood signal from Doppler blood flow sensor 74 to determine the period of time that the constant pressure is applied in order to displace a significant volume of blood from the portion of limb 6 surrounded by exsanguinating cuff 62. As exsanguinating cuff 62 inflates, the amplitude of the pulsatile signal detected by Doppler blood flow sensor 74 decreases, thereby providing an indication that arterial inflow is being reduced. After the amplitude of the residual blood signal has fallen below a threshold near zero, the pressure is maintained at the constant level for two minutes, after which the portion of limb 6 surrounded by exsanguinating cuff 62 is considered to be adequately exsanguinated. For unusual situations in which a residual blood signal cannot be obtained by microcomputer 20 from sensor 74, provision is made for the user to define the period of time exsanguinating cuff 62 is to remain inflated. Microcomputer 20 then generates an applied pressure control signal to inflate cuff 2 to the lowest constant reference pressure previously estimated as described above. This stops blood flow past cuff 2 in the exsanguinated portion of limb 6 distal to cuff 2. Thereafter, microcomputer 20 continues to automatically regulate the maximum pressure applied to limb 6 by cuff 2 near the lowest constant reference pressure to stop blood flow past cuff 2 for a period of time suitably long for the performance of a surgical procedure.
After exsanguination, cannula 34 is inserted into a vein in limb 6 distal to cuff 2, and cannula 42 is inserted into a vein in limb 6 appropriate for introduction of the anesthetic fluid mixture. Microcomputer 20 is then instructed by the user through user panel 78 to deliver the anesthetic fluid mixture at a maximum pressure such that the anesthetic fluid mixture does not flow proximally past cuff 2. Microcomputer 20 analyses the applied pressure signal from limb pressure sensor 26 and the delivery pressure signal from transducer 46 in order to generate a delivery control signal such that the ratio of the delivery pressure signal to the applied pressure signal is less than 0.75. Microcomputer 20 does not allow the delivery pressure to exceed a maximum level of 100 mmHg for safety reasons. In an unusual clinical situation when the delivery pressure cannot be controlled, such as when the user may have to pressurize anesthetic container 50 manually, provision is included for stopping the flow of the anesthetic fluid mixture past cuff 2 proximally by increasing the pressure applied to the limb. This is done by having microcomputer 20 monitor the delivery pressure signal by means of transducer 46 and generate an applied pressure control signal such that the ratio of the delivery pressure signal to the applied pressure signal is less than 0.75.
Once the anesthetic fluid mixture has been delivered to a vein in limb 6, it must be retained in the portion of limb 6 distal to cuff 2 during most of the surgical procedure and released near the end of the surgical procedure. The flow of anesthetic fluid mixture past cuff 2 is controlled according to the following algorithm. Microcomputer 20 monitors the applied pressure signal from sensor 26 and the venous fluid pressure signal from transducer 38. Microcomputer 20 then generates an applied pressure control signal such that the maximum pressure applied by cuff 2 is regulated at a pressure at least 50 mmHg above the venous fluid pressure. Because the maximum applied pressure is at least 50 mmHg greater than the venous fluid pressure, the anesthetic fluid mixture is retained within limb 6.
When release of the anesthetic fluid mixture from limb 6 is desired, microcomputer 20 generates an applied pressure control signal such that the maximum pressure applied by cuff 2 is regulated at a level below the venous fluid pressure to allow outflow of the anesthetic fluid mixture. In clinical cases where it is important to identify bleeding arterial vessels in the surgical site prior to completion of surgery without releasing the anesthetic fluid mixture from limb 6, the user can cause microcomputer 20 to generate an applied pressure control signal such that the maximum pressure applied by cuff 2 is regulated at a pressure less than the lowest constant reference pressure previously determined, but above the venous fluid pressure. In this way, arterial blood flows past cuff 2 distally, but venous fluid does not flow past cuff 2 proximally. This provision significantly extends the range of surgical procedures in which intravenous regional anesthesia can be used.
In a condition where it is not possible to use cannula 34 and transducer 38 to estimate venous fluid pressure, provision is included for microcomputer 20 to substitute 20 mmHg for the venous fluid pressure.
Near the end of the surgery, the user instructs microcomputer 20 to release the anesthetic fluid mixture from limb 6 in a controlled manner over a period of time with user panel 78. This is accomplished as follows. First, microcomputer 20 generates an applied pressure control signal so that the maximum pressure applied by cuff 2 is regulated at a pressure which allows venous outflow from limb 6 for a period of 10 s to allow a portion of the anesthetic fluid mixture to be released from the vein of limb 6. Microcomputer 20 then generates an applied pressure control signal so that the maximum pressure applied by cuff 2 is regulated at a higher pressure so that any flow of the anesthetic fluid mixture past cuff 2 is stopped. This higher pressure is regulated for a period of 60 s in order to allow assimilation of the anesthetic fluid mixture and venous blood into the general circulation. The foregoing sequence of increasing and decreasing the maximum pressure applied to limb 6 by cuff 2 is repeated three times, after which cuff 2 is completely depressurized. This procedure allows for complete release of the anesthetic fluid mixture from limb 6 in a safe manner. Provision has been made so that the time interval over which the applied pressure remains at the lower pressure, the time interval over which the applied pressure remains at the higher pressure, and the number of times that the applied pressure is cyclically decreased and then increased can be overridden or changed.
FIG. 3 shows details of inflatable tourniquet cuff 2. Cuff 2 is fabricated as described by Robinette-Lehman in U.S. Pat. No. 4,635,635. In contrast to Robinette-Lehman, as can be seen in FIGS. 3 and 4, cuff 2 has no stiffener, is not arcuate in shape, includes locating strip 4 for positioning cuff 2 on limb 6 at a predetermined distance from an anatomical landmark, is substantially different in width, and is otherwise different as described below.
As can be seen in FIG. 3, tourniquet cuff 2 has an inflatable chamber 86 which includes a plurality of elongated tubular portions 88 which are connected in a generally parallel array, and which are in fluid communication by passageways 90. Tubular portions 88 are formed by joining together at seams 96 two plastic layers 92,94 which form the walls of inflatable chamber 86. Cuffs having chamber widths of 15, 20 and 25 cm, instead of the conventional maximum width of less than 9 cm, were fabricated. Fabrication of these wider cuffs was possible because the plurality of tubular portions 88 in inflatable chamber 86 act to significantly reduce the forces on seams 96, because the forces on seams 96 are generally proportional to the total internal area bounded by seams 96 multiplied by the inflation pressure.
The tubular portions 88, their adjacent seams 96, and passageways 90 are hereinafter referred to as flutes 98. The plurality of elongated tubular portions 88 in inflatable chamber 86 stiffens cuff 2 and allows for a desired distribution of pressure to be applied to limb 6 by choosing appropriate distances between seams 96, since varying these distances results in a change in the pressure distribution underlying cuff 2. Cuff 2 is wrapped about limb 6 and is held in place by female Velcro strips 58 and male Velcro strips 60. Cuff 2 is further held in place by tying together the ends of strap 100 after cuff 2 has been applied to limb 6. Cuff 2 is inflated with gas via ports 102.
FIG. 4 is a sectional view of inflatable tourniquet cuff which shows inflatable chamber 86 and two outer layers 104,106.
For certain surgical procedures of long duration, dual-bladder cuff 108 depicted in FIGS. 5, 6, and 7 is used for increased comfort. In cuff 108, two bladders 110, 112 overlap and are permanently bonded together such that 30 percent of the width of each bladder lies within the overlapping region 114. Bladders 110, 112 are independently and selectably inflatable by appropriate valves and switching. The overlapping of bladders 110,112 around limb 6 in a predefined relationship distributes the pressure applied by each bladder over a greater length along limb 6 than would be possible if narrower bladders which did not overlap occupied the same total width. Distribution of pressures over a greater length along the limb in this manner lowers the maximum pressure which must be applied to prevent fluid flow past cuff 108 thereby resulting in a reduced risk of underlying nerve injury and greater comfort for the patient. Locating strip 4, which is 1.5 inches wide, cannot be inflated. Locating strip 4 permits an unskilled user to accurately and consistently apply cuff 108 at a fixed distance from an anatomical reference site. In lower limb surgery, for example, the top of locating strip 4 is positioned on the head of the fibula so that the top of cuff 108 encircles limb 6 approximately 1.5 inches distal to the head of the fibula. This reduces the likelihood of a compression injury to the peroneal nerve below the head of the fibula following pressurization of cuff 108.
It is to be understood that the invention is not to be limited to the details herein given but may be modified within the scope of the appended claims. | Tourniquet apparatus for use in intravenous regional anesthesia and limb surgery includes a pressurizing cuff for substantially encircling a limb and applying a varying pressure to an underlying vein in response to variations in a pressure control signal, applied venous pressure sensing means for producing an applied venous pressure signal representative of a pressure applied by the cuff to the underlying vein, venous pressure estimation means for producing a venous fluid pressure signal representative of the pressure of fluid in the vein distal to the cuff, and pressure control means responsive to the venous fluid pressure signal and applied venous pressure signal for generating a pressure control signal to maintain a predetermined relationship between the applied venous pressure signal and the venous fluid pressure signal. The apparatus automatically controls the introduction, retention and release of anesthetic fluid in the limb. | 0 |
This application is a continuation of application Ser. No. 08/126,105, filed Sep. 22, 1993 now abandoned which is a continuation of application Ser. No. 07/894,928, Jun. 8, 1992, now abandoned.
INVENTION FIELD
A process is described for the purification of the hepatitis A virus (HAV) in which the material from the culture cells, after cell lysis and centrifugation, is submitted to gel filtration and the thus obtained eluate is submitted to ion exchange chromatography.
STATE OF THE ART
The hepatitis A virus (HAV) is a icosahedral morphology Picornavirus with 32 capsomeres on its surface, which presents four important structural polypeptides; VP1 with a molecular weight MSW 30.000-33.000, VP2 24.000-27.000, VP3 21.000-23.000, VP4 7.000-14.000.
Said four proteins ape the ones responsible for the antigenic virus power and are therefore the ones which the purification processes tend to put in evidence and to isolate in order to obtain, with a good degree of purity, an inactivated vaccine. The purification processes seek to eliminate cellular contaminants and growth factors which are employed in the virus production process.
Various methods for the partial virus purification, both for vaccination and for virus characterization purposes, have been described. For example, through the virus sedimentation by means of a 20% sucrose pad and successive centrifugation in a cesium chloride gradient [P. J. Provost et al. J. of Medical Virology 19, p. 23-31 (1986)], through ammonium sulphate precipitation and sedimentation with a 20% sucrose pad and cesium chloride gradient [Flehmig B. et al., J. of Medical Virology 22, p. 7-16 (1987)], with a lysis buffer, freezing, defrosting, sonication to set the virus free, ultrafiltration with tangential flow and purification in cesium chloride gradient [Flehmig et al., The Lancet, May 13, p. 1039 (1989)], through various clarification cycles and successive freon or chloroform extraction followed by gel filtration, ion exchange chromatography and purification in cesium chloride gradient [S. A. Locarnini, Intervirology 10, 300-308 (1978)].
All the above mentioned processes employ, at least in one step, ultracentrifugation systems and high cost materials such as cesium chloride, and therefore, although yielding excellent results on a small scale, are hardly suitable for an industrial production, in which process duration, costs and availability of suitable personnel have to be taken into consideration.
In the European Patent Application EP-A-302692 a process for the purification of hepatitis A virus is described, which employs sonication for the cell lysis, followed by extraction with organic solvents and successive concentration, chromatography on anion exchange resins and, finally, gel filtration chromatography. Also this process, particularly in view of the use of sonication and of organic phase extractions and concentrations, presents, on an industrial scale, certain operative difficulties.
DETAILED DESCRIPTION OF THE INVENTION
The process according to the present invention allows to obviate the mentioned drawbacks and is therefore a valid contribution to the purification on an industrial scale and the production of a purified HAV virus suitable for the use as a vaccine.
Diploid human cells MRC-5 designated by the World Health Organization as suitable for the production of vaccines for human use, cultivated and collected according to conventional techniques, were used.
The cells were infected with HAV at the 30th passage. After 21 days incubation, the cell substrate was washed with PBS-A to eliminate as much as possible the fetal bovine serum present in the culture medium and indispensable for the substrate.
The infected cells were taken up with trypsin EDTA following traditional methods and re-suspended in hypotonic buffer (Tris 10 mM, NaCl 10 mM, pH 7.5), this causing cell lysis and therefore setting the virus free, and frozen.
At the time of purification the material is defrosted and treated with 2% Triton-X-100 for 30 min. at room temperature, stirring about every 5 min.; the material is then collected by centrifugation, so as to remove the cell fragments; this treatment allows the solubilization of membrane lipids with which the virus is strictly associated. The next step is gel filtration, employing gel filtration beds of both agarose and dextran, e.g. SEPHAROSE CL-4B resin (Pharmacia) equilibrated in TNE buffer (Tris 10 mM, NaCl 150 mM, EDTA 1 mM, pH.7.2-7.6), containing 0.1-0.2% Triton-X-100 or glycine buffer 0.1 M with 0.2% deoxycholate, pH 8.5. The eluated material is collected in 20 ml fractions which are tested for the presence of HAV by an ELISA assay. With this passage, yields of 85-95% are obtained with an approximate eight-fold purity increase (30-50 μg virus per mg of protein).
The eluate obtained in the preceding step is then submitted to ion exchange chromatography employing anion exchange resins, such as e.g. DEAE SEPHAROSE CL-6B resin equilibrated in TNE containing 0.1%-0.2% Triton-X-100; in these conditions the virus is adsorbed on the bed while part of the contaminants are not retained.
After washing the column with TNE, to eliminate the detergent, eluition is performed decreasing the pH and increasing the ion strength. To this end a phosphate buffer may be employed with a continuous pH gradient from 7.4 to 4 and ionic strength from 0 to 0.3M NaCl . The yield in this second step is of the order of 50% with respect to the preceding step and the purity of the collected virus is increased 6 to 10 times (with an average virus contents of 70% on the total protein). The thus purified material is filtered on a membrane of 0.22 μm porosity and inactivated with 1:2000 formalin at 35° C. for 5 days under continuous stirring.
During the inactivation period, disaggregating treatments are performed, the 2nd day the material is sonicated at 50-60 W 1 sec/ml. The third day the material is filtered on a 0.22 μm membrane and L-lysine.HCl 25 mM is added. After inactivation, the suspension is dialyzed against PBS A (1:100 v/v) for about 36 hrs, with an intermediate buffer substitution. After dialysis, the material is submitted to a sterilizing filtration and the product undergoes all the required controls: sterility, pyrogenicity, inactivation, antigenicity, pH, stability, residual formalin.
Experimental Section
MRC-5 cells at the 30th passage in rotating 850 cm 2 bottles are infected with HAV (strain LSH/S ATCC VR 2266) at a 0.5 MOI. After a 20 day incubation period, the cellular substrate is washed 3 times with serum-free medium maintaining the last washing overnight. The following day the cells are removed with trypsin-EDTA following traditional methods, and suspended again in hypotonic buffer (Tris 10 mM, NaCl 10 mM, pH 7.5) 1 ml for each 100 cm 2 cell culture and frozen.
60 ml of the frozen suspension, deriving from approximately 5.700 cm 2 culture are defrosted and treated with a non ionic detergent (2% Triton-X-100) for 20 to 30 minutes at room temperature under moderate stirring every 5-10 minutes.
The sample is centrifuged at 400 g for 10 minutes while cooling to remove cellular fragments. The supernatant is purified through gel filtration on a agarose resin (SEPHAROSE CL4B resin Pharmacia)column 5×90 cm (K 50/100 column, Pharmacia) equilibrated with Tris 10 mM, NaCl 150 mM, EDTA 1 mM buffer, pH 7.4, containing 0.1% Triton-X-100 at a 75 ml/h flow rate. The eluted material is collected in 20 ml fractions which are tested for the presence of HAV by a ELISA assay. The HAV containing fractions are collected, obtaining approximately 400 ml. This material is further purified by ion exchange chromatography seeding about 200 ml, at a flow rate of 100 ml/h on a anionic resin (SEPHAROSE CL6B resin Pharmacia) column 5×5 (column XK 50/30 Pharmacia) which had previously been equilibrated in Tris 10 mM, NaCl 150 mM, EDTA 1 mM, pH 7.4 buffer containing 0.1% Triton-X-100. Under such conditions the virus is adsorbed on the matrix. The matrix is washed with Triton-X-100 free buffer to remove the detergent and the virus is eluted at a flow of approximately 160 ml/h, applying a continuous pH gradient and ionic strength, starting from pH 7.4 and NaCl 0 mM to pH 4 and NaCl 0.3M. The eluted material is collected in fractions of about 10 ml and the fractions found positive for the presence of HAV at a ELISA assay are put together.
A virus content of 70% on the total protein is thus obtained. The thus purified material is filtered on 0.22 μm porous membrane and inactivated with formalin 1.2000 at 35° C. for 5 days under continuous stirring. During the inactivation period, disaggregation treatments are performed: on the 2nd day the material is sonicated at 50-60 W per 1 second/1 ml; on the 3rd day it is filtered on a 0.22 μm membrane and L-lysine. HCl 25 mM is added. After inactivation, the suspension is dialyzed against PBS-A (KCl2.7 mM, KH 2 PO 4 1.5 mM, NaCl 137 mM, NaH 2 PO 4 8.1 mM, pH 7.4) in a 1:100 v/v ratio for 36 hours with an intermediate buffer substitution. After dialysis, the material undergoes a sterilizing filtration and is then submitted to the usual controls for sterility, pyrogenicity, inactivation, antigenicity, pH, stability and residual formalin.
Hepatitis A virus, strain LSH/H, purified as outlined above was deposited with the American Type Culture Collection(ATCC), 12301 Parklawn Dr., Rockville, Md. 20852, on Oct. 24, 1989. The deposit was made pursuant to the Budapest Treaty. The deposit was assigned ATCC accession number VR 2266. | A process is described for the purification of the hepatitis A virus, which allows one to obtain with good yields a pure product, in which organic material collected by centrifugation after lysis of the culture cells is submitted to gel filtration and successively to ion exchange chromatography. | 0 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application claims priority to Korean Patent Application No. 10-2008-0082461 on Aug. 22, 2008, the entire contents of which is incorporated herein for all purposes by this reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a radiator of an automobile, and more particularly, to a cooling system which efficiently cools an internal combustion engine and an electric side in a hybrid vehicle driven by an electric motor using a battery and an internal combustion engine using fuel such as gasoline.
[0004] 2. Description of Related Art
[0005] A hybrid vehicle is a vehicle which obtains a driving force by combining an engine and a motor and simultaneously or selectively driving them.
[0006] Here, electric parts including a driving motor generate heat when activated, and there is a need to install a cooling device for suppressing a temperature rise of the parts in order to keep input/output characteristics of the parts in their best conditions.
[0007] Especially, a battery should be kept at an appropriate temperature in order to keep the overall charging and discharging efficiency in its best condition. Therefore, heat generated by charging and discharging the battery is cooled down by the cooling device to maintain an appropriate temperature.
[0008] FIG. 1 is a schematic view of a conventional cooling system for a hybrid vehicle.
[0009] FIG. 1 involves a well-known technology in Japan by Japan's Toyota Motor (JP 1998-259721A). A power source cooling device for a hybrid vehicle includes a first cooling water circulation passage 10 through which cooling water for cooling an internal combustion engine side flows, a second cooling water circulation passage 20 through which cooling water for cooling an electric motor side flows, a single radiator 30 which is installed with respect to the first cooling water circulation passage 10 and the second cooling water circulation passage 20 , and through which the cooling water 50 for cooling the internal combustion engine side and the cooling water 50 for cooling the electric motor side flow in the same direction, and a first cap 40 A installed on the first cooling water circulation passage 10 and a second cap 40 B installed on the second cooling water circulation passage 20 .
[0010] The first cooling water circulation passage 10 sequentially connect an internal combustion engine 11 , the radiator 30 , and a water pump 12 along a cooling water flow direction. Water is added to fill cooling water after removing the first cap 40 A, and the first cap 40 A is mounted again on the radiator 30 after pouring water.
[0011] The second cooling water circulation passage 20 sequentially connect an electric motor 21 for driving the wheels of the vehicle, an electric generator 22 , the radiator 30 , a cooling water storage tank 25 , an inverter 23 for converting direct current and alternating current, and a water pump 24 along the cooling water flow direction.
[0012] Water is added to fill cooling water after removing the second cap 40 B, and the second cap 40 B is mounted again on the storage tank 25 after pouring water.
[0013] A partition 34 for partitioning off the first cooling water circulation passage 10 and the second cooling water circulation passage 20 is installed on an upstream tank 31 and a downstream tank 32 , respectively. Due to this, a core portion 33 , too, is divided into a part 33 A in which the cooling water flowing through the first cooling water circulation passage flows and a part 33 B in which the cooling water flowing through the second cooling water circulation passage flows.
[0014] FIG. 2 is a schematic view of another conventional cooling system for a hybrid vehicle.
[0015] FIG. 2 involves an internationally well-known technology disclosed in Modine Manufacturing Company's global patent application (U.S. Pat. No. 6,124,644). Briefly put, a vehicle employs a system which has first a single radiator 68 divided into first and second sections 60 and 62 , the first section 60 being isolated from fluid communication with the second section 62 , the first section 60 being in fluid communication with a first heat exchange circuit 64 , and the second section 62 being in fluid communication with a second heat exchange circuit 66 . Further, the first section 60 and the second section 62 are hydraulically isolated from each other.
[0016] However, the aforementioned conventional technologies have a problem that heat transfer may occur from a radiator for an engine with a high temperature to a radiator for an electric field loading apparatus because the radiator of the electric field loading apparatus and the engine radiator are integrally formed. Owing to this, the cooling effect of the electric field loading apparatus is deteriorated, and hence the output and efficiency of the electric field loading apparatus is deteriorated due to a temperature rise of the electric field loading apparatus.
[0017] Additionally, the conventional technologies have a problem that in the case of vehicles coming with large engine displacement and vehicle weight, such as large-sized SUV and RV vehicles, it is difficult to set a high-capacity heat exchanger due to vehicle package constraints, thus making it difficult to use an integrated-type heat exchanger having a top-bottom structure (top part for an internal combustion engine and bottom part for an electric field) or a left-right structure (left side for an internal combustion engine and right side for an electric field).
[0018] The information disclosed in this Background of the Invention section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
BRIEF SUMMARY OF THE INVENTION
[0019] Various aspects of the present invention are directed to provide a radiator of an automobile, which can efficiently exchange heat with an internal combustion engine and an electric field apparatus, can be easily arranged in an engine room because of its simple structure, and can cut down costs and weight.
[0020] In an aspect of the present invention, the radiator of an automobile, may include a tank portion into which cooling water flows; and a plurality of core portions connected to the tank portion, and arranged in a front-rear direction of the automobile each other, wherein the plurality of core portions includes a core portion for an internal combustion engine in which cooling water for cooling the internal combustion engine flows and a core portion for an electric field system in which cooling water for cooling the electric field system flows.
[0021] The tank portion may be partitioned into a plurality of spaces by a partition such that the cooling water entered into the tank portion is supplied separately to the core portion for the internal combustion engine and the core portion for the electric field system, wherein the partition is provided with at least a communication hole to communicate the cooling water between the plurality of spaces for preventing damage caused by abrupt pressure fluctuations.
[0022] The tank portion may be partitioned into a plurality of spaces, and a pocket for reducing heat transfer is arranged between the spaces, wherein the pocket is provided with communication holes to communicate the cooling water between the plurality of spaces for preventing damage caused by abrupt pressure fluctuations.
[0023] The tank portion may be partitioned into a plurality of spaces by a partition.
[0024] The plurality of core portions may be arranged to be spaced by a predetermined gap in the front-rear direction of the automobile.
[0025] The core portion for the electric field system may be arranged more forwardly on a front part of the automobile than the core portion for the internal combustion engine.
[0026] In another aspect of the present invention, the plurality of core portions may further include a core portion for an air conditioner system for cooling the air conditioner system, and the core portion for the internal combustion engine and the core portion for the air conditioner system are arranged to be spaced in the front-rear direction of the automobile wherein the tank portion is partitioned into a plurality of spaces by a partition to form a plurality of tank portions, wherein the partition is provided with at least a communication hole to communicate the cooling water between the plurality of spaces for preventing damage caused by abrupt pressure fluctuations, wherein a pocket for blocking heat transfer is arranged between the plurality of tank portions, and wherein the pocket is provided with communication holes to communicate the cooling water between the plurality of spaces for preventing damage caused by abrupt pressure fluctuations.
[0027] In further another aspect of the present invention, the plurality of core portions may further include a core portion for an air conditioner system for cooling the air conditioner system, and the core portion for the electric field system and the core portion for the air conditioner system are arranged to be spaced in the front-rear direction, wherein the tank portion is partitioned into a plurality of spaces by a partition to form a plurality of tank portions, wherein the partition is provided with at least a communication hole to communicate the cooling water between the plurality of spaces for preventing damage caused by abrupt pressure fluctuations, wherein a pocket for blocking heat transfer is arranged between the plurality of tank portions, and wherein the pocket is provided with communication holes to communicate the cooling water between the plurality of spaces for preventing damage caused by abrupt pressure fluctuations.
[0028] In another aspect of the present invention, the tank portion may be provided in plural form so as to correspond to the plurality of core portions, and the plurality of tank portions are arranged to be bonded to each other.
[0029] In further another aspect of the present invention, the tank portion is provided in plural form so as to correspond to the plurality of core portions, and the radiator comprises a header connecting the tank portions and the core portions.
[0030] The radiator according to various aspects of the present invention can simplify the structure, cut down weight and costs, and reduce assembly process by coupling a plurality of core portions to a single header and a single tank portion.
[0031] Furthermore, by arranging the plurality of core portions in a front-rear direction, the structure is simplified and it becomes easier to secure an installation space, thus allowing the radiator according to the present invention to be applied to more cars.
[0032] Furthermore, by configuring the tank portion so as to be partitioned by a pocket or the like, heat transfer between the cooling water cooling the internal combustion engine and the cooling water cooling the electric field system is blocked, thereby improving cooling efficiency much more.
[0033] The methods and apparatuses of the present invention have other features and advantages which will be apparent from or are set forth in more detail in the accompanying drawings, which are incorporated herein, and the following Detailed Description of the Invention, which together serve to explain certain principles of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0034] FIG. 1 is a schematic view of a conventional cooling system for a hybrid vehicle.
[0035] FIG. 2 is a schematic view of another conventional cooling system for a hybrid vehicle.
[0036] FIG. 3 is a front view showing a radiator of an automobile according to a first exemplary embodiment of the present invention.
[0037] FIG. 4 is a cross-sectional view showing part A-A of FIG. 3 .
[0038] FIG. 5 is a cross-sectional view showing part B-B of FIG. 4 .
[0039] FIG. 6 is a schematic view showing a cooling system according to the first exemplary embodiment of the present invention.
[0040] FIG. 7 is a cross-sectional view showing another radiator of an automobile according to second and third exemplary embodiments of the present invention.
[0041] FIG. 8 is a cross-sectional view showing yet another radiator of an automobile according to a fourth exemplary embodiment of the present invention.
[0042] FIG. 9 is a cross-sectional view showing a radiator of an automobile according to a fifth exemplary embodiment of the present invention.
[0043] It should be understood that the appended drawings are not necessarily to scale, presenting a somewhat simplified representation of various features illustrative of the basic principles of the invention. The specific design features of the present invention as disclosed herein, including, for example, specific dimensions, orientations, locations, and shapes will be determined in part by the particular intended application and use environment.
[0044] In the figures, reference numbers refer to the same or equivalent parts of the present invention throughout the several figures of the drawing.
DETAILED DESCRIPTION OF THE INVENTION
[0045] Reference will now be made in detail to various embodiments of the present invention(s), examples of which are illustrated in the accompanying drawings and described below. While the invention(s) will be described in conjunction with exemplary embodiments, it will be understood that present description is not intended to limit the invention(s) to those exemplary embodiments. On the contrary, the invention(s) is/are intended to cover not only the exemplary embodiments, but also various alternatives, modifications, equivalents and other embodiments, which may be included within the spirit and scope of the invention as defined by the appended claims.
[0046] Hereinafter, a radiator of an automobile according to an exemplary embodiment of the present invention is limited to a radiator of a hybrid automobile (hereinafter, referred to as “automobile”) which combines an internal combustion engine, such as an engine, and electric field parts, such as a motor, and drive them, and will be described in detail with reference to the accompanying drawings.
[0047] FIG. 3 is a front view showing a radiator of an automobile according to a first exemplary embodiment of the present invention. FIG. 4 is a cross-sectional view showing part A-A of FIG. 3 . FIG. 5 is a cross-sectional view showing part B-B of FIG. 4 . FIG. 6 is a schematic view showing a cooling system according to the first exemplary embodiment of the present invention.
[0048] Referring to FIGS. 3 to 5 , the radiator of the automobile according to the first exemplary embodiment includes a tank portion 140 for temporarily storing cooling water, a header 150 coupled to the tank portion 140 , and a plurality of core portions 110 and 120 located in a front-rear direction, one side of which is installed on the header 150 .
[0049] Here, the plurality of core portions 110 and 120 includes a core portion 110 for an internal combustion engine in which cooling water for cooling the internal combustion engine side flows and a core portion 120 for an electric field system in which cooling water for cooling the electric field system side flows.
[0050] The core portion 110 for the internal combustion engine and the core portion 120 for the electric field system may be arranged to be spaced by a predetermined gap in the front-rear direction, or may be arranged to be in contact with each other in the front-rear direction. The following description will be given of a case where the core portion 110 for the internal combustion engine and the core portion 120 for the electric field system are arranged to be spaced by a predetermined gap in the front-rear direction.
[0051] As shown in FIG. 5 , when viewed from a vehicle travel direction, it is preferable that the core portion 120 for the electric field system is arranged on the front part of the vehicle and the core portion 110 for the electric field system is arranged on the rear part of the vehicle. That is, the core portion 120 for the electric field system is arranged more forwardly on the front part of the vehicle than the core portion 110 for the internal combustion engine.
[0052] Since a temperature of the cooling water circulating through the core portion 120 for the electric field system is lower than a temperature of the cooling water circulating through the core portion 110 for the internal combustion engine, it is preferable that the core portion 120 for the electric field system is arranged on the front part so that outside air passed through the core portion 120 for the electric field system passes through the core portion 110 for the internal combustion engine.
[0053] The core portion 110 for the internal combustion engine and the core portion 120 for the electric field system may be each include a plurality of tubes and radiating fins.
[0054] The tank portion 140 is provided with a first cap 144 c corresponding to the core portion 110 for the internal combustion engine and a second cap 142 c corresponding to the core portion 110 for the electric field system.
[0055] The first cap 144 c is opened when a cooling water pressure in the core portion 110 for the internal combustion engine rises higher than a predetermined pressure, thus to allow the cooling water in the core portion 110 for the internal combustion engine to flow to a tank portion 144 for the internal combustion engine. Also, the first cap 144 c is opened when a cooling water pressure in the core portion 110 for the internal combustion engine is lower than the predetermined pressure, thus to allow the cooling water in the tank portion 144 for the internal combustion engine to flow to the core portion 110 for the internal combustion engine.
[0056] The second cap 142 c also performs a similar function to the first cap 144 c . However, a set pressure of the first cap 142 c and a set pressure of the second cap 142 c may not be equal.
[0057] The tank portion 140 is formed to be opened at one side, and the header 150 is coupled to cover the open surface of the tank portion 140 .
[0058] The header 150 is mounted on the open surface of the tank portion 140 to thus form a cooling water flowing space enclosed by the tank portion 140 and the header 150 .
[0059] The core portion 110 for the internal combustion engine and the core portion 120 for the electric field system are installed to penetrate the header 150 .
[0060] The core portion 110 for the internal combustion engine and the core portion 120 for the electric field system are separated from each other but both are installed together on the single tank portion 140 and the single header 150 .
[0061] The tank portion 140 may be partitioned into a plurality of spaces, and a pocket 160 for reducing heat transfer between the spaces may be arranged between the spaces. The tank portion 140 can be partitioned into a plurality of spaces by a separate member, or can be partitioned into a plurality of spaces by the pocket 160 . The description set forth herein will be directed to the case in which the tank portion 140 is partitioned into a plurality of spaces by the pocket 160 .
[0062] The cooling water in the tank portion 140 is separated with the pocket 160 interposed therebetween, thus flowing to the core portion 110 for the internal combustion engine 110 and the core portion 120 for the electric field system, respectively.
[0063] The tank portion 140 is divided into a tank portion 144 for the internal combustion engine and a tank portion 142 for the electric field system.
[0064] The pocket 160 has a structure which includes two panels spaced apart by a predetermined gap and forms a layer with a small flow of cooling water or air between the two panels.
[0065] Accordingly, the pocket 160 serves to divide the inside of the tank portion 140 into two spaces and reduce heat transfer between the cooling water entering the core portion 110 for the internal combustion engine and the cooling water entering the core portion 120 for the electric field system.
[0066] The pocket 160 may be provided with communication holes 160 a for preventing damage caused by abrupt pressure fluctuations.
[0067] Referring to FIGS. 4 and 5 , the top part of the tank portion 142 for the electric field system is provided with an inlet port 142 a into which high-temperature cooling water flows, and the bottom part thereof is provided with an outlet port 142 b from which the cooling water cooled while circulating through the core portion 120 for the electric field system flows out.
[0068] Further, the top part of the tank portion 144 for the internal combustion engine is provided with an inlet port 144 a into which high-temperature cooling water flows, and the bottom part thereof is provided with an outlet port 144 b from which the cooling water cooled while circulating through the core portion 110 for the internal combustion engine flows out.
[0069] An operation of the radiator of the automobile thus-constructed according to the first exemplary embodiment of the present invention will be described below.
[0070] Referring to FIG. 6 , in the case of a hybrid automobile, the radiator includes a cooling water circulation system 100 for an internal combustion engine in which cooling water for cooling the internal combustion engine side flows and a cooling water system 200 for an electric field system in which cooling water for cooling the electric field system side flows.
[0071] In the cooing water circulation system 100 for the internal combustion engine, when a driving pump 111 on the internal combustion engine side is activated, cooling water flows to the internal combustion engine by the activation of the driving pump 111 on the internal combustion engine side, is heated to a high temperature while passing through the internal combustion engine 12 , and then flows into the core portion 110 for the internal combustion engine.
[0072] The cooling water flown into the core portion 110 for the internal combustion engine is cooled while circulating through the core portion 110 for the internal combustion engine, and then is circulated again to the internal combustion engine 12 .
[0073] On the other hand, in the cooling water circulation system 200 for the electric field system, when a driving pump 121 on the electric field system side is activated, cooling water sequentially passes through an inverter 122 , the tank portion 144 for the electric field system, and a motor 123 by the activation of the pump 121 for the electric field system, and then flows into the core portion 120 for the electric field system.
[0074] The cooling water flown into the core portion 120 for the electric field system is cooled while circulating through the core portion 120 for the electric field system, and then is circulated again to the inverter 122 side.
[0075] As described above, upon activation, the cooing water circulation system 100 for the internal combustion engine and the cooling water circulation system 200 for the electric field system are separately activated, but configured as a single radiator as the core portion 110 for the internal combustion engine and the core portion 120 for the electric field system are coupled by the tank portion 140 in terms of structure.
[0076] Therefore, activation can be performed so as to conform to respective target temperatures of the cooling water of the first cooling water circulation system 100 ranging from about 110° C. to about 100° C. and the cooling water of the second cooling water circulation system 200 ranging from about 80° C. to about 60° C., for example. Thus, the cooling efficiency can be improved.
[0077] In FIG. 6 , reference numeral 80 denotes an automatic transmission cooling system, reference numeral 81 denotes an automatic transmitter, and reference numeral 82 denotes oil cooler water.
[0078] While the present invention has been described with reference to the exemplary embodiment illustrated in the drawings, it is to be understood by those skilled in the art that the invention is not limited thereto and various modifications or other exemplary embodiment can be made within the equivalent scope of the present invention. Therefore, the true scope of the present invention should be defined by the appended claims.
[0079] FIG. 7 is a cross-sectional view showing another radiator of an automobile according to a second exemplary embodiment of the present invention.
[0080] Referring to FIG. 7 , the radiator 130 ′ of the automobile according to the second exemplary embodiment of the present invention includes a tank portion 140 ′ forming a flow passage and a plurality of core portions 110 ′ and 120 ′ located in a front-rear direction, one side of which is installed on the tank portion 140 . The plurality of core portions includes a core portion 120 ′ for a water cooling type air conditioner system in which cooling water for cooling the air conditioner system for cooling indoor air flows and a core portion 110 ′ for an internal combustion engine in which cooling water for cooling the internal combustion engine flows.
[0081] The core portion 110 ′ for the internal combustion engine and the core portion 120 ′ for the water cooling type air conditioner system 120 ′ are installed by inserting their one side into the single tank portion 140 ′.
[0082] The tank portion 140 ′ is divided into a tank portion 144 ′ for the internal combustion engine to be connected to the core portion 110 ′ for the internal combustion engine and a tank portion 142 ′ for the air conditioner system to be connected to the core portion 120 ′ for the water cooling type air conditioner system.
[0083] The core portion 120 ′ for the water cooling type air conditioner system and the core portion 110 ′ for the internal combustion engine are arranged at the front and rear of the tank portion 140 ′.
[0084] A pocket 160 ′ for partitioning a space is installed at the central part of the tank portion 140 ′. A cross-section of the tank portion 140 ′ is formed in a closed curve, and the inside space thereof is partitioned into two spaces by the pocket 160 ′. The pocket 160 ′ may be provided with communication holes for preventing damage caused by abrupt pressure fluctuations.
[0085] Referring to FIG. 7 , a radiator of an automobile according to a third exemplary embodiment of the present invention has the same construction and operation as the second exemplary embodiment except that the plurality of core portions 110 ′ and 120 ′ coupled to the tank portion 140 ′ includes a core portion 120 ′ for a water cooling type air conditioner system in which cooling water for cooing the air conditioner system for cooling indoor air flows and a core portion 110 ′ for an electric field system in which cooling water for cooling the electric field system flows. Thus, other detailed descriptions are omitted.
[0086] The core portion 110 ′ for the electric field system and the core portion 120 ′ for the water cooling type air conditioner system 120 ′ are installed by inserting their one side into the single tank portion 140 ′.
[0087] The tank portion 140 ′ is divided into a tank portion 144 ′ for the electric field system to be connected to the core portion 110 ′ for the electric field system and a tank portion 142 ′ for the air conditioner system to be connected to the core portion 120 ′ for the water cooling type air conditioner system.
[0088] The core portion 120 ′ for the water cooling type air conditioner system and the core portion 110 ′ for the electric field system are arranged at the front and rear of the tank portion 140 ′.
[0089] A pocket 160 ′ for partitioning a space is installed at the central part of the tank portion 140 ′. A cross-section of the tank portion 140 ′ is formed in a closed curve, and the inside space thereof is partitioned into two spaces by the pocket 160 ′.
[0090] The pocket 160 ′ may be provided with communication holes for preventing damage caused by abrupt pressure fluctuations.
[0091] FIG. 8 is a cross-sectional view showing yet another radiator of an automobile according to a fourth exemplary embodiment of the present invention.
[0092] Referring to FIG. 8 , the radiator of the automobile according to the fourth exemplary embodiment of the present invention has the same construction and operation as the first exemplary embodiment except that the tank portion 140 ″ is provided in plural form and the plurality of tank portions 140 ″ are coupled to each other and integrally formed by bonding means, such as welding or compression. Thus, detailed description thereof is omitted.
[0093] Here, a tank portion 142 ″ for an electric field system of the tank portion 140 ″ is formed to be opened, and a tank portion 144 ″ for the internal combustion engine may be inserted so as to cover the open surface of the tank portion 142 ″ for the electric field system.
[0094] A pocket 160 ″ for blocking heat transfer is formed on the tank portion 144 ″ for the internal combustion engine. The pocket 160 ″ may be provided with communication holes for preventing damage caused by abrupt pressure fluctuations.
[0095] FIG. 9 is a cross-sectional view showing a radiator of an automobile according to a fifth exemplary embodiment of the present invention.
[0096] Referring to FIG. 9 , the radiator 200 of the automobile according to the fifth exemplary embodiment has the same construction and operation as the first exemplary embodiment except that the radiator 200 includes a tank portion 201 for temporarily storing cooling water, a header 202 coupled to the tank portion 201 , and a plurality of core portions 203 and 204 located in a front-rear direction, one side of which is installed on the header 202 , and the tank portion 201 is partitioned by a partition 210 . Thus, detailed description thereof is omitted.
[0097] The partition 210 may be formed in a flat-plate shape, and may be provided with communication holes 210 a for preventing damage caused by abrupt pressure fluctuations.
[0098] The present invention involves an improvement of a radiator of an automobile which can increase heat efficiency by arranging an internal combustion engine and an electric field system, or an air conditioner system and an electric field system, or an air conditioner system and an internal combustion engine in a front-rear direction and installing them on a single tank portion. Especially, the present invention can be used for large-sized passenger vehicles such as SUV and RV vehicles.
[0099] For convenience in explanation and accurate definition in the appended claims, the terms “upper”, “lower”, “front”, and “rear” are used to describe features of the exemplary embodiments with reference to the positions of such features as displayed in the figures.
[0100] The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise forms disclosed, and obviously many modifications and variations are possible in light of the above teachings. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and their practical application, to thereby enable others skilled in the art to make and utilize various exemplary embodiments of the present invention, as well as various alternatives and modifications thereof. It is intended that the scope of the invention be defined by the Claims appended hereto and their equivalents. | Disclosed is a radiator which can simplify the structure, cut down weight and costs, and reduce assembly process by coupling a plurality of core portions to a single header and a single tank portion. Furthermore, by arranging the plurality of core portions in a front-rear direction, the structure is simplified and it becomes easier to secure an installation space, thus allowing the radiator according to the present invention to be applied to more cars. Furthermore, by configuring the tank portion so as to be partitioned by a pocket or the like, heat transfer between the cooling water cooling the internal combustion engine and the cooling water cooling the electric field system is blocked, thereby improving cooling efficiency much more. | 5 |
BACKGROUND OF THE INVENTION
The O-alkylated halopyridinates corresponding to Formula I are a known class of herbicides. ##SPC1##
In I, each X is independently hydrogen or halo and at least one X is halo (i.e., fluoro, chloro, bromo or iodo); Y is hydrogen, halo or NR'R" wherein R' and R" are each independently hydrogen or lower alkyl of 1 to 4 carbon atoms; R 1 is hydrogen or methyl; and R 2 is lower alkyl. As used herein, the term "lower alkyl" shall mean an alkyl radical of from 1 to 4 carbon atoms (i.e., methyl, ethyl, propyl and butyl).
Compounds of Formula I have been prepared by reacting (a) an alkali metal halopyridinate corresponding to the formula ##SPC2##
Wherein M is an alkali metal and X and Y have the aforesaid meaning, with (b) a lower alkyl ester of α-chloro or bromo acetic acid (or propionic acid) corresponding to the formula ##EQU1## wherein R 1 and R 2 have the aforesaid meaning and R 3 is chloro or bromo. The reaction has been conducted under various and miscellaneous reaction conditions and has been plagued by the low reaction rates, concurrent formation of N-alkylated by-products, and so forth.
SUMMARY OF THE INVENTION
It has now been discovered that compounds of Formula I can be prepared in excellent yield and purity by reacting II in solid particulate form with III in an inert organic liquid reaction medium under alkaline conditions and in the presence of a quaternary ammonium salt catalyst.
DETAILED DESCRIPTION OF THE INVENTION
The catalysts: Essentially any compound from the known class of quaternary ammonium compounds can be used in the instant invention. Suitable quaternary ammonium salts have a minimum solubility of at least about 1 weight percent in the liquid reaction medium at 25°C and normally have a total aggregate carbon content of at least about 10 carbon atoms and preferably from about 12 to about 31 carbon atoms. The ammonium salts can be represented by the formula R 1 'R 2 'R 3 'R 4 'N +A - , where R 40 '-R 4 ' are hydrocarbyl groups (e.g., alkyl, aryl, alkaryl, aralkyl, cycloalkyl, etc.). Additionally, R 1 ' can join with R 2 ' to form a 5- or 6-membered heterocyclic compound having at least 1 quaternized nitrogen atom in the ring and may also contain one non-adjacent atom of nitrogen, oxygen or sulfur within the ring. Typically, R 1 '-R 4 ' are hydrocarbyl groups of from 1 to about 12 carbon atoms. A - is an inert neutralizing anion and may be varied to convenience. Chloride and bromide are the preferred anions but other suitable anions include, for example, fluoride, iodide, bisulfate, perchlorate, nitrate, acetate, benzoate, tosylate, etc. The following compounds are illustrative: tetraalkylammonium salts, such as tetra-n-butyl-, tetrahexyl-, tri-n-butylmethyl-, and trioctylmethyl- and tridecylmethyl-ammonium chlorides, bromides, bisulfates, tosylates, etc.; aralkyl ammonium salts, such as tetrabenzyl ammonium chloride, benzyltrimethyl-, benzyltriethyl-, benzyltributyl-, and then ethyltrimethyl ammonium chlorides, bromides, etc.; aryl ammonium salts, such as triphenylmethyl ammonium fluoride, chloride or bromide, N,N,N-trimethylaniliniumbromide, N,N-diethyl-N-ethylaniliniumbisulfate, trimethylnapthylammonium chloride, p-methylphenyl trimethyl ammonium chloride or tosylate, etc.; 5- and 6-membered heterocyclic compounds containing at least one quaternized nitrogen atom in the ring, such as N-methylpyridinium chloride or methyl sulfate, N-hexylpyridinium iodide, 4-pyridyltrimethyl ammonium iodide, 1-methyl-1-azabicyclo[2.2.1]heptane bromide, N,N-dibutyl morpholinium chloride, N-ethylthiazolium chloride, N-butylpyrrolium chloride, etc., and other like compounds.
The preferred catalysts are benzyltrimethyl-, benzyltriethyl- and tetra-n-butylammonium salts.
The quaternary ammonium salts are used in the process in small but catalytic amounts. For example, satisfactory reaction rates have been achieved using the ammonium salts in amounts from about 0.25 to about 20 mole percent, based on the reactants, but amounts of from 0.5 to about 10 mole percent are generally preferred.
The reactants: The reactants in this process comprise two well-known classes of reactants.
The alkali metal halopyridinates are represented by Formula II. The sodium and potassium salts and particularly the sodium salts of such halopyridinates are preferred.
The lower alkyl esters of α-chloro or bromo acetic acid (or propionic acid) are likewise well known. In this particular instance, the lower alkyl esters of α-chloro acetic acid are the preferred reactants and the methyl and ethyl esters of α-chloro acetic acid are the most preferred reactants.
Obviously, one skilled in the art will be able to select the appropriate reactants within groups II and III above to produce any particular compound within I. Suitable combinations will be further illustrated, however, in the Examples below.
Process parameters: The process is conducted in an inert organic liquid reaction medium under alkaline conditions and preferably with efficient blending. By the term "an inert inorganic liquid reaction medium" we mean to include any organic liquid which is inert in the reaction and does not react with either reactants II or III or with the final product I. Suitable such solvents include conventional hydrocarbon solvents (e.g., hexane, benzene, toluene, xylene, etc.) and chlorinated hydrocarbon solvents (e.g., methylene chloride, methyl chloroform, perchloroethylene, etc.) and other like solvents. Also included within the stated term is the use of the lower alkyl esters of α-chloro or bromo acetic acid (or propionic acid) in excess as the liquid reaction medium. The use of the latter compounds as the liquid reaction medium is preferred.
The alkaline conditions of the reacting mixture may be established by the addition of an alkali or alkaline earth metal, oxide or hydroxide, or the like to the reaction mixture or, the alkaline conditions may be established merely by the presence of the alkali metal halopyridinate.
The following Examples will further illustrate the invention.
EXAMPLE 1
Essentially equimolar amounts of sodium 3,5,6-trichloropyridinate and methyl α-chloroacetate in toluene were blended together in the presence of from 2 to 5 mole percent of benzyltriethylammonium chloride and the mixture refluxed at 105°C for 3 hours. The product, methyl α-(3,5,6-trichloropyridyl)acetate, was thus obtained in approximately 90 percent yield.
EXAMPLE 2
Sodium 6-chloropyridinate and excess methyl α-chloroacetate were blended together with 2 mole percent of benzyltriethylammonium chloride and the mixture warmed at 50°C for 0.5 hours. The product, methyl α-(6-chloropyridyloxy)acetate was thus obtained in 95 percent yield. In the absence of catalyst, very little reaction occurred.
Other compounds within the scope of Formula I can be likewise produced using the same quaternary ammonium catalyst or other quaternary ammonium catalysts having the aforesaid properties. For example, tetra-n-butyl ammonium chloride could have been used in Examples 1 and 2 above to give similar results. In like manner, ethyl α-(3,5-dichloro-6-fluoropyridyloxy)acetate can be prepared by reacting the appropriate reactants in II and III together in the presence of benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetra-n-butylammonium bisulfate, etc. Ethyl α-(3,5-dichloro-6-fluoro-4-aminopyridyloxy)acetate can be prepared by mixing the appropriate reactants from II and III with benzyltriethylammonium chloride or bromide, benzyltrimethylammonium chloride, tetrabutylammonium bisulfate or chloride, etc. Other compounds can be similarly prepared. | The reaction between the alkali metal halopyridinates with the lower alkyl esters of α-chloro or bromo acetic acid (or propionic acid) to form the corresponding O-alkylated halopyridinates is catalyzed by quaternary ammonium salts. For example, methyl α-(6-chloropyridinyloxy)acetate was prepared in excellent yield by reacting sodium 6-chloropyridinate with excess methyl α-chloroacetate in the presence of 2 mole percent of benzyl triethyl ammonium chloride. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a national phase application under 35 U.S.C. §371 of International Application No. PCT/US2012/038458 filed May 17, 2012, which claims priority to International Patent Application No. PCT/CN2011/074165 filed May 17, 2011, the disclosure of each of which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
The invention relates to the pharmaceutical field, in particular relates to the preparation of 4-anilinyl-6-butenamidoyl-7-alkoxy-quinazolin derivatives and the pharmaceutical composition containing these derivatives and their use as therapeutic agents particularly as inhibitors of pan-ErbB family kinases.
BACKGROUND OF THE INVENTION
Cellular signal transduction is a fundamental mechanism. During the signal transduction, the extracellular stimulation is transmitted intracellularly, to modulate various cellular processes including cell proliferation, differentiation, apoptosis and cell migration. A lot of signal transductions are mediated by growth factors binding to protein tyrosine kinase (PTK) trans-membrane receptor protein tyrosine kinases (RTK).
When RTK is inappropriately or constitutively activated, abnormal RTK activity such as that caused by overexpression or mutations results in uncontrolled cell proliferation or differentiation, and leads to diseases. Known diseases caused by abnormal activity of RTKs include psoriasis, rheumatoid arthritis, many types of cancer, angiogenesis, atherosclerosis and so on. RTK is comprised of many families, and one of them is ErbB family which is comprised of EGFr (also named ErbB1), HER2 (ErbB2), HER3 (ErbB3) and HER4 (ErbB4). These RTKs contain an extracellular glycoxylated domain for ligand binding, a transmembrane domain, and an intracellular cytoplasma catalyticaldomain capable of phosphorylating tyrosines of proteins. HER3 does not have an intracellular cytoplasma catalyticaldomain capable of phosphorylating tyrosines of protein. The RTK catalytic activity can be activated either by receptor overexpression or by ligand mediated dimerization. The ErB family RTKs can form homodimers or heterodimers. An example of homodimerization comes from EGFr binding with EGF family ligand (including EGF, transforming growth factor, becellulin epiregulin, etc). The heterodimerization between EGFr family RTKs can be accelerated by heregulin (also named nerregulin) binding. Even though HER3 does not have receptor kinase activity, its heterodimerization with HER2 or HER4 can greatly enhance the receptor kinase dimerization and the tyrosine phosphoryzation catalytic activity. Overactivation of EGFr has been associated with proliferation diseases such as NSCLC, bladder cancer, head and neck cancer, brain cancer and other cancers, while HER2 hyperactivity has been associated with breast cancer, ovarian cancer, uterine cancer, gastric cancer, and pancreatic cancer, etc. Therefore, inhibition of ErbB family RTKs may provide a treatment of the diseases associated with characteristic abnormal erbB family RTK activities. Many publications have discussed the biological activities of erB family RTKs, and their relationship with different diseases, such as the following papers and patents: Reid, A., et al. Eur. J. Cancer, 2007, 43, 481; Doebele, R. C., et al. Lung Cancer, 2010, 69, 1-12; Ocana, A.; Amir, E. Cancer Treat. Rev. 2009, 35, 685-91; Minkovsky, N., et al. Current Opinion in Investigational Drugs 2008, 9, 1336-1346; WO2002/66445, WO1999/09016, U.S. Pat. No. 6,627,634, etc.
Many patents have revealed RTK inhibitors or quinazoline derivatives related technology, for examples: WO9630347 (Chinese patent application CN96102992.7) revealed some 4-anilinylquinazoline derivatives for the treatment of excessive proliferative diseases. WO9738973 (Chinese application CN97194458) and WO2009/140863 (Chinese application CN2009000557) disclosed the preparation and pharmaceutical application of irreversible tyrosine kinase inhibitors. WO0006555 (Chinese application CN99808949) disclosed that certain quinazoline derivatives inhibited RTK activities. WO9935146 (Chinese application CN99803887) disclosed a series of fused heteryl aromatic compounds including quinazolines as active as RTK kinase inhibitors. In addition, Chinese patent applications such as CN01817895, CN93103556, CN98807303, CN96193526, CN01812051, CN99803887, CN0410089867, CN03811739; U.S. Pat. No. 5,521,884, U.S. Pat. No. 6,894,051, U.S. Pat. No. 6,958,335, U.S. Pat. No. 5,457,105, U.S. Pat. No. 5,616,582, U.S. Pat. No. 5,770,599, U.S. Pat. No. 5,747,498, U.S. Pat. No. 6,900,221, U.S. Pat. No. 6,391,874, U.S. Pat. No. 6,713,485, U.S. Pat. No. 6,727,256, U.S. Pat. No. 6,828,320, U.S. Pat. No. 7,157,466 all disclosed that various types of quinazoline derivatives could inhibit the activities of many types of RTKs. Several quinazoline based kinase inhibitors have been approved in US, Europe and many other countries for the treatment of cancer, for example, gefitinib (trade name Irresa), erlotinib (trade name Tarceva), lapatinib (trade name Tykerb), etc. With continued improvement in research of biological mechanism, diagnosis and treatment of cancer treatment of proliferative diseases, especially cancer, is becoming more precise, targeted and personalized. Therefore, there is still an urgent need for clinical applications to develop highly efficacious and highly targeted drugs against proliferative diseases and cancer.
BRIEF SUMMARY OF THE INVENTION
This invention provides for quinazoline-7-ether derivatives of the formula (I) or any variations detailed herein, and pharmaceutically acceptable salts and prodrugs thereof, that are useful in the treatment of cancers where RTK is implicated. Specifically, the present invention relates to compounds of the formula (I), or any variations detailed herein, that act as EGFR and ErbB2 inhibitors. Also provided are formulations containing compounds of the formula (I) and methods of using the compounds in treating an individual in need thereof. In addition, described are processes for preparing the inhibitory compounds of the formula (I).
In one aspect, provided is a compound of the formula (I):
or a salt, solvate, polymorph, metabolite or prodrug thereof, wherein:
Ar is a monocyclic aryl or monocyclic heteroaryl, optionally substituted with 0 to 4 substituents independently selected from the group consisting of halogen, trifluoromethyl, trifluoromethoxy, C 1 -C 3 alkyl, ethynyl, ethenyl, C 1 -C 3 alkoxy, —O(CH 2 ) n Ar 1 ; —(CH 2 ) m Ar 2 and —S(O) 2 Ar 3 ;
m and n are independently 0 or 1;
each Ar 1 , Ar 2 and Ar 3 is independently a monocyclic aryl or 5 or 6 membered heteroaryl, where each aryl or heteroaryl is optionally substituted with 0 to 3 substituents independently selected from the group consisting of halogen, trifluoromethyl, trifluoromethoxy, C 1 -C 3 alkyl, C 2 -C 3 alkynyl, C 2 -C 3 alkenyl and C 1 -C 3 alkoxy;
L is a bond or CH 2 ; and
M is a 6-10 membered bicyclic heterocycle containing one or more annular heteroatoms independently selected from O, N and S, optionally substituted with one or more substituents independently selected from the group consisting of halogen, C 1 -C 3 alkyl, hydroxyl and C 1 -C 3 alkoxy.
In some embodiments, the compound is of the formula (I), or salt, solvate, polymorph, metabolite or prodrug thereof, wherein Ar is 3-chloro-4-fluorophenyl, L is a bond or CH 2 , and M is hexahydro-3-methoxyfuro[3,2-b]furan-6-yl, 3-oxabicyclo[3.1.0]hexan-6-yl or 3-oxabicyclo[3.1.0]hexan-1-yl. In a particular variation, L is CH 2 and M is 3-oxabicyclo[3.1.0]hexan-6-yl.
In another aspect, provided are methods for treating receptor protein tyrosine kinase-related disease in an individual in need thereof comprising administering to the individual an effective amount of a compound of the formula (I), or salt, solvate, polymorph, metabolite or prodrug thereof. In some embodiments, the receptor protein tyrosine kinase-related disease is a cancer (e.g., breast cancer, colorectal cancer, lung cancer, papillary carcinoma, prostate cancer, lymphoma, pancreatic cancer, ovarian cancer, cervical cancer, central nervous system cancer, osteogenic sarcoma, kidney cancer, liver cancer, bladder cancer, gastric cancer, head and neck squamous cell carcinoma, melanoma, or leukemia).
The invention also provides pharmaceutically acceptable salts, pharmaceutically acceptable prodrugs, and pharmaceutically active metabolites of the compound of the formula (I) or any variations described herein. Methods of making the compounds of the formula (I) are also described.
Also provided are pharmaceutical compositions comprising a compound detailed herein such as a compound of the formula (I), or a pharmaceutically acceptable prodrug, pharmaceutically active metabolite, or pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable carrier or excipient. Compounds as detailed herein or a pharmaceutically acceptable salt thereof are also provided for the manufacture of a medicament for the treatment of cancer. Kits comprising a compound detailed herein are provided, which optionally includes instructions for use in the methods detailed herein (e.g., in treating a receptor protein tyrosine kinase-related disease such as cancer).
It is to be understood that one, some, or all of the features of the various embodiments described herein may be combined to form other embodiments of the present invention. These and other aspects of the invention will become apparent to one of skill in the art.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the anticancer effect of Compound NT112 on the H1975 xenograft in the nude mice in comparison with erlotinib and afatinib.
FIG. 2 shows the anticancer effect of Compound NT112 to the NCI-N87 xenograft in the Balb/c nude mice.
FIGS. 3-A and B show the mouse pharmacokinetics data for Compound NT112 and afatinib respectively.
FIGS. 4-A and B show the rat pharmacokinetics data for Compound NT112 and afatinib respectively. The structure of afatinib (also known as BIBW-2992) is also shown in FIG. 4-B .
DETAILED DESCRIPTION OF THE INVENTION
This invention provides compounds that are inhibitors of receptor tyrosine kinases, and have advantageous pharmacokinetic properties. Compounds and compositions provided herein have superior pharmacokinetic properties to those of the standard therapies (e.g., afatinib) and better bioavailability, thus may have better efficacy and/or require lower doses to achieve the same therapeutic effect.
DEFINITIONS
Except as expressly defined otherwise, the following definition of terms is employed throughout this specification.
The term “alkyl” as used herein refers to a saturated linear or branched-chain hydrocarbon of 1 to 20 carbon atoms. Preferred are alkyl radicals of 1 to 6 carbon atoms (“C 1 -C 6 alkyl”), such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and the like. More preferred are lower alkyl radicals of 1 to 3 carbon atoms (“C 1 -C 3 alkyl”), such as methyl, ethyl, propyl, isopropyl. An alkyl radical may be unsubstituted or substituted with one or more substituents described herein, such as hydroxyl, halogen and the like.
“Aryl” refers to an aromatic carbocyclic group having at least a one aromatic ring, and an aromatic ring system is a conjugated it electron system.
“Heteroaryl” as used herein refers to an aromatic radical containing 1-4 ring heteroatoms, the remaining ring atoms being carbon.
“Bicyclic heterocycle” as used herein refers to a fused or spiro bicyclic group, containing at least 6-10 ring atoms, with 1-3 ring heteroatoms selected from N, O or S(O) n (where n is 0, 1 or 2), the remaining ring atoms being carbon. The bicyclic heterocycle group may contain one or more double bonds. The bicyclic heterocycle group may be substituted or unsubstituted, or optionally substituted with one or more substituents, preferably with one, two or three, and even more preferably with one or two substituents independently selected from lower alkyl, trifluoromethyl, halogen, lower alkoxy, cyano, and the like.
“Halogen” refers to fluorine, chlorine, bromine, or iodine. Likewise, the term “halo” represents fluoro, chloro, bromo or iodo. Preferred “halogens” are fluorine and chlorine.
“Hydroxyl” refers to the “—OH” group.
“Alkoxy” refers to “—O-alkyl”, including but not limited to methoxy, ethoxy, propyloxy, cyclopropyloxy, butoxy, cyclobutyloxy, and the like.
“Optional” means that the event or situation described thereafter may occur but may not necessarily occur. The terms “optionally substituted” and “substituted or unsubstituted” used herein are exchangeable. The term “substituted” in general means that one or more hydrogen atoms of the described structure are replaced by specific substituents. Except as expressly defined otherwise, an optionally substituted group may have one substituent substituted at each substitutable position. When a given structure has more than one position substitutable with one or more substituting groups, the substituents can be the same or different at each position. The substituents include, but are not limited to, hydroxyl, amino, halogen, cyano, aryl, heteroaryl, alkoxy, alkyl, alkenyl, alkynyl, heterocyclyl, thiol, nitro, aryloxyl, and the like.
Compounds
In one aspect, provided is a compound of the formula (I):
or a salt, solvate, polymorph, metabolite or prodrug thereof, wherein:
Ar is a monocyclic aryl or monocyclic heteroaryl, optionally substituted with 0 to 4 substituents independently selected from the group consisting of halogen, trifluoromethyl, trifluoromethoxy, C 1 -C 3 alkyl, ethynyl, ethenyl, C 1 -C 3 alkoxy, —O(CH 2 ) n Ar 1 ; —(CH 2 ) m Ar 2 and —S(O) 2 Ar 3 ;
m and n are independently 0 or 1;
each Ar 1 , Ar 2 and Ar 3 is independently a monocyclic aryl or 5 or 6 membered heteroaryl, where each aryl or heteroaryl is optionally substituted with 0 to 3 substituents independently selected from the group consisting of halogen, trifluoromethyl, trifluoromethoxy, C 1 -C 3 alkyl, C 2 -C 3 alkynyl, C 2 -C 3 alkenyl and C 1 -C 3 alkoxy;
L is a bond or CH 2 ; and
M is a 6-10 membered bicyclic heterocycle containing one or more annular heteroatoms independently selected from O, N and S, optionally substituted with one or more substituents independently selected from the group consisting of halogen, C 1 -C 3 alkyl, hydroxyl and C 1 -C 3 alkoxy.
In some embodiments, the compound is of the formula (I), or salt, solvate, polymorph, metabolite or prodrug thereof, wherein Ar is a phenyl optionally substituted with 0 to 4 substituents independently selected from the group consisting of halogen, trifluoromethyl, trifluoromethoxy, C 1 -C 3 alkyl, ethynyl, ethenyl, C 1 -C 3 alkoxy, —O(CH 2 ) n Ar 1 ; —(CH 2 ) m Ar 2 and —S(O) 2 Ar 3 . In some embodiments, Ar is a phenyl substituted with 1 to 3 substituents independently selected from the group consisting of halogen, trifluoromethyl, trifluoromethoxy, C 1 -C 3 alkyl, ethynyl, ethenyl, C 1 -C 3 alkoxy, —O(CH 2 ) n Ar 1 ; —(CH 2 ) m Ar 2 and —S(O) 2 Ar 3 , where Ar 1 , Ar 2 , Ar 3 , m and n are as defined for formula (I).
In some embodiments, Ar is a substituted phenyl selected from the group consisting of:
In some preferred embodiments, Ar is 3-chloro-4-fluorophenyl.
In some embodiments, Ar is a monocyclic heteroaryl optionally substituted with 0 to 4 substituents independently selected from the group consisting of halogen, trifluoromethyl, trifluoromethoxy, C 1 -C 3 alkyl, ethynyl, ethenyl, C 1 -C 3 alkoxy, —O(CH 2 ) n Ar 1 ; —(CH 2 ) m Ar 2 and —S(O) 2 Ar 3 , where Ar 1 , Ar 2 , Ar 3 , m and n are as defined for formula (I).
In some embodiments, Ar is a substituted heteroaryl selected from the group consisting of:
In some embodiments, the compound is of the formula (I), or salt, solvate, polymorph, metabolite or prodrug thereof, wherein L is a bond or CH 2 . In some embodiments, L is a bond. In some embodiments, L is CH 2 .
In some embodiments, the compound is of the formula (I), or salt, solvate, polymorph, metabolite or prodrug thereof, wherein M is a 6-10 membered bicyclic heterocycle containing one or more annular heteroatoms independently selected from O, N and S, substituted with one or more substituents selected from the group consisting of halogen, C 1 -C 3 alkyl, hydroxyl and C 1 -C 3 alkoxy. In some of these embodiments, M is
In some embodiments, M is an unsubstituted 6-10 membered bicyclic heterocycle containing one or more annular heteroatoms independently selected from O, N and S. In some of these embodiments, M is a 6-10 membered bicyclic heterocycle containing one annular heteroatom selected from O, N and S. In some of these embodiments, M is a 6-10 membered bicyclic heterocycle containing one annular heteroatom which is oxygen, e.g., 3-oxabicyclo[3.1.0]hexan-6-yl and 3-oxabicyclo[3.1.0]hexan-1-yl.
It is understood and clearly conveyed herein that each and every variation of Ar, L or M described herein may be combined with each and every variation of other variables described herein, where applicable, as if each and every combination were listed separately. For example, in one variation, provided is a compound of the formula (I), or salt, solvate, polymorph, metabolite or prodrug thereof, wherein Ar is 3-chloro-4-fluorophenyl, L is a bond or CH 2 , and M is hexahydro-3-methoxyfuro[3,2-b]furan-6-yl, 3-oxabicyclo[3.1.0]hexan-6-yl or 3-oxabicyclo[3.1.0]hexan-1-yl. In a particular variation, L is CH 2 and M is 3-oxabicyclo[3.1.0]hexan-6-yl.
In some embodiments, the compound is of formula (I), or salt, solvate, polymorph, metabolite or prodrug thereof, wherein the compound is selected from the group consisting of:
(E)-N-(7-((3R,3aS,6S,6aS)-hexahydro-3-methoxyfuro[3,2-b]furan-6-yloxy)-4-(3-chloro-4-fluorophenylamino)quinazolin-6-yl)-4-(dimethylamino)but-2-enamide, (Compound 1); (E)-N-(7-((3-oxa-bicyclo[3.1.0]hexan-6-yl)methoxy)-4-(3-chloro-4-fluorophenylamino)quinazolin-6-yl)-4-(dimethylamino)but-2-enamide, (Compound 2); (E)-N-(7-(((1R,5S,60-3-oxa-bicyclo[3.1.0]hexan-6-yl)methoxy)-4-(3-chloro-4-fluorophenylamino)quinazolin-6-yl)-4-(dimethylamino)but-2-enamide, (Compound 2-A); (E)-N-(7-(((1R,5S,6s)-3-oxa-bicyclo[3.1.0]hexan-6-yl)methoxy)-4-(3-chloro-4-fluorophenylamino)quinazolin-6-yl)-4-(dimethylamino)but-2-enamide, (Compound 2-B); (E)-N-(7-(((1S,5S)-3-oxa-bicyclo[3.1.0]hexan-1-yl)methoxy)-4-(3-chloro-4-fluorophenylamino)quinazolin-6-yl)-4-(dimethylamino)but-2-enamide, (Compound 3); (E)-N-(7-(((1R,5R)-3-oxa-bicyclo[3.1.0]hexan-1-yl)methoxy)-4-(3-chloro-4-fluorophenylamino)quinazolin-6-yl)-4-(dimethylamino)but-2-enamide, (Compound 4); and (E)-N-(7-((3-oxa-bicyclo[3.1.0]hexan-1-yl)methoxy)-4-(3-chloro-4-fluorophenylamino)quinazolin-6-yl)-4-(dimethylamino)but-2-enamide, (Compound 5).
In some embodiments, the compound is of formula:
or a salt, solvate, polymorph, metabolite or prodrug thereof. The invention embraces all stereoisomers, or mixtures thereof, such as a compound of the formula (2-A) or (2-B), or a mixture thereof:
In some embodiments, provided is a compound obtained by following the synthetic and purification steps described in Example 2, or a salt, solvate, polymorph, metabolite or prodrug thereof.
In some embodiments, the compound is of the formula (I):
or a salt, solvate, polymorph, metabolite or prodrug thereof, wherein:
Ar is a substituted monocyclic phenyl or monocyclic heteroaryl, optionally substituted with 0-4 groups selected from halogen, trifluoromethyl, trifluomethoxy, C 1-3 alkyl, ethynyl, ethenyl, C 1-3 alkoxyl; or O(CH 2 ) n Ar 1 , where n is 0 or 1;
Ar 1 is selected from monocyclic aryl or 5-6 membered heteroaryl group, and the aryl or heteroaryl may be substituted with 0-3 groups selected from halogen, trifluoromethyl, trifluomethoxy, C 1-3 alkyl, C 2-3 alkynyl, C 2-3 alkenyl, and C 1-3 alkoxyl;
L is selected from (CH 2 ) m , where m is 0 or 1;
M is a 6-10 membered bicyclic heterocycle, containing one or more O, N, or S atoms, and the heterocycle may be further substituted with one or more halogen, C 1-3 alkyl, hydroxyl, or C 1-3 alkoxyl.
Preferred examples of Ar in the formula (I) include, but are not limited to:
In some embodiments, the term “alkenyl” refers to linear or branched-chain hydrocarbon radical of two to twelve carbon atoms, containing at least one double bond, such as ethenyl, propenyl, and the like, wherein the alkenyl radical may be optionally substituted independently with one or more substituents described herein, and includes radicals having “cis” and “trans” orientations, or alternatively, “E” and “Z” orientations. The preferred alkenyl radicals are those with 2 to 6 carbon atoms (“C 2 -C 6 alkenyl”).
In some embodiments, the term “alkynyl” refers to a linear or branched hydrocarbon radical of two to twelve carbon atoms containing at least one triple bond. Examples include ethynyl, propynyl, and the like, wherein the alkynyl radical may be optionally substituted independently with one or more substituents described herein. Preferred alkynyl radicals are those having 2 to 6 carbon atoms (“C 2 -C 6 alkynyl”).
In some embodiments, an aryl is an aromatic carbocyclic group having a single ring (e.g., phenyl), multiple rings (e.g., biphenyl), or multiple condensed rings in which at least one is aromatic, (e.g., 1,2,3,4-tetrahydronaphthyl, naphthyl), which is optionally mono-, di-, or trisubstituted with, e.g., halogen, lower alkyl, lower alkyloxy, trifluoromethyl, aryl, heteroaryl, and hydroxy.
In some embodiments, a heteroaryl is a monocyclic aromatic radical of 5 to 10 ring atoms or a polycyclic aromatic radical, containing one to four ring heteroatoms selected from nitrogen, oxygen, or sulfur, the remaining ring atoms being carbon. The aromatic radical is optionally substituted independently with one or more substituents described herein. Examples include, but are not limited to, furyl, thienyl, pyrrolyl, pyridyl, pyrazolyl, pyrimidinyl, imidazolyl, pyrazinyl, indolyl, thiophen-2-yl, quinolyl, benzopyranyl, thiazolyl, and derivatives thereof. Other non-limiting examples of heteroaryl include [1,2,4]triazolo[1,5-a]pyridinyl, imidazo[1,2-a]pyridinyl and indazolyl.
In some embodiments, the term “heterocyclyl” refers to a saturated or partially unsaturated cyclic radical of 3 to 14 ring atoms in which at least one ring atom is a heteroatom selected from nitrogen, oxygen and sulfur, the remaining ring atoms being carbon where one or more ring atoms may be optionally substituted independently with one or more substituent described herein. The radical may be a carbon radical or heteroatom radical. “Heterocyclyl” also includes radicals where heterocycle radicals are fused with aromatic or heteroaromatic rings. A “heterocyclyl” may be mono-cyclic, bicyclic, multi-cyclic. Spiro moieties are also included within the scope of this definition. Examples of “heterocyclyl” include, but are not limited to, pyrrolidinyl, piperidinyl, piperazinyl, tetrahydrofuranyl, tetrahydropyranyl, morpholinyl, thiomorpholinyl, homopiperazinyl, phthalimidyl, 3-oxabicyclo[3.1.0]hexyl (e.g., 3-oxabicyclo[3.1.0]hexan-6-yl and 3-oxabicyclo[3.1.0]hexan-1-yl), and derivatives thereof.
Certain examples of compounds of the invention are listed in Table 1.
TABLE 1
Entry No.
Structure
Name
1
(E)-N-(7-((3R,3aS,6S,6aS)-hexahydro-3- methoxyfuro[3,2-b]furan-6-yloxy)-4-(3-chloro- 4-fluorophenylamino)quinazolin-6-yl)-4- (dimethylamino)but-2-enamide
2
(E)-N-(7-((3-oxa-bicyclo[3.1.0]hexan-6- yl)methoxy)-4-(3-chloro-4- fluorophenylamino)quinazolin-6-yl)-4- (dimethylamino)but-2-enamide
3
(E)-N-(7-(((1S,5S)-3-oxa-bicyclo[3.1.0]hexan- 1-yl)methoxy)-4-(3-chloro-4- fluorophenylamino)quinazolin-6-yl)-4- (dimethylamino)but-2-enamide
4
(E)-N-(7-(((1R,5R)-3-oxa-bicyclo[3.1.0]hexan- 1-yl)methoxy)-4-(3-chloro-4- fluorophenylamino)quinazolin-6-yl)-4- (dimethylamino)but-2-enamide
5
(E)-N-(7-((3-oxa-bicyclo[3.1.0]hexan-1- yl)methoxy)-4-(3-chloro-4- fluorophenylamino)quinazolin-6-yl)-4- (dimethylamino)but-2-enamide
Salts of these compounds can be formed with the acids including, but are not limited to, malic acid, lactic acid, maleic acid, fumaric acid, succinic acid, hydrochloric acid, methanesulfonic acid, toluenesulfonic acid, benzenesulfonic acid, sulfuric acid, phosphoric acid, citric acid, tartaric acid, acetic acid, propionic acid, caprylic acid, caproic acid, and benzoic acid.
Except as expressly defined otherwise, the described structures of this invention include all the isomeric forms (such as enantiomers, non-enantial isomers, geometric isomers, and stereoisomers (diasteromers)): such as (R)- or (S)-conformers from asymmetric centers, (Z) and (E)-isomers from double bond, and (Z) and (E) conformation isomers. Accordingly, single stereochemical isomers of the compounds of the invention or its enantiomer, non-enantial isomers, or mixture of geometric isomers (or conformers) all belong to the scope of this invention.
The compounds of the invention may contain asymmetric centers or chiral centers, therefore the existence of different stereoisomers. All stereoisomeric forms of compounds of the invention, including but not limited to, diastereomers, enantiomers, asymmetric rotamers and their mixtures, such as the racemic mixture, comprised part of this invention. Many organic compounds exist in optically active form, ie they have the ability to rotate the plane of plane polarized light. When the optical activities are described, prefix D, L or R, S are used to describe the absolute configuration. Prefixes d, l or (+), (−) are used to described the direction of rotation, with (−) or l indicating rotating left, and (+) or d for rotating right. Theses stereoisomers have the same two dimensional formula, but their three dimensional structures are different. Specific sterepisomers can be enantiomers (mirror image isomers), and the mixture of isomers is referred to mixture of enantiomers. A 50:50 mixture of enantiomers are referred to racemates. The term “racemate” refers to equal molar mixture of two optical enantiomers, and thus lacking optimal activity.
The term “tautomer” or “tautomeric form” used in this invention refers to that isomers of different energy can cross the low energy barrier and become exchangeable. For example, proton tautomers (proton migration) include the isomers resulting from proton migration, such as ketone-enol and imine-enamine isomers. Valence tautomers include isomers resulting from rearrangement of bond electrons.
Except as expressly defined otherwise, the compounds in this invention include all the tautomers.
Unless indicated otherwise, all stereo isomers, geometric isomers, tautomers, N-oxides, hydrates, solvates, metabolites, salts and pharmaceutically acceptable prodrugs of a compound of the invention are within the scope of the invention.
The term “prodrug” as used herein refers to a compound that may be converted in vivo to a compound of the formula (I). The conversion is affected by hydrolysis in blood or enzymatic conversion in blood or in tissue of the prodrug to the parent structure.
A “metabolite” is a product produced through metabolism in the body of a specified compound or its salt. Metabolites of a compound may be identified by using routine techniques known in the art and their activities determined using tests such as those described herein. Such products can be obtained from the parent compound via oxidation, reduction, hydrolysis, amidation, amide hydrolysis, esterification, ester hydrolysis, enzyme catalyzed fragmentation, etc. Accordingly, this invention includes all the metabolites of the compounds, and includes all the metabolites after the compounds are sufficiently exposed in mammals for a period of time.
“Pharmaceutically acceptable salts” in the invention refer to organic or inorganic of the compounds of this invention. Pharmaceutically acceptable salts are well known in the art.
Pharmaceutically acceptable salts formed from non-toxic acids include, but not limited to the salts formed from mineral acids reacting with an amino group, such as hydrochloric acid salt, hydrobromic acid salt, phosphoric acid salt, sulfuric acid salt, nitric acid salt; and with an organic acid such as acetic acid salt, oxalic acid salt, maleic acid salt, tartric acid salt, citric acid salt, succinic acid salt, malonic acid salt; or salts can also be prepared by alternative methods as described in literature, such as ion-exchange methods. Other pharmaceutically acceptable salts include Adipate, Alginate, ascorbate, aspartate, benzenesulfonate salt, benzoate salt, heavy sulfate, borate, butyrate, camphor, salts, camphor sulfonate, cyclopentyl C formategluconate, sodium dodecyl sulfate, ethylene sulfonate, formate, fumarate salts, glucoheptonate salts, glycerol phosphate, gluconate, semi-sulfate, heptanoic acid salts, caproic acids alt, iodate2-hydroxyethylsulfonate, lactobionate, lactate, laurate, lauryl sulfate, malate, malonate, methanesulfonate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, palmitic acid salt, pamoic acid salt, pectic acid salts, persulfate salts, 3-phenylpropionate, picrate, pentyl formate, propionate, stearate, thiocyanate, tosylate, undecanoate, valerate, etc. Salts prepared from reaction with an appropriate base include alkaline, alkaline earth metal, ammonium, and N + (C 1 -C 4 Alkyl) 4 . This invention also include any quarternary salt from compounds containing an “N” group, water soluble or lipid soluble or suspension can also be obtained via quaternary ammonium method. Alkaline and alkaline earth metal salts include sodium, lithium, potassium, calcium, magnesium, etc. Pharmaceutically acceptable salts further include appropriate harmless ammonium, quaternary ammonium, and ions to counter ammonium cations such as halide, hydroxide, carboxylate, sulfate, phosphate, C 1 -C 3 alkanesulfate and arylsulfate.
Specifically, the salt is a pharmaceutically acceptable salt. The term “pharmaceutically acceptable” includes the substance or composition that must be suitable chemically or toxicologically to form formulation with other components of the preparation and to treat mammals.
When a compound of the invention is a base, the desired pharmaceutically acceptable salt may be prepared by any suitable method available in the art, for example, treatment of the free base with an inorganic acid, such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid and the like, or with an organic acid, such as acetic acid, maleic acid, succinic acid, mandelic acid, fumaric acid, malonic acid, pyruvic acid, oxalic acid, glycolic acid, salicylic acid, a pyranosidyl acid such as glucuronic acid or galacturonic acid, an alpha-hydroxy acid such as citric acid or tartaric acid, an amino acid such as aspartic acid or glutamic acid, an aromatic acid such as benzoic acid or cinnamic acid, a sulfonic acid such as p-toluenesulfonic acid or ethanesulfonic acid, or the like.
When a compound of the invention is an acid, the desired pharmaceutically acceptable salt may be prepared by any suitable method, such as an inorganic or organic base, such as an amine (primary, secondary or tertiary), an alkali metal hydroxide or alkaline earth metal hydroxide, or the like. Suitable salts include, but are not limited to, organic salts derived from amino acids, such as glycine and arginine, ammonia, primary, secondary, and tertiary amines, and cyclic amines, such as piperidine, morpholine and piperazine, and inorganic salts derived from sodium, calcium, potassium, magnesium, manganese, iron, copper, zinc, aluminum and lithium.
The term “solvate” refers to an aggregate of a compound of this invention with one or more solvent molecules. Solvents that form solvate include, but not limited to, water, isopropanol, ethanol, methanol, methyl sulfoxide, ethyl acetate, acetic acid, aminoethanol. The term “hydrate” refers to an aggregate formed with water as solvent molecules.
The compounds in the invention exist as parent forms, or appropriate pharmacetutically acceptable derivatives. Based on this invention, the pharmacetutically acceptable derivatives include, but not limited to pharmacetutically acceptable prodrugs, salts, esters, salts of esters, or other derivatives or compositions prepared based directly or indirectly on the needs of patients, or otherwise described compounds in this invention or their metabolites, or other degradation products.
Synthesis
In one aspect, provided is a method for making a compound of the formula (I):
wherein:
Ar is a monocyclic aryl or monocyclic heteroaryl, optionally substituted with 0 to 4 substituents independently selected from the group consisting of halogen, trifluoromethyl, trifluoromethoxy, C 1 -C 3 alkyl, ethynyl, ethenyl, C 1 -C 3 alkoxy, —O(CH 2 ) n Ar 1 ; —(CH 2 ) m Ar 2 and —S(O) 2 Ar 3 ; m and n are independently 0 or 1; each Ar 1 , Ar 2 and Ar 3 is independently a monocyclic aryl or 5 or 6 membered heteroaryl, where each aryl or heteroaryl is optionally substituted with 0 to 3 substituents independently selected from the group consisting of halogen, trifluoromethyl, trifluoromethoxy, C 1 -C 3 alkyl, C 2 -C 3 alkynyl, C 2 -C 3 alkenyl and C 1 -C 3 alkoxy; L is a bond or CH 2 ; and M is a 6-10 membered bicyclic heterocycle containing one or more annular heteroatoms independently selected from O, N and S, optionally substituted with one or more substituents independently selected from the group consisting of halogen, C 1 -C 3 alkyl, hydroxyl and C 1 -C 3 alkoxy,
comprising the steps of:
Step 1: reacting compound of formula (Ia):
with a compound of formula ArNH 2 to obtain a compound of the formula (Ib):
Step 2: treating an alcohol of the formula M-L-OH with a strong base, and then adding the compound of the formula (Ib) to obtain a compound of the formula (Ic):
Step 3: reducing the compound of the formula (Ic) to produce a compound of the formula (Id):
Step 4: coupling the compound of the formula (Id) with an acid of the formula (Ie):
using a coupling reagent to form an amide of the formula (If):
and
Step 5: producing a compound of the formula (I) by a Wittig reaction of the compound of the formula (If) with 2-dimethylaminoacetaldehyde.
In some embodiments, provided is a method for making a compound of the formula (I) comprising performing the synthetic steps shown in Scheme 1:
In some embodiments, 4-Chloroquinazoline Ia (reference: Rewcastle, G. W., et al. J. Med. Chem., 1996, vol. 39, 918-928) is reacted with an aniline compound to give compound Ib. The corresponding alcohol M-L-OH is treated with a strong base (sodium hydride), and to it is added compound Ib. The resulted compound Ic is reduced to amine Id. The reduction method can be platinum-carbon catalyzed hydrogenation, or iron powder in acid. The amine Id prepared by this method formed amide with a coupling agent such as CDI (N,N′-carboyldiimidazole) and acid Ie to give a compound If. Wittig reaction of compound If with freshly prepared 2-dimethylaminoacetaldehyde affords a compound of general Formula (I).
In some embodiments, provided is a method for making a compound of formula (I), comprising the steps described above, wherein:
Ar is a substituted monocyclic phenyl or monocyclic heteroaryl, optionally substituted with 0-4 groups selected from halogen, trifluoromethyl, trifluoromethoxy, C 1-3 alkyl, ethynyl, ethenyl, C 1-3 alkoxyl; or O(CH 2 ) n Ar 1 , where n is 0 or 1;
Ar 1 is selected from monocyclic aryl or 5-6 membered heteroaryl group, and the aryl or heteroaryl may be substituted with 0-3 groups selected from halogen, trifluoromethyl, trifluomethoxy, C 1-3 alkyl, C 2-3 alkynyl, C 2-3 alkenyl, and C 1-3 alkoxyl;
L is selected from a bond or CH 2 ;
M is a 6-10 membered bicyclic heterocycle, containing one or more O, N, or S atoms, and the heterocycle may be further substituted with one or more halogen, C 1-3 alkyl, hydroxyl, or C 1-3 alkoxyl.
As a preferred embodiment, the strong base in step 2 is sodium hydride; and as another preferred embodiment, the reduction in step 3 is carried out with platinum-carbon catalyzed hydrogenation, or iron powder-acid reduction.
Methods of Treatment
In another aspect, provided is method for treating a receptor protein tyrosine kinase-related disease in an individual in need thereof comprising administering to the individual an effective amount of a compound of the formula (I), or any variation thereof described herein, such as a compound listed in Table 1 and in the Examples 1-5 (e.g., NT112), or a salt, solvate, polymorph, metabolite or prodrug thereof. In some embodiments, the receptor protein tyrosine kinase-related disease is a cancer selected from the group consisting of breast cancer, colorectal cancer, lung cancer, papillary carcinoma, prostate cancer, lymphoma, colonpancreatic cancer, ovarian cancer, cervical cancer, central nervous system cancer, osteogenic sarcoma, kidney cancer, liver cancer, bladder cancer, gastric cancer, head and neck squamous cell carcinoma, melanoma and leukemia. In some embodiments, the cancer is a breast cancer, gastric cancer, lung cancer, colorectal cancer, central nervous system cancer, or head and neck squamous cell carcinoma. In some embodiments, the cancer is an erlotinib-resistant cancer (e.g., an erlotinib-resistant non-small cell lung cancer).
In some embodiments, “treatment” or “treating” is intended to mean at least the mitigation of a disease condition in a mammal, such as a human, that is affected, at least in part, by the activity of one or more receptor protein tyrosine kinases, and includes, but is not limited to, preventing the disease condition from occurring in a mammal, particularly when the mammal is found to be predisposed to having the disease condition but has not yet been diagnosed as having it; modulating and/or inhibiting the disease condition; and/or alleviating the disease condition.
In some embodiments, “delaying development of a disease” means to defer, hinder, slow, retard, stabilize, and/or postpone development of the disease (such as cancer). This delay can be of varying lengths of time, depending on the history of the disease and/or individual being treated. As is evident to one skilled in the art, a sufficient or significant delay can, in effect, encompass prevention, in that the individual does not develop the disease. For example, a late stage cancer, such as development of metastasis, may be delayed.
In some embodiments, the term “individual” as used herein refers to a mammal, including but not limited to, bovine, horse, feline, rabbit, canine, rodent, or primate (e.g., human). In some embodiments, an individual is a human. In some embodiments, an individual is a non-human primate such as chimpanzees and other apes and monkey species. In some embodiments, an individual is a farm animal such as cattle, horses, sheep, goats and swine; pets such as rabbits, dogs and cats; laboratory animals including rodents, such as rats, mice, and guinea pigs; and the like. The invention may find use in both human medicine and in the veterinary context. In some embodiments, the individual is suffering from a receptor protein tyrosine kinase-related disease (e.g., cancer), or has been diagnosed to have a receptor protein tyrosine kinase-related disease (e.g., cancer).
In one embodiment, the invention provides a pharmaceutical composition, containing a compound of Formula (I), or its pharmaceutically acceptable salts or prodrugs and pharmaceutically acceptable carriers or excipients, and the preparation of drugs to treat receptor tyrosine kinase related diseases or inhibitors of receptor tyrosine kinases, especially the application of erbB family receptor tyrosine kinase inhibitors.
Also provided is a method for modulating receptor protein tyrosine kinases (RTKs), including the binding of RTK with a compound of formula (I) or a pharmaceutically acceptable salt thereof.
Further provided is a method of applying compounds or its pharmaceutical composition to treat diseases related to receptor tyrosine protein kinases, including giving patients the appropriate doses of these compounds or the pharmaceutical composition containing these compounds.
Therapeutically effective amounts of the compounds of the invention may be used to treat diseases mediated by modulation or regulation of receptor protein tyrosine kinases (RTKs). An “effective amount” is intended to mean that amount of compound that, when administered to a mammal in need of such treatment, is sufficient to effect treatment for a disease mediated by the activity of one or more RTKs. Thus, for example, a therapeutically effective amount of a compound of the formula (I), or a salt, active metabolite or prodrug thereof, is a quantity sufficient to modulate, regulate, or inhibit the activity of one or more RTKs such that a disease condition which is mediated by that activity is reduced or alleviated. In the case of cancer or tumor, an effective amount of the drug may have the effect in reducing the number of cancer cells; reducing the tumor size; inhibiting (i.e., slow to some extent and preferably stop) cancer cell infiltration into peripheral organs; inhibit (i.e., slow to some extent and preferably stop) tumor metastasis; inhibiting, to some extent, tumor growth; and/or relieving to some extent one or more of the symptoms associated with the disorder. An effective dosage can be administered in one or more administrations. For purposes of this invention, an effective dosage of drug, compound, or pharmaceutical composition is an amount sufficient to accomplish prophylactic or therapeutic treatment either directly or indirectly.
The amount of a given agent that will correspond to such an amount will vary depending upon factors such as the particular compound, disease condition and its severity, the identity (e.g., weight) of the mammal in need of treatment, but can nevertheless be routinely determined by one skilled in the art.
Compounds of this invention has shown superior pharmacokinetic properties compared to a known standard compound afatinib. Higher oral bioavailability and better PK profile may translate to a lower dose to achieve the same efficacy; and potentially lower side effect as a smaller dose is required.
In order to use a compound of the formula (I), or a pharmaceutically acceptable salt or in vivo cleavable prodrug thereof, for the therapeutic treatment (including prophylactic treatment) of mammals including humans, it is normally formulated in accordance with standard pharmaceutical practice as a pharmaceutical composition. According to this aspect of the invention there is provided a pharmaceutical composition that comprises a compound of the formula (I), or a pharmaceutically acceptable salt or in vivo cleavable prodrug thereof, as defined hereinbefore in association with a pharmaceutically acceptable diluent or carrier.
The compounds of the invention are administered either singly or in combination to a mammal to treat a receptor protein tyrosine kinase-related disease, such as various types of cancer, e.g., cancer of the colon, ovary, bladder, stomach, lung, uterus, and prostate. The compound may be administered via any acceptable route, e.g., intra venous, oral, intra muscular, via suppository, etc. The compounds can be formulated as oral dosage forms, e.g., tablets, capsules, liquid suspension, etc, as suppositories, or may be prepared as a liquid for injection, for example. The skilled practitioner can select the appropriate route and dosage amount for treatment of the specific receptor protein tyrosine kinase-related disease to be treated.
Formulations
“Pharmaceutical composition” is a mixture of one or more compounds of this invention or their pharmaceutically acceptable salts or prodrugs with other compounds, other components are physiologically or pharmaceutically acceptable carriers or excipients. The purpose of a pharmaceutical composition is to facilitate administration of the compound to a living thing.
As described in this invention, a pharmaceutically acceptable composition in the present invention further contains a pharmaceutically acceptable carrier, adjuvant, or excipient, as in the application of the present invention, including any solvent, diluents, or other liquid excipients, dispersing agent or suspending agent, surfactants, isotonic agents, thickeners, emulsifiers, preservatives, solid binders or lubricants, etc., suitable for specific target formulations
A pharmaceutically acceptable carrier includes, but is not limited to, ion exchange agents, aluminum, aluminum stearate, lecithin, serum proteins, such as human serum protein, buffers, such as phosphate, glycine, sorbic acid, potassium sorbate, saturated vegetable oil and partial glycerol ester mixture, water, salt or electrolyte, protamine sulfate, disodium hydrogen phosphate, potassium hydrogen phosphate, sodium chloride, zinc salts, colloidal silica, magnesium trisilicate, polyvinyl pyrrolidone, polyacrylic acid lipid, wax, polyethylene-polyoxypropylene-blocking polymer, lanolin, sugar, lactose, glucose and sucrose; Starch such as corn starch and potato starch; cellulose and its derivatives such as sodium carboxymethyl cellulose, ethyl cellulose and cellulose acetate; tree wax powder; malt; gelatin; talc; excipients such as cocoa bean butter and suppository waxtilting; Oils such as peanut oil, cottonseed oil, safflower oil, sesame oil, olive oil, corn oil and soybean oil; diols such as propylene glycol and polyethylene glycol; esters such as ethyl oleate and ethyl laurate; agar; buffering agent such as magnesium hydroxide and aluminum hydroxide; alginate; pyrogen water; isotonic saline; Stringer solution; ethanol, phosphate buffer solution, and other non-toxic suitable lubricant, such as baysodium sulfate and magnesium stearate, coloring agents, release agents, coating agent, sweeteners, flavoring agents and spices, preservatives and antioxidants.
The compositions of the invention may be in a form suitable for oral use, for injection, for inhalation, for topical use, for rectal dosing, for administration by insufflations, for sublingual use, for vaginal dosing, or for implant use. The term “for injection” refers to subcutaneous, intravenous, intramuscular, joint, intra-synovial membrane (cavity), intra-sternum, intra-membrane, intraocular, intrahepatic, intralesional and intracranial injection or infusion technology, preferred composition is for oral use, intraperitoneal use, and for intravenous injection. Sterile injection of the composition of this invention can be water or oily suspensions. These suspensions can be prepared with publicly known technology using suitable formula of dispersing agents, wetting agents and suspending agent. Sterile injection can be a sterile solution or suspension of non-toxic acceptable diluent or solvent, such as 1,3-butanediol. The acceptable excipient and solvents can be water, Ringer solution, and isotonic sodium chloride solution. Furthermore, sterile non volatile oil can be used solvent or suspension medium, according to the prior art.
For this purpose, any mild, non-volatile oil may be the synthetic mono or diacylglycerol. Fatty acids such as oleic acid and its glyceride derivatives can be used for the preparation of the intravenous injectable, natural pharmaceutically acceptable oils, such as olive oil or castor oil, especially their polyoxyethylene derivatives can also be used. These oil solutions or suspensions can contain long-chain alcohol diluent or dispersant such as carboxymethyl cellulose or similar dispersing agents; pharmaceutical acceptable dosage forms include emulsions and suspensions. Other commonly used surfactants, such as Tween, Span class, and other emulsifiers or biological drug efficiency enhancer, pharmaceutically acceptable solid, liquid, or other dosage forms can be applied to the target pharmaceutical preparation.
The pharmaceutically acceptable composition of the present invention can be an acceptable oral formulation for oral administration, including but not limited to, capsules, tablets, water suspension or solution. For oral tablets, carriers generally include lactose and corn starch. Lubricants such as magnesium stearate, are typically added. For oral capsule administration, suitable diluents include lactose and dried corn starch. When oral formulation is a water suspension, the active ingredients can be comprised of emulsifier and suspending agent. For these formulations, sweeteners, flavoring agents or colorants can be added.
In addition, the pharmaceutically acceptable compositions of the present invention can be in the form of a rectal suppository. These can be prepared by mixing the agent with the appropriate non-perfusion adjuvant. The mixture prepared this way is a solid at room temperature, but it become a liquid at rectal temperature and releases the drug in the rectum. Such substances include cocoa fat, beeswax, and polyethylene glycol. The pharmaceutically acceptable compositions of the present invention can be used for localized drug delivery, especially when treatment goal is easier to reach with topical drug delivery on certain treatment region or organs, such as disease of eye, skin or intestine. Suitable topical formulations can be prepared and applied to these areas or organs.
Rectal suppositories (see above) or a suitable enema can be applied to the local administration of the lower intestinal tract. Local skin spots can also be medicated the same way. For local administration, the pharmaceutically acceptable compositions can be prepared accordingly into a suitable ointment, the ointment containing the active ingredient suspended in or dissolved in one or more carriers. Localized drug delivery carriers of this invention include, but are not limited to mineral oil, liquid paraffin, white petrolatum, propylene glycol, polyoxyethylene, polyoxypropylene compound, emulsified wax and water. In addition, the pharmaceutically acceptable compositions can be prepared into a suitable lotion or cream, the lotion or cream containing the active ingredient is suspended in or dissolve in one or more pharmaceutically acceptable carriers. A suitable carrier, including, but not limited to, mineral oil, Span 60 (sorbitan monostearate), Tween 60 (polysorbate 60), cetyl ester wax, palm alcohol, 2-octyl dodecanol, benzyl alcohol and water.
A pharmaceutically acceptable composition for eye application can be prepared into formulations such as particulate suspensions in isotonic, pH adjusted sterile saline or other aqueous solutions, preferably isotonic solution and pH adjusted sterile saline or other aqueous solutions. The disinfection of preservatives such as benzalkonium chloride can be added to the formulation. In addition, the pharmaceutically acceptable compositions for the eye can be prepared into the ointment such as Vaseline. Administration of a pharmaceutically acceptable composition of the present invention can be applied via the gas solvents or inhalants thorough nose. This composition can be prepared from known formula and technology, or can be prepared as a salt solution using benzyl alcohol or other suitable preservatives, absorption enhancers, fluorocarbons, or other conventional solubilizing agent or dispersing agent to improve the bioavailability.
Liquid formulations for oral administration include, but not limited to, pharmaceutically acceptable emulsions, micro-emulsion, solution, suspension, syrup and elixir. In addition to the active compounds, the liquid dosage forms may contain inert diluents known in the art, for example, water or other solvent, solubilizer and emulsifier, such as ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butanediol, dimethylformamide, oils and fats (in particular, cottonseed, groundnut, corn, microbes, olive, castor and sesame oil), glycerin, 2-tetrahydrofuranmethanol, polyethyleneglycol, dehydrated sorbitol fatty acid esters, and their mixtures. Addition to inert diluents, the oral compositions can also contain adjuvants such as wetting agents, emulsifiers or suspending agent, sweeteners, flavorings and fragrances.
The solid dosage forms for oral administration include capsules, tablets, pills, powders and granules. In these formulations, the active compounds are mixed with at least one pharmaceutically acceptable inert excipients or carrier, such as sodium citrate or calcium phosphate or filling agents, or (a) fillers such as starch, lactose, sucrose, glucose, mannitol and silicic acid; (b) adhesives such as carboxymethylcellulose, alginates, gelatin, polyethylene pyrrole ketone, sucrose and gum arabic; (c) moisturizing agents such as glycerol; (d) disintegrating agents such as agar, calcium carbonate, potato starch or tapioca starch, alginic acid, certain silicates and sodium carbonate; (e) blocker solution, such as paraffin; (f) absorption promoter such as quaternary ammonium compounds; (g) wetting agents such as decahexanyl alcohol and glycerol monostearate; (h) absorbents such as kaolin and bentonite, (i) lubricants such as talc, calcium stearate, magnesium stearate, solid polyethylene glycol, laurylsodium sulfate, and mixtures thereof. Formulations such as capsules, tablets and pills can contain buffer.
Injection, such as sterile injection or oily suspensions can be prepared by well known technology using suitable dispersing agents, wetting agents and suspending agent. Sterile injection can be prepared at the location of application by a non-toxic locally acceptable diluent or solvent to give sterile injection, suspension or emulsion, for example, 1,3-butanediol solution. Acceptable excipients and solvents are water, Ringer's solution, USP and isotonic sodium chloride solution. In addition, sterile, non-volatile oil has been used as the solvent or suspension medium. Any mild, non-volatile oil used for this purpose may include the synthetic mono or di-glucosyl diacylglycerol. In addition, fatty acids such as oleic acid can be used in injection.
Injection can be sterile, such as filtration through a sterilization filter, or incorporation of a sterilizing agent in the form of sterile solid compositions. Sterilizing agent can be dissolved in or dispersed in sterile water or sterile injection medium prior to use. In order to prolong the effect of the compounds of the invention, subcutaneous or intramuscular injection can be used to slow the absorption of compounds. The problem of poor water solubility of the crystal or non-crystalline material can be solved by using liquid suspension. The absorption rate of the compound depends on its dissolution, in turn depends on grain size and crystal shape. In addition, the compound is dissolved or dispersed in the oil excipient to delay absorption of the compound injection.
Preferably, the compounds of the invention are formulated into unit dosage forms in order to reduce the amount of drug administered and to obtain dose uniformity. The term “unit dosage form” as used herein refers to physical drug dispersion unit that patients will receive for the appropriate treatment. However, the total daily dosage of the compounds or compositions of the present invention will be determined by the physician based on the reliable range of medical judgment. The specific effective dose level for a particular patient or organism will depend on many factors, including the disease or condition treated and the severity of the disease or condition, the activity of specific compounds, the specific composition, the patient's age, body weight, health status, gender, dietary habits, time of administration, route of administration and excretion rate of the specific compound used, the duration of treatment, drug combination or drug used in tandem with another specific compounds, as well as some other pharmacological factors known in the art.
EXAMPLES
The following specific examples further illustrate the present invention. However, it is well understood that the examples below are intended to illustrate embodiments of the invention, and are not intended to limit the scope of the specification or claims in any way. Compounds of the invention can be prepared following the methods described herein or methods known in the art.
The structures of compounds are determined by nuclear magnetic resonance (NMR) and mass spectroscopy (MS). NMR shift (δ) has units of parts-per-million (ppm). NMR spectra were measured using a Bruker-300 NMR spectrometer. MS spectra were taken on an Agilent LC-MS (ESI+) mass spectrometer.
Unless otherwise specified, the reactions are carried out under nitrogen atmosphere.
Column chromatography and preparative thin layer chromatography were done using silica or thin-layer-silica plate manufactured by Merck.
Example 1
Preparation of (E)-N-(4-((3-chloro-4-fluorophenyl)-7-(((3S,3aS,6R,6aS)-6-methoxyhexahydrofuro[3,2-b]furan-3-yl)oxy)quinazolin-6-yl)-4-(dimethylamino) but-2-enamide (1)
Step 1: preparation of N-(3-chloro-4-fluorophenyl)-7-(((3S,3aS,6R,6aS)-6-methoxyhexahydrofuro[3,2-b]furan-3-yl)oxy)-6-nitroquinazolin-4-amine (1b)
NaH (60% dispersion in mineral oil, 493 mg, 12.32 mmol) was added in portions to a stirring solution of dianhydro-D-glucitol (1.5 g, 10.26 mmol) in DMF (20 mL) at room temperature under N 2 (g) atmosphere. After 20 min, methyl iodide (639 μL, 10.26 mmol) was added, the mixture stirred for 30 min, cooled to 0° C., followed by stepwise addition of DMF (20 mL) and NaH (493 mg, 12.32 mmol). N-(3-chloro-4-fluorophenyl)-7-fluoro-6-nitroquinazolin-4-amine 1a (500 mg, 1.48 mmol, prepared according to Smaill, J. B., et al., Journal of Medicinal Chemistry, 2000, 43, 1380-1397) was added after 20 min and the reaction was quenched 30 min later at 0° C. by a slow addition of saturated NH 4 Cl, followed by extraction with EtOAc (100 mL). The organic layer was washed with H 2 O (2×100 mL), brine (100 mL), dried over MgSO 4 , and concentrated to a yellow residue 1b. MS m/z (ESI+), 477 [M+1].
Step 2: preparation of N 4 -(3-chloro-4-fluorophenyl)-7-(((3S,3aS,6R,6aS)-6-methoxyhexahydrofuro[3,2-b]furan-3-yl)oxy)-6-nitroquinazoline-4,6-diamine (1c)
Glacial acetic acid (3 mL) was added to a stirring solution of 1b (700 mg, 1.47 mmol) in EtOH:H 2 O (90 mL, 2:1 (v/v)), followed by reduced iron (328 mg, 5.87 mmol). The mixture was refluxed for 1 hr and cooled to room temperature. 5M NaOH was added to adjust the pH to 7-8, diluted with EtOAc (100 mL), stirred vigorously for 30 min, and filtered through celite. The black cake was washed with warm EtOAc (2×100 mL) and the filtrates concentrated. The residue was diluted in H 2 O (100 mL), extracted with MeOH:DCM (2×100 mL, 1:9 (v/v)), the organic layer was washed with brine (100 mL), dried over MgSO 4 , and concentrated to a yellow green residue (1c). LCMS m/z (ESI+): 447 [M+1].
Step 3: preparation of Diethyl(2-((4-(3-chloro-4-fluorophenyl)-7-(((3S,3aS,6R,6aS)-6-methoxyhexahydrofuro[3,2-b]furan-3-yl)oxy)quinazolin-6-yl)amino-2-oxoethyl)phosphonate (1d)
1,1-Carbonyldiimidazole (CDI, 310 mg, 1.91 mmol) and diethylphosphonoacetic acid (375 mg, 1.91 mmol) in THF (10 mL) were stirred at 40° C. for 30 min. A solution of 1c (657 mg, 1.47 mmol) in THF (3 mL) was added and the mixture stirred at 45° C. overnight. Once concentrated, the residue was diluted in EtOAc (100 mL), washed with sat. NaHCO 3 (50 mL), H 2 O (100 mL), brine (100 mL), dried over MgSO 4 , and concentrated. The gray solid was sonicated in ether (30 mL), filtered and dried in vacuo. The resulting reside 1d was used for the synthesis of 1 without further purification. LCMS m/z (ESI+): 625 [M+1].
Step 4: preparation of (E)-N-(4-((3-chloro-4-fluorophenyl)-7-(((3S,3aS,6R,6aS)-6-methoxyhexahydrofuro[3,2-b]furan-3-yl)oxy)quinazolin-6-yl)-4-(dimethylamino)but-2-enamide 1
Lithium chloride monohydrate (105 mg, 1.28 mmol) was added to a solution of 1d (400 mg, 0.64 mmol) in EtOH (10 mL), followed by KOH (45% (wt), 1 mL) at room temperature. After 5 min, a solution of dimethylaminoacetaldehyde-hydrogen sulphite adduct (214 mg, 1.28 mmol, prepared according to method in WO2007/85638) in H 2 O (4 mL) was added, stirred for 15 min, concentrated, diluted in DCM (200 mL), washed with H 2 O (2×100 mL), brine (100 mL), dried over MgSO 4 , and concentrated. Column chromatography (0-20% MeOH/DCM, gradient), followed by lyophilization afforded 1 as white solids (246 mg, 68.9%). 1 HNMR (CDCl 3 , 300 MHz) δ 9.16 (s, 1H), 8.66 (s, 1H), 8.04 (s, 1H), 7.90 (d, 1H), 7.75 (s, 1H), 7.56 (m, 1H), 7.40 (s, 1H), 7.17 (m, 1H), 7.06 (m, 1H), 6.25 (d, 1H), 5.05 (s, 1H), 4.85 (t, 1H), 4.74 (d, 1H), 4.32 (m, 2H), 4.01 (m, 2H), 3.78 (t, 1H), 3.54 (s, 2H), 3.20 (d, 2H), 2.35 (s, 6H). LCMS (ESI) m/z=559 (MH + ).
Example 2
Preparation of (E)-N-(7-((3-oxabicyclo[3.1.0]hexan-6-ylmethoxy)-4-((3-chloro-4-fluorophenyl)amino)quinazolin-6-yl)-4-(dimethylamino)but-2-enamide (2)
Step 1: preparation of 7-((3-oxabicyclo[3.1.0]hexan-6-ylmethoxy)-N-(3-chloro-4-fluorophenyl)-6-nitroquinazolin-4-amine (2b)
NaH (60% dispersion in mineral oil, 480 mg, 12.0 mmol) was added in portions to a stirring solution of (3-oxa-bicyclo[3.1.0]hexan-6-yl)methanol (570 mg, 5.0 mmol; prepared according to procedures described in WO2012/021591A1) in DMF (40 mL) at room temperature under N 2 (g) atmosphere. After 20 min, the mixture was cooled to 0° C., followed by addition N-(3-chloro-4-fluorophenyl)-7-fluoro-6-nitroquinazolin-4-amine 1a (1.54 g, 4.6 mmol, prepared according to Smaill, J. B., et al., Journal of Medicinal Chemistry, 2000, 43, 1380-1397). The reaction was quenched after stirring 30 min at 0° C. by a slow addition of saturated NH 4 Cl, followed by extraction with EtOAc (100 mL). The organic layer was washed with H 2 O (2×50 mL), brine (50 mL), dried over MgSO 4 , and concentrated to a yellow residue 2b, product was used directly for the next step. MS m/z (ESI+), 431 [M+1].
Steps 2, 3 and 4: preparation of (E)-N-(7-((3-oxabicyclo[3.1.0]hexan-6-ylmethoxy)-4-((3-chloro-4-fluorophenyl)amino)quinazolin-6-yl)-4-(dimethylamino)but-2-enamide (2)
The title compound (2) was prepared using the same procedures as in steps 2, 3 and 4 in Example 1, except that 2b was used in place of 1b. 1 HNMR (CDCl 3 , 300 MHz) δ 9.17 (s, 1H), 8.66 (s, 1H), 8.17 (s, 1H), 7.96 (m, 1H), 7.75 (s, 1H), 7.56 (m, 1H), 7.22 (s, 1H), 7.16 (m, 1H), 7.05 (m, 1H), 6.25 (d, 1H), 4.16 (d, 1H), 4.02 (d, 1H), 3.79 (d, 1H), 3.20 (d, 1H), 2.35 (s, 4H), 1.78 (s, 2H), 1.73 (s, 6H), 1.47 (m, 1H). MS (ESI) m/z=513 (MH + ).
The compound isolated after purification was predominantly the isomer of the structure (2-A), also referred to as “NT112”.
Example 3
Preparation of (E)-N-(7-((1S,5S)-3-oxabicyclo[3.1.0]hexan-1-yl)methoxy)-4-((3-chloro-4-fluorophenyl)amino)quinazolin-6-yl)-4-(dimethylamino)but-2-enamide (3)
Step 1: preparation of (1R,5S)-1-((benzyloxy)methyl)-3-oxa-bicyclo[3.1.0]hexan-2-one (3b)
To a stirred solution of (1R,5S)-1-(hydroxymethyl)-3-oxa-bicyclo[3.1.0]hexan-2-one (3a, 100 mmol, prepared according to Moon, H. R., et al. Nucleosides, Nucleotides and Nucleic Acids, 2007, 26, 975-978) in THF (200 mL) at 0° C. was added NaH (60% in mineral oil, 4.80 g, 120 mmol). After 10 min, BnBr (120 mmol) was added. After stirring at room temperature for 12 h, the reaction was cooled to 0° C., and to the reaction was added saturate aqueous NH 4 Cl (50 mL) and water (50 mL). The mixture was extracted with ether (300 mL). The organic layer was washed with water (100 mL), brine (50 mL), dried over MgSO 4 , and concentrated. The residue was purified by column (0-20 ethyl acetate in hanexane) to give a colorless liquid (3b). LCMS (ESI) m/z=219 (M+1).
Step 2: Preparation of (1S,5S)-1-((benzyloxy)methyl)-3-oxa-bicyclo[3.1.0]hexane (3c)
The conditions in Sakai, N., et al. Synthesis, 2008 3533-3536 was used for this step. To a stirred mixture of (1R,5S)-1-((benzyloxy)methyl)-3-oxa-bicyclo[3.1.0]hexan-2-one (3b, 50 mmol) and InBr 3 (1.0 mmol) in chloroform (200 mL) was added triethylsilane (200 mmol). The mixture was then heated and stirred at 65° C. for 16 h, then cooled to room temperature. The reaction was concentrated. The residue was purified by column (0-10 ethyl acetate in hexane) to give a colorless liquid as pure (1S,5S)-1-((benzyloxy)methyl)-3-oxa-bicyclo[3.1.0]hexane (3c). MS (ESI) m/z=205 (M+1).
Step 3: Preparation of ((1R,5S)-3-oxa-bicyclo[3.1.0]hexan-1-yl)methanol (3d)
A mixture of (1S,5S)-1-((benzyloxy)methyl)-3-oxa-bicyclo[3.1.0]hexane (3c, 40 mmol) and Pd on carbon (wet, 5%) in MeOH (50 mL) was hydrogenated by a hydrogen balloon for 3 h. The mixture was then filtered through Celite™, and concentrated in vacuum to give the title compound ((1R,5S)-3-oxa-bicyclo[3.1.0]hexan-1-yl)methanol (3d), which was used for next step without purification.
Steps 4, 5, 6, and 7: preparation of (E)-N-(7-(((1S,5S)-3-oxa-bicyclo[3.1.0]hexan-1-yl)methoxy)-4-(3-chloro-4-fluorophenylamino)quinazolin-6-yl)-4-(dimethylamino)but-2-enamide (3)
The title compound (3) was prepared by exactly the same procedures as in steps 1, 2, 3 and 4 in example 2, except 3d was used in place of 2a. 1 HNMR (CD 3 OD, 300 MHz) δ 8.78 (s, 1H), 8.48 (s, 1H), 8.01 (m, 1H), 7.67 (m, 1H), 7.25 (m, 2H), 7.01 (m, 1H), 6.47 (d, 1H), 4.62 (s, 1H), 4.53 (d, 1H), 4.37 (d, 1H), 4.01 (d, 1H), 3.85 (m, 2H), 3.24 (d, 2H), 2.34 (s, 6H), 1.77 (m, 1H), 1.29 (s, 1H), 1.00 (m, 1H), 0.79 (m, 1H), 0.11 (s, 1H). MS (ESI) m/z=513 (MH + ).
Example 4
Preparation of (E)-N-(7-((1R,5R)-3-oxabicyclo[3.1.0]hexan-1-yl)methoxy)-4-((3-chloro-4-fluorophenyl)amino)quinazolin-6-yl)-4-(dimethylamino)but-2-enamide (4)
The title compound, (E)-N-(7-(((1R,5R)-3-oxa-bicyclo[3.1.0]hexan-1-yl)methoxy)-4-(3-chloro-4-fluorophenylamino)quinazolin-6-yl)-4-(dimethylamino)but-2-enamide (4) was prepared by the same procedures as in Example 3, except that 4a was used in place of 3a. 1 HNMR (CD 3 OD, 300 MHz) δ 8.73 (s, 1H), 8.44 (s, 1H), 8.00 (m, 1H), 7.67 (m, 1H), 7.20 (m, 2H), 7.01 (m, 1H), 6.50 (d, 1H), 4.52 (s, 1H), 4.53 (d, 1H), 4.38 (d, 1H), 4.01 (d, 1H), 3.85 (m, 3H), 3.24 (d, 2H), 2.34 (s, 6H), 1.77 (m, 1H), 0.9 (m, 1H), 0.81 (s, 1H), 0.78 (m, 1H). LCMS (ESI) m/z=512 (M+1).
Example 5
Preparation of (±)-(E)-N-(7-((3-oxa-bicyclo[3.1.0]hexan-1-yl)methoxy)-4-(3-chloro-4-fluorophenylamino)quinazolin-6-yl)-4-(dimethylamino)but-2-enamide (5)
The title compound, (±)-(E)-N-(7-((3-oxa-bicyclo[3.1.0]hexan-1-yl)methoxy)-4-(3-chloro-4-fluorophenylamino)quinazolin-6-yl)-4-(dimethylamino)but-2-enamide (5) was prepared by the same procedures as in Example 3, except that 5a was used in place of 3a.
Example 6
Kinase Inhibition Assay
1) The compound is dissolved in DMSO to prepare a 10 mM solution, and was diluted to 100 micoM with water. When used for IC 50 measurement, series dilutions of 10 fold from 100 micoM are used. Kinase activity was determined with time-resolved Fret (TR-FRET) assay (LanthaScreen® kinase activity assay, from InVitrogen).
2) The assay is performed in a Black 384-well plate (from Corning). The kinase and the compound was incubated for 30 mM at room temperature. ATP (1 mM) and fluorescein-poly GT were added, and the reaction was incubated for 15 mM. Detection agent SA-XL665 (from Cisbio Assay) and TK Ab-Cryptate detection antibody (from InVitrogen) were added to stop the reaction.
3) The 384-well plate was sealed and incubated for 1 hour. The fluorescence was then measured at 620 nM (Cryptate) and 665 nM (XL655) wavelength.
4) Each concentration of compound was done in triplicate, and vehicle (without compound) and a positive control were used.
Data process: the ratio of fluorescence is calculated (value of fluorescence 665 nM over 620 nM). The results are calculated from: signal=compound fluorescence ratio−vehicle ratio, and the IC 50 was calculated based on inhibition curve.
The results, shown in Table 2, demonstrated that the EGFr and Her2 kinase inhibition IC 50 for compounds tested were below 100 nM.
Example 7
Cell Proliferation Inhibition Assay for BT474
1) Human breast cancer BT474 cells were plated 10000 cells/well in a 96-well clear tissue culture plate. The cells were incubated for 24 h at 37° C. to allow adherence.
2) A serials of concentrations of each compound (ranging from 30 uM to 0.16 nM, 5-fold dilution) in 96-well plate, and incubated for 72 h. Each concentration was tested in triplicate. During the cell proliferation assay, BT474 cells were cultured in the complete cell culture solution (low-glucose DMEM containing 5% FBS, 50 ug/ml gentamicin).
3) The culture medium was removed via aspiration, and the cell viability was detected by CCK-8 cell proliferation kit.
4) The EC 50 was calculated based on the proliferation curve.
The results in Table 2 show that BT474 cell growth inhibition EC 50 for compounds tested are below 100 nM.
TABLE 2
EGFR and ErbB2 (HER2) kinase inhibition, and BT474 cell
proliferation inhibition assay results.
Compound
EGFR Inhibition
HER2 Inhibition
BT474 Inhibition
Example No.
IC 50 (nM)
IC 50 (nM)
IC 50 (nM)
1
0.4
25
35.9
2
0.13
6
19.1
3
0.54
23
31.8
4
0.51
22
25.6
5
0.37
91
157
Example 8
In Vivo Efficacy in NCI-H1975 Xenograft Mouse Model
H1975 cells were purchased from ATCC were cultured in RPMI1640+10% FBS+1% P/S antibiotics. Balb/c nude mice, female, 6-8 week, 18+2 g were purchased from Shanghai Laboratory Animal Co. Ltd. The purchased mice were adapted to the environment for 7 days before use, and were housed at 22-25° C. with humidity 40-70%, and light cycle with fluorescent light for 12-hour light (8:00-20:00) 12-hour dark.
Formulation: Erlotinib, afatinib (BIBW2992), and NT112 were dissolved in 2% DMA and 98% (40% HP-β-CD in deionized water).
The cancer cells (H1975) were amplified and implanted into the nude mice (right flank) with 5.0×10 6 cells in PBS and 1:1 with matrigel in a total volume of 0.1 ml/mouse. When the tumor reaches a volume of 200 (150-200) mm 3 , the tumor-bearing nude mice derived from H1975 cells were randomly assigned into several groups (10 mice/group), Group 1 served as vehicle; Groups 2 to 5 were administrated with afatinib at 20 mg/kg (p.o. q.d.), Compound NT112 at 10 mg/kg (po, qd); Compound NT112 at 20 mg/kg (po, qd) and erlotinib at 100 mg/kg (free base, p.o. q.d.); respectively. The animals were sacrificed after 4 weeks.
The mice were monitored twice daily for appearance and behavior, and for signs of morbidity and/or mortality. The tumor volume was measured twice a week, and the body weight was measured immediately before measuring the tumor volume throughout the whole study.
At end of the experiment (compound administration for four weeks), all the tumor-bearing mice were sacrificed by cervical dislocation under deep anesthesia. The tumor mass was resected, and weighed.
Tumor sizes were measured twice weekly in two dimensions using a caliper, and the volume was expressed in mm 3 using the formula: V=½×a×b 2 where a and b are the long and short diameters of the tumor, respectively. The tumor mass was weighed at the end of the experiment after harvested.
V= ½ ×a×b 2 ( a, b is maximum and minimum diameters respectively).
RTV(Relative Tumor Volume)= Vt/Vo
Vo is the tumor volume when the test article is initial administrated Vt is the tumor volume of every measurement day after test article administration
T/C (%)=TRTV/CRTV×100%
TRTV: RTV of test article-treatment group; CRTV: RTV of control group Inhibition rate (%)=(average tumor volume of control group−average cancer volume of test article treatment group)/average tumor volume of control group×100%
Significant effective: T/C %<40%, P<0.05
Non-significant effective: T/C %>40%.
As shown in FIG. 1 , Compound NT112 in this model is significantly more effective than erlotinib; and comparable with afatinib.
Example 9
In Vivo Efficacy in NCI-N87 Xenograft Mouse Model
NCI-N87 cell line was purchased from ATCC (American Type Culture Collection) and was cultured in RPMI1640+10% FBS+1% P/S antibiotics.
Male Balb/c nude mice, 6-8 week, 18±2 g (supplier: Shanghai SLAC Laboratory Animal Co. Ltd.) were used for the experiment. The purchased mice were adapted to the environment for 7 days before use, and were housed at 22-25° C. with humidity 40-70%, and light cycle with fluorescent light for 12-hour light (8:00-20:00) 12-hour dark. The mice have free access to food and water.
The cancer cells (NCI-N87) were implanted subcutaneous into the nude mice (right flank) with 5.0×10 6 cells in 0.1 ml PBS (50 mice). When the tumor size reaches a volume of 200 (150-200) mm 3 , the tumor-bearing nude mice were randomly assigned into groups (10 mice/group), one group was served as vehicle, one group was administrated with Lapatinib ditosylate monoydrate (80 mg/kg, free base of Lapatinib, not salt, p.o. bid). The other two groups were administrated with NT112 (15 and 30 mg/kg, p.o. q.d, respectively). The administration period lasted for 4 weeks.
The mice were monitored twice daily for appearance and behavior, and for signs of morbidity and/or mortality. The tumor volume was measured twice a week, and the body weight was measured immediately before measuring the tumor volume throughout the whole study.
At end of the experiment (compound administration for four weeks), all the tumor-bearing mice were sacrificed by cervical dislocation under deep anesthesia. The tumor mass was resected, and weighed.
Tumor sizes were measured twice weekly in two dimensions using a caliper, and the volume was expressed in mm 3 using the formula: V=½×a×b 2 where a and b are the long and short diameters of the tumor, respectively. The tumor mass was weighed at the end of the experiment after harvested.
V= ½ ×a×b 2 ( a, b is maximum and minimum diameters respectively).
RTV(Relative Tumor Volume)= Vt/Vo
Vo is the tumor volume when the test article is initial administrated Vt is the tumor volume of every measurement day after test article administration
T/C (%)=TRTV/CRTV×100%
TRTV: RTV of test article-treatment group; CRTV: RTV of control group Inhibition rate (%)=(average tumor volume of control group−average cancer volume of test article treatment group)/average tumor volume of control group×100%
The tumor-bearing mice were treated for 4 weeks with different doses of NT112 (15 mg/kg, 30 mg/kg, po, qd) and Lapatinib, 80 mg/kg, p.o., bid, 7 days/week. At the day-7 after treatment, the RTV T/C NT112 (15 mg/kg, 30 mg/kg) groups were <30%, and the tumor growth inhibition was >70%, but the RTV T/C was 31% and tumor growth inhibition rat was 69% in the lapatinib group. The same result was observed as well when it comes to the tumor weight. On day 28 after treatment, all the tumor-bearing mice were sacrificed, and all the tumor masses were harvested to weigh.
Lapatinib (GlaxoSmithKline), a small-molecule kinase inhibitor of EGFR and ErbB2, led to a tumor inhibition rate of 92.9% on day 28 (the last day of the study).
NT112 treatment with 30 mg/kg, p.o., qd, 7 days/week led to body weight loss in the NCI-N87 xenograft tumor model. The body weight started to decrease in NT112-treated on the day 3 after dosing in the 30 mg/kg, p.o., qd, 7 days/week, and continued to decrease until reached the maximal body weight loss on day 11. The administration of the high dose (30 mg/kg) NT112 was stopped and never resumed. The body weight recovered to normal by day 28. The 15 mg/kg, po, qd dosing group was continued without predefined side effect. See FIG. 2 .
As used herein, the term “po”, “p.o.” or “PO”, used in combination with the term “qd” or “q.d.”, means oral administration, once a day.
Example 10
Pharmacokinetics Studies in Mice
Sample Preparation:
The test article each was dissolved in 10% DMSO and 90% of (40% HP-β-CD in deionized water) to yield concentration at 0.4 mg/mL for intravenous administration, and 1 mg/mL for oral administration.
Method development and plasma samples analysis were performed by Analytical Sciences Division of the Testing Facility by means of LC-MS/MS. The analytical results were confirmed using quality control samples for intra-assay variation (within day variation). The accuracy of >66% of the quality control samples was between 80-120% of the known value(s).
Each group is consisted 30 CD-1 mice (supplied by Sino-British SIPPR/BK Lab. Animal Ltd., Co, Shanghai), 5-8 week old, 20-28 g body weight. The test articles were administered by a single bolus intravenous injection or via oral gavage.
All animals were observed for morbidity, mortality, injury, and availability of food and water twice per day during the acclimation and study periods. Any animals in poor health were identified for further monitoring or possible euthanasia.
Blood samples (at least 300 μL/sample) were collected via cardiac puncture after euthanasia by carbon dioxide inhalation at appropriate time points for determination of the plasma concentrations of the test article. Samples were placed in tubes containing K 3 -EDTA and stored on ice until centrifuged.
Three mice in each group were used for blood collection at each of the 10 time points (Groups 1-10): Pre-dose and post-dose at 5 min, 15 min, 30 min, 1 h, 2 h, 4 h, 6 h, 8 h and 24 h.
Analysis:
The PK blood samples were centrifuged at approximately 8000 rpm for 6 minutes at 2-8° C. and the resulting plasma were separated and stored frozen at approximately −80° C. (following separation, the plasma may be initially placed on ice prior to being stored in the −80° C. freezer). All the plasma samples were labeled with detailed information such as study number, animal number, matrix, time points of collection and date of collection.
Standard set of parameters including Area Under the Curve (AUC (0-t) and AUC (0-∞) ), elimination half-live (T 1/2 ), maximum plasma concentration (C max ), time to reach maximum plasma concentration (T max ), clearance (CL), and volume of distribution (V z ) were calculated using noncompartmental analysis modules in FDA certified pharmacokinetic program WinNonlin Professional v5.2 (Pharsight, USA) by the Study Director. Furthermore, the Bioavailability was estimated using the following formula:
F
=
AUC
(
0
-
∞
)
(
PO
)
×
Dose
IV
AUC
(
0
-
∞
)
(
IV
)
×
Dose
(
PO
)
×
100
%
ABBREVIATIONS
AUC (0-t) Area under the curve from the time of dosing to the last measurable concentration
AUC (0-∞) Area under the curve from the time of dosing extrapolated to infinity, based on the last observed concentration
CL Total body clearance, CL=Dose/AUC
C max Maximum observed concentration, occurring at T max
F Bioavailability
MRT (0-∞) Mean residence time from the time of dosing to infinity
T max Time of maximum observed concentration
T 1/2 Terminal half-life=ln(2)λz
V z Volume of distribution based on the terminal phase
Mouse pharmacokinetics (PK) of NT112 (Compound 2-A) and afatinib (BIBW-2992) are shown in FIG. 3 , Panels A and B respectively; and the rat PK parameters are listed in Tables 3 and 4 respectively.
TABLE 3
Mouse PK parameters measured for Compound NT112
CL
AUC 0-t
AUC 0-∞
Plasma PK
C max
T 1/2
L/h/
V z
ng*hr/
ng*hr/
Parameters
ng/mL
hr
Kg
L/Kg
mL
mL
F %
IV 1 mg/
236
4.44
1.69
3.26
575
592
100
Kg
PO 5 mg/
272
11.1
3.40
16.4
1420
1471
49.7
Kg
TABLE 4
Mouse PK parameters measured for afatinib (BIBW-2992)
Plasma PK
C max
MRT
CL
V z
AUC 0-t
Parameters
ng/mL
hr
L/h/Kg
L/Kg
ng*hr/mL
F %
IV 1 mg/Kg
109
1.6
0.52
1.3
54
100
PO 5 mg/Kg
17.6
9.3
0.84
6.3
167
62.0
Based on the PK data generated from mouse and rat, it is likely that NT112 will have superior pharmacokinetic properties in human and other mammals, therefore possibly exhibit superior anticancer activities.
Example 11
Pharmacokinetics Studies in Rats
Sample Preparation:
The test article each was dissolved in 10% DMSO and 90% of (40% HP-β-CD in deionized water) to yield concentration at 0.4 mg/mL for intravenous administration, and 1 mg/mL for oral administration.
Method development and plasma samples analysis were performed by Analytical Sciences Division of the Testing Facility by means of LC-MS/MS. The analytical results were confirmed using quality control samples for intra-assay variation (within day variation). The accuracy of >66% of the quality control samples was between 80-120% of the known value(s).
Each group consisted 3 male Sprauge Dawley rats (7-8 week old, 200-300 g body weight). The test articles were administered by a single bolus intravenous injection via the lateral tail vein or via oral gavage.
Blood samples (approximately 300 μl) were collected via retro-orbital puncture after anaesthesia using mixed gas (CO 2 :O 2 =7:3) into tubes containing EDTA-K3 anticoagulant at appropriate time points. 10 time points (Groups 1-2): Pre-dose and post-dose at 5 min, 15 min, 30 min, 1 h, 2 h, 4 h, 6 h, 8 h and 24 h.
Analysis:
The PK blood samples were processed and analyzed using the same methods as in Example 10.
Rat pharmacokinetics (PK) of NT112 (Compound 2-A) and afatinib (BIBW-2992) are shown in FIG. 4 , Panels A and B respectively; and the rat PK parameters are listed in Tables 5 and 6 respectively.
TABLE 5
Rat PK parameters measured for Compound NT112
Plasma PK
C max
T 1/2
CL
V z
AUC 0-t
AUC 0-∞
Parameters
ng/mL
hr
L/h/Kg
L/Kg
ng*hr/mL
ng*hr/mL
F %
IV 1 mg/Kg
59.3
6.05
4.03
10.58
220
248
100
PO 5 mg/Kg
74.9
20.03
5.93
51.55
434
843
68.0
Note:
estimate of oral bioavailability may contain large uncertainty due to the flat nature of the PO data at the last three observable data points. As a comparison, if using AUC(0-t) instead of AUC(0-∞), the calculated oral bioavailability becomes 39.5%.
TABLE 6
Rat PK parameters measured for afatinib (BIBW-2992)
Plasma PK
C max
T 1/2
CL
V z
AUC 0-t
AUC 0-∞
Parameters
ng/mL
hr
L/h/Kg
L/Kg
ng*hr/mL
ng*hr/mL
F %
IV 1 mg/Kg
55.6
5.12
6.82
15.17
137
147
100
PO 5 mg/Kg
49.2
11.02
15.26
73.02
215
328
44.7
Note:
estimate of oral bioavailability may contain large uncertainty due to the flat nature of the PO data at the last three observable data points. As a comparison, if using AUC(0-t) instead of AUC(0-∞), the calculated oral bioavailability becomes 31.4%.
Compound NT112 showed higher exposure and better oral bioavailability with oral administration, compared to afatinib (bibw-2992), a structurally similar compound.
As used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural reference unless the context clearly indicates otherwise.
It is understood that aspect and variations of the invention described herein include “consisting” and/or “consisting essentially of” aspects and variations.
FURTHER EMBODIMENTS OF THE INVENTION
Embodiment 1
A compound of Formula (I):
or a stereoisomer, geometric isomer, tautomer, hydrate, solvate, polymorph, metabolite, pharmaceutically acceptable salt or prodrug, thereof, wherein:
Ar is a substituted monocyclic phenyl or monocyclic heteroaryl, optionally substituted with 0-4 groups selected from halogen, trifluoromethyl, trifluomethoxy, C 1-3 alkyl, ethynyl, ethenyl, C 1-3 alkoxyl; or O(CH 2 ) n Ar 1 , wherein n is 0 or 1;
Ar 1 is selected form monocyclic aryl or 5-6 membered heteroaryl group, and the aryl or heteroaryl may be substituted with 0-3 groups selected from halogen, trifluoromethyl, trifluomethoxy, C 1-3 alkyl, C 2-3 alkynyl,
C 2-3 alkenyl, and C 1-3 alkoxyl;
L is a bond or CH 2 ;
M is a 6-10 membered bicyclic heterocycle, containing one or more O, N, or S atoms, and the heterocycle may be further substituted with one or more halogen, C 1-3 alkyl, hydroxyl, or C 1-3 alkoxyl.
Embodiment 2
The compound of embodiment 1, wherein Ar is selected from the following structures:
Embodiment 3
The compound of embodiment 1, wherein the compound is selected from:
Embodiment 4
The compound of embodiment 1, wherein the pharmaceutically acceptable salt thereof is a salt is formed with an acid selected from: malic acid, lactic acid, maleic acid, fumaric acid, succinic acid, hydrochloric acid, methanesulfonic acid, toluenesulfonic acid, benzenesulfonic acid, sulfuric acid, phosphoric acid, citric acid, tartaric acid, acetic acid, propionic acid, caprylic, caproic acid, and benzoic acid.
Embodiment 5
A pharmaceutical composition comprising a compound of embodiment 1, or a stereoisomer, geometric isomer, tautomer, hydrate, solvate, polymorph, metabolite, pharmaceutically acceptable salt or prodrug, and a pharmaceutically acceptable carrier, excipient, diluent, adjuvant, vehicle, or a combination thereof.
Embodiment 6
Use of a compound of any one of embodiments 1-4 or a pharmaceutical composition of embodiment 5 in the manufacture of a medicament for the treatment of a receptor protein tyrosine kinase-related disease or an inhibitor of receptor protein tyrosine kinase.
Embodiment 7
The use according to embodiment 6, wherein the receptor protein tyrosine kinase-related disease, includes but not limited to: breast cancer, colorectal cancer, lung cancer, papillary carcinoma, prostate cancer, lymphoma, colonpancreatic cancer, ovarian cancer, cervical cancer, central nervous system cancer, osteogenic sarcoma, kidney cancer, liver cancer, bladder cancer, gastric cancer, head and neck squamous cell carcinoma, melanoma and leukemia.
Embodiment 8
A method for the treatment of a receptor protein tyrosine kinase-related disease comprising administering to a subject in need thereof an effective dose of a compound of embodiment 1 or a pharmaceutical composition of embodiment 5.
Embodiment 9
A method for making a compound of embodiment 1, comprising the steps of:
Step 1: reacting compound Ia with aniline to obtain compounds Ib;
Step 2: treating alcohol M-L-OH with strong base, and then adding compound Ib to obtain compound Ic;
Step 3: reducing compound Ic to produce compounds Id;
Step 4: coupling Id with acid Ie using a coupling reagent to form amide If;
Step 5: producing a compound of formula (I) by a Wittig reaction of compound If with 2-dimethylaminoacetaldehyde.
wherein:
Ar is a substituted monocyclic phenyl or monocyclic heteroaryl, optionally substituted with 0-4 groups selected from halogen, trifluoromethyl, trifluomethoxy, C 1-3 alkyl, ethynyl, ethenyl, C 1-3 alkoxyl; or O(CH 2 ) n Ar 1 , wherein n is 0 or 1;
Ar 1 is selected form monocyclic aryl or 5-6 membered heteroaryl group, and the aryl or heteroaryl may be substituted with 0-3 groups selected from halogen, trifluoromethyl, trifluomethoxy, C 1-3 alkyl, C 2-3 alkynyl, C 2-3 alkenyl, and C 1-3 alkoxyl;
L is a bond or CH 2 ;
M is a 6-10 membered bicyclic heterocycle, containing one or more O, N, or S atoms, and the heterocycle may be further substituted with one or more halogen, C 1-3 alkyl, hydroxyl, or C 1-3 alkoxyl.
Embodiment 10
The method of embodiment 9, wherein the strong base in step 2 is sodium hydride.
Embodiment 11
The method of embodiment 9, wherein the reducing in step 3 is Pt-C catalyzed hydrogenation, iron powder-acid catalyzed.
Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, it is apparent to those skilled in the art that certain minor changes and modifications will be practiced in light of the above teaching. Therefore, the description and examples should not be construed as limiting the scope of the invention.
The disclosures of all patent and scientific literature cited herein are expressly incorporated in their entirety by reference. | The invention provides quinazoline-7-ether derivatives, particularly 4-anilinyl-6-butenamido-quinazoline-7-ether derivatives that are inhibitors of the receptor protein tyrosine kinases (RTK). The compounds are useful in the treatment of diseases and disorders where RTK activity is implicated such as a hyperproliferative diseases (e.g., cancer). Also provided are methods of preparation of the quinazoline derivatives and methods of use as therapeutic agents alone or in a drug combination. | 2 |
This invention relates to polishing of thin workpieces such as silicon wafers used in semiconductors.
BACKGROUND OF THE INVENTION
In machining processes such as polishing or planarization of thin workpieces, such as silicon substrates or wafers used in integrated circuits, a wafer is disposed between a carrier or pressure plate and a rotatable polishing table carrying on its surface a polishing pad. The pressure plate applies pressure so as to effect removal of a determined amount of oxide coating and to produce a surface of substantially uniform thickness on the wafer.
Generally, the polishing apparatus includes a rigid pressure plate or carrier to which unpolished wafers are adhered, with the wafer surfaces to be polished exposed to a polishing pad which engages the same with polishing pressure. The polishing pad and carrier are then typically both rotated at differential velocities to cause relative lateral motion between the polishing pad and the wafer front side surfaces. An abrasive slurry, such as a colloidal silica slurry, is generally provided at the polishing pad-wafer surface interface during the polishing operation to aid in the polishing.
The preferred type of machine with which the present invention is used includes a rotating polishing wheel which is rotatably driven about a vertical axis. Typically, the polishing wheel comprises a horizontal ceramic or metallic platen covered with a polishing pad that has an exposed abrasive surface of, for example, cerium oxide, aluminum oxide, fumed/precipitated silica or other particulate abrasives. The polishing pads can be formed of various materials, as is known in the art, and which are available commercially. Typically, the polishing pad is a blown polyurethane, such as the IC and GS series of polishing pads available from Rodel Products Corporation of Scottsdale, Ariz. The hardness and density of the polishing pad is routinely selected based on the type of material that is to be polished. The polishing pad is rotated about a vertical axis and has an annular polishing surface on which the work pieces are placed in confined positions so that movement of the polishing wheel and the superimposed attached polishing pad relative to the work pieces brings about abrasive wear of the latter at their surfaces in engagement with said polishing surface. Of importance in all such machines is the maintenance of the polishing pad surface in planar condition and substantially free of surface irregularities. The polishing pads tend to wear unevenly in the polishing operation and surface irregularities develop therein, and these problems must be corrected.
In wafer planarization processes for oxide layer polishing, the polishing pad may too rapidly become "out of flat" by virtue of a groove called a "track" being formed in the pad. Grooving or tracking of the polishing pad is caused by the leading edge of the wafer dipping and digging into the pad. Abrasive dressing of the pad to remove the track also wears out the polish pad prematurely. In polishing silicon wafers individually secured to power driven flat platens, the wear rate of the polishing pad generally occurs farther out from the center axis.
OBJECTS OF THE INVENTION
It is therefore a principal object of this invention to provide for conditioning of polishing pads to remove surface irregularities and achieve a planar pad condition.
It is another object of this invention to minimize the need for a separate aggressive pad conditioning after each polishing operation.
A further object of the invention is to provide for better management of the polishing pad surface profile and roughness by achieving high polishing removal rates and improved removal uniformity across the surface of the wafer.
A further object of the invention is to minimize surface grooves or tracks which form in the pad due to polishing.
A further object of the invention is to control and maximize uniformity of wear of polishing pads.
A still further object of the invention is to provide consistency from polishing run to run due to the minimization of pad damage which occurs during polishing.
SUMMARY OF THE INVENTION
The present invention is directed to conditioning a polishing pad so as to control the surface profile and achieve uniformity in wear of a polishing pad by causing the workpiece and polishing pad to oscillate radially relative to one another with the extent of the oscillating movement being sufficient so that the workpiece extends over the edges of the polishing pad. The relative oscillating movement is conducted while the pad and workpiece are rotating, as is conventional.
The present invention provides a method of polishing a workpiece with a rotating polishing wheel having a polish pad thereon to improve the flatness of the surface being polished. The method comprises bringing the workpiece to be polished into contact with the polishing pad and applying pressure therebetween while both the polishing pad and workpiece are simultaneously rotated. While the pad and workpiece are rotating they are radially oscillated relative to one another to the extent that the workpiece extends over the edges of the polishing pad to avoid tracking and distribute wear over the surface of the polishing pad.
When the polishing pad is in annular form having inner edges and outer edges, the rotating workpiece is oscillated in an arc sufficient to extend over both edges. Preferably, the workpiece is oscillated so that about one-sixth of its diameter extends over the edges when the workpiece is at the extremes of oscillation.
Apparatus advantageously used for practice of the present invention comprises a rotatable polishing pad mounted over a motor driven platen and a rotatable carrier or head for carrying one or more workpieces to be polished. The carrier head is adapted for vertical movement to bring the workpiece into contact with the polishing pad and also for radially oscillating movement to an extent that a workpiece is radially oscillated over and beyond the edges of the polishing pad.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of an exemplary apparatus for practice of the invention.
FIG. 2 is a plan view of a polishing pad showing the preferred extent of radial oscillation of a 6-inch diameter workpiece being polished.
DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 illustrates the present invention and shows a workpiece 11, such as a thin silicon wafer, which is to be polished carried by a rigid head or carrier 13. Various means are known in the art for securing the workpiece to the head, including vacuum means or wet surface tension. The head 13 is attached to operating arm 16 which is adapted for vertical movement so as to raise and lower the workpiece 11 out of and into engagement with the polishing pad 18. The operating arm 16 is adapted for vertical and horizontal movement through pressure cylinder 20. Arm 16 is also adapted for oscillating horizontal movement so that the workpiece 11 traverses the entire top surface of pad 11 and extends over the inner edge 18A and outer edge 18B of the pad when at extreme limits of its arc of oscillation. The specific structure of operating arm 16 is not of concern with respect to the present invention. Operating arms which function to exert both vertical and horizontal oscillation movement are known to the art. For example, an operating arm such as arm 16 can be of the type described in U.S. Pat. No. 4,141,180.
FIG. 2 shows the preferred minimum extent of radial oscillation of a 6-inch diameter workpiece relative to the polishing pad. In this figure an annular polishing pad 18 has an overall outside diameter of 32 inches and an annular pad width of 81/2 inches, with the open center portion thus having a diameter of 15 inches. With a circular workpiece, such as a thin silicon wafer, having an outer diameter of 6 inches, the preferred radial oscillation of the workpiece is approximately 4.5 inches with the result that at the extremes of oscillation the wafer extends one inch (i.e., one-sixth wafer diameter) over the inner edge 18A and outer edge 18B of the pad,18.
It will be appreciated that during the polishing operation oscillation of the workpiece over the polishing pad is accomplished while both the workpiece and pad are rotating. Usually the pad and workpiece rotate in the same direction but at different speeds. For example, a typical preferred speed of rotation for the polishing pad is about 15 revolutions per minute and about 35 revolutions per minute for the wafer workpiece. The extent or arc of oscillation will vary depending upon the size of the workpieces and the size of the polishing pad. The extent of oscillation can be routinely determined for different size workpieces and polishing pads so as to achieve the requirement that the rotating workpiece be oscillated a sufficient amount so as to exceed or extend over the edges of the polishing pad. Workpieces such as silicon wafers having diameters of 6, 8, 10, etc. can be polished according to this invention.
The invention is applicable to operations wherein a plurality of wafers are polished simultaneously. This is accomplished by securing the wafers to a carrier or head which is movable both vertically and horizontally. Apparatus of this type is known to the art and described, for example, in U.S. Pat. No. 4,239,567 and U.S. Pat. No. 5,329,732 which discloses the polishing of five wafers simultaneously.
In cases where the polishing pad is badly worn with undesired tracks therein, conditioning of the pad can be accomplished by this invention. This is accomplished by securing the carrier head 13 to operating arm 16 through a self-aligning bearing which permits the head to swivel and cause the leading edges of the workpiece to dip and dig into the polishing pad so as to eventually eliminate the tracks or grooves therein. U.S. Pat. No. 4,270,314 is exemplary of known prior art for swivel mounting of a pressure plate.
Practice of the present invention significantly extends the life of polishing pads. By maintaining the desired flatness of the pads and avoiding the formation of tracks therein, the uniformity of the polishing operation is significantly improved and removal of material from the workpiece is achieved at predictable rates.
Those modifications and equivalents which fall within the spirit of the invention are to be considered a part thereof. | Conditioning of a polishing pad so as to control the surface profile and achieve uniformity in wear of a polishing pad by causing the workpiece and polishing pad to oscillate radially relative to one another with the extent of the oscillating movement being sufficient so that the workpiece extends over the edges of the polishing pad. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS AND PATENT
This application is related to copending U.S. application Ser. No. 07/132,790, filed Dec. 10, 1987, entitled "TREATMENT OF COTTON", and which application is a divisional application to U.S. application Ser. No. 06/833,987, filed Feb. 26, 1986, entitled "TREATMENT OF COTTON", now U.S. Pat. No. 4,796,334, granted Jan. 10, 1989, which is related also to copending U.S. application Ser. No. 07/207,252, filed June 15, 1988, entitled "TREATMENT OF COTTON", and which application is a continuation application to the aforementioned parent application, namely U.S. application No. 06/833,987. This application is also related to the commonly assigned U.S. application Ser. No. 07/359,495, filed May 31, 1989, and entitled "METHOD OF AND APPARATUS FOR TREATING COTTON CONTAMINATED WITH HONEYDEW" and also related to the commonly assigned, copending U.S. application Ser. No. 07/363,784 filed June 9, 1989, entitled "METHOD OF AND APPARATUS FOR REDUCING THE STICKINESS OF THE FIBERS OF COTTON FLOCKS CONTAMINATED WITH HONEDEW".
BACKGROUND OF THE INVENTION
The present invention broadly relates to treating contaminated cotton fibers or flocks when such are being continuously processed and, more specifically pertains to a new and improved method of reducing the stickiness or tackiness of the fibers of cotton flocks contaminated with honeydew. The present invention also relates to a new and improved apparatus for reducing the stickiness or tackiness of the fibers of cotton flocks contaminated with honeydew.
Generally speaking, the present invention relates to a new and improved method of the aforementioned type and which method entails heating the cotton flocks for a brief period of time.
It is known that cotton flocks of many provenances or origins are more or less contaminated with insect secretions which contain sugar. These sugar-containing secretions are generally termed "honeydew". There is known a laboratory method by means of which such honeydew is allowed to caramelize by heating cotton flock samples or specimens in an oven with the aim of thereby producing a discoloration or change of color of the cotton, in order to determine the degree of contamination thereof with honeydew from the resulting change in the color of the cotton flocks. This is namely very important because, in the event of heavy contamination of the cotton flocks, the cotton flocks become sticky and tend to adhere to various parts of the yarn production plant or to form laps or coils at rolls or rollers or at other rotatable members. This result is very undesirable since it causes frequent interruptions of the yarn manufacturing process.
A method of the aforementioned type is disclosed in European Patent Application No. 86102352.1, published Oct. 8, 1986, under Publication No. 196,449. The object of this known method is to convert any contaminating honeydew into a non-tacky or non-adhesive and brittle state or condition by supplying heat for a short period of time, but without causing any discoloration or change of color of the cotton flocks, so that the brittle sugar or caramellized deposits can be crushed and removed in the course of the subsequent treatment.
A number of devices or apparatus for performing this prior art method have been proposed in the abovementioned European Patent Application No. 86102352.1, published under Publication No. 196,449. The object of one disclosed device or apparatus is to heat the cotton flocks already in the course of opening the raw cotton bales, i.e. directly at the start of the yarn manufacturing process. Other devices or apparatus are intended for treating fiber slivers before drafting.
SUMMARY OF THE INVENTION
Therefore, with the foregoing in mind it is a primary object of the present invention to provide a new and improved method of reducing the stickiness or tackiness or adhesiveness of the fibers of cotton flocks, which method can be performed or applied at any processing or treatment stage of the cotton flocks, i.e. during ginning and cleaning as well as before carding and drafting.
Another and more specific object of the present invention aims at providing a new and improved method of reducing the stickiness or tackiness of cotton flocks and by means of which a uniform and rapid heat transfer into the fiber batt is attainable and detrimental or undesired effects of uncontrolled heating are obviated.
Now to implement these and still further objects of the invention, which will become more readily apparent as the description proceeds, the method of the present invention of reducing the stickiness or tackiness of the fibers of cotton flocks contaminated with honeydew is manifested, among other things, by the steps of pressing together the cotton flocks to form a fiber batt or web or the like, then guiding such fiber batt over at least three and preferably five rotating heated rolls or rollers and clamping the fiber batt therebetween. The fiber batt is continuously moved and subsequently opened again into fiber flocks, such fiber flocks being transferred to an immediately following unit which conveys or processes the fiber flocks.
As alluded to above, the invention is not only concerned with the aforementioned method aspects, but also relates to a new and improved construction of apparatus for carrying out the inventive method.
To achieve the aforementioned measures, the inventive apparatus, in its more specific aspects, among other things, comprises a fiber feeding device by means of which the fiber flocks are compressed into a fiber batt or web and fed in this condition or form to a plurality of heatable rolls or rollers following thereupon. Downstream of such heatable rolls or rollers, as viewed in the conveying direction of the fiber batt or web, there are provided opening and infeeding means for opening the fiber batt or web again into fiber flocks and infeeding such fiber flocks to fiber conveyor means.
The inventive method of reducing the stickiness or tackiness of cotton flocks and the apparatus constructed according to the invention are based on the finding that the amount of heat that can be applied to or brought into a fiber batt or web at a press nip or clamping location between two heatable rolls or rollers or at locations directly upstream or directly downstream of the press nip or clamping location is far greater than the amount of heat that can be applied to or brought into the very same fiber batt or web, when the latter simply embraces or wraps around a heated roll or roller.
This is due not only to the fact that the fiber batt or web in the press nip or clamping location is heated from both sides, but rather also due to the fact that the conductivity of the fiber batt or web in the compressed state is higher, by virtue of the reduction of the amount of air contained in the fiber batt or web, than in a fiber batt or web which is only wrapped around a heated roll or roller and thus freely exposed on one side.
According to the invention, the best results are obtained when cotton in the press nip or clamping location of the rolls or rollers is compressed to a density of 100 to 400 kg/m 3 , preferably about 250 kg/m 3 .
A particularly preferred variant of the method according to the invention comprises the steps of applying at least one belt or band which revolves around at least two rotating heated rolls or rollers, providing at least one further rotating heated roll or roller forming press nip or clamping locations with the at least two rotating heated rolls or rollers, and clamping the fiber batt or web against the at least one further rotating heated roll over a part of the surface thereof. The resulting improvement in heat transfer is due to the fact that the length of the press nip or clamping location is artificially extended or enlarged by the revolving belt or band.
A further particularly preferred variant of the method according to the invention comprises the step of at least partially exposing or laying bare at least one surface of the fiber batt or web, preferably the upper or top surface thereof, to allow water vapor to escape during the heating operation. If this step is omitted and no provision is made for the vapors generated during the heating process to escape, there is the risk of the cotton flocks remaining sticky or tacky even after the heat treatment has been effected.
In a preferred embodiment of the apparatus constructed according to the invention for reducing the stickiness or tackiness of the fibers of cotton flocks, the plurality of heatable rolls or rollers are arranged in a preferably ascending chimney or flue through which an air current or flow is effected by means of a blower or fan. In this manner, any generated vapors are sucked out or blown away.
The chimney is preferably located between a flock feed chute and an opening roll or roller which opens the fiber batt or web into fiber flocks. Such an arrangement renders possible the space-saving and economical integration of the inventive apparatus in an existing feeder of a card or carding machine.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein throughout the various figures of the drawings, there have been generally used the same reference characters to denote the same or analogous components and wherein:
FIG. 1 shows a schematic side view of an exemplary embodiment of the inventive apparatus for reducing the stickiness or tackiness of cotton flocks;
FIG. 2 schematically shows a side view of a modified embodiment of the heatable rolls or rollers of the apparatus illustrated in FIG. 1;
FIG. 3 schematically shows a side view of a further embodiment of heatable rolls or rollers which can be used instead of the heatable rolls or rollers in the exemplary embodiment of the inventive apparatus illustrated in FIGS. 1 and 2; and
FIG. 4 schematically shows a variant of the apparatus illustrated in FIG. 1.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Describing now the drawings, it is to be understood that to simplify the showing thereof, only enough of the structure of the apparatus for realizing the inventive method of reducing the stickiness or tackiness of the fibers of cotton flocks contaminated with honeydew or the like has been illustrated therein as is needed to enable one skilled in the art to readily understand the underlying principles and concepts of the present invention. Turning attention now specifically to FIG. 1 of the drawings, the apparatus illustrated therein by way of example and not limitation will be seen to comprise a lower or bottom part of a flock chute or shaft 11 such as is normally used upstream of a card or carding machine. At the lower end of this flock chute or shaft 11, which is disposed in a flock chute housing 12, there are arranged two take-up or delivery rolls or rollers 13 and 14. While the axis of rotation of the take-up or delivery roll or roller 14 is fixedly arranged in space, the axis of rotation of the other take-up or delivery roll or roller 13 is displaceable in the direction of the double-headed arrow 15, in order to adjust the desired thickness of a fiber feed or fiber batt.
A further rotatable roll or roller 16 is provided upstream of the take-up or delivery roll or roller 13 and is arranged in spaced relationship with respect to the take-up or delivery roll or roller 14. This further rotatable roll or roller 16 performs a guide function for the cotton flocks in the flock chute or shaft 11. A fiber batt or web 17 produced by the take-up or delivery rolls or rollers 13 and 14 is conducted, instantly downstream of the take-up or delivery rolls 13 and 14, between clamping means and a counter element here shown as two clamping rolls 18 and 19 which serve to clamp the fiber batt or web 17 in the event of any interruption or stoppage of the manufacturing process and thus prevent any further conveyance of cotton flocks. The take-up or delivery rolls 13 and 14 are stopped during this operation.
In normal operation, the fiber batt or web 17 then passes on through an exit slot or opening 21 located at the bottom end of the flock chute housing 12 and over a guide plate 22 to an arrangement or array of heatable rolls or rollers. This heatable roll arrangement or array here comprises, for instance, five individual heatable rolls or rollers 23, 24, 25, 26 and 27 which are alternately arranged in a downwardly inclined row on both sides of the fiber batt or web 17. All five heatable rolls or rollers 23 through 27 are driven so that the fiber batt or web 17 is drawn or pulled through the rolls or rollers 23 through 27.
As will be apparent from FIG. 1, four press nip or clamping locations 28, 29, 31 and 32 are provided between the five heatable rolls or rollers 23 through 27. These four press nip or clamping locations 28, 29, 31 and 32 preferably have a press nip or clamping width of 4 mm or less. Before entering the press nip or clamping location 28, the fiber batt or web 17 on the guide plate 22 has a thickness of about 100 mm. Therefore, the fiber or flock batt or web 17 undergoes a 20 to 25 times compression in the press nip.
Between the heatable rolls or rollers 23 through 27 and downstream of the heatable roll or roller 27 there are free or exposed regions or areas 33, 34, 35 and 36 of the fiber batt or web 17 where the vapors produced by the heating operation can escape. This can be assisted by an air current or flow 37 produced by a suitable blower or fan which is not particularly shown in the drawing, but which could be, for instance, flanged at a pipe connection or spigot 40. This pipe connection or spigot 40 is located at the top or upper end of a chimney or flue 38 in which the heatable roll or roller arrangement or array is accommodated. This chimney 38 vertically extends or ascends between the flock chute or shaft 11 and a feeding device or system for a card or carding machine.
After leaving the last heatable roll or roller 27, the compressed and heated fiber batt or web 17 passes over a guide plate 39 to an opening roll or roller 41 of an infeeding or infeed device 56. Here, the fiber batt or web 17 is again opened into individual cotton flocks, which are blown or sucked into a rising or ascending line or conduit 42 which finally leads to a subsequent machine in the ginning process or in the cleaning department of the spinning mill. A line or conduit 43 serves to admit or allow for the ingress of an air current or flow substantially tangentially in the direction of movement of the opening roll or roller 41, in order to promote the pneumatic conveyance or transport of the loosened cotton flocks in a line or conduit 42. The opening roll or roller 41 is located at the lower or bottom end of a separating or partition wall 60 which forms a lateral or side wall of the chimney 38.
FIG. 2 shows a modified embodiment of the heatable roll or roller arrangement or array of FIG. 1 in which a revolving belt or band 44 wraps around the three heatable rolls or rollers 23, 25 and 27 arranged below the fiber batt or web 17. This revolving belt or band 44 is driven at the same speed as the circumferential speed of the heatable rolls or rollers 23 through 27, either by the heatable rolls or rollers 23 through 27 themselves or by a driven deflection roll or roller 45. Two further deflection rolls or rollers 46 and 47 as well as a tension roll or roller 48 provide uniform movement or travel of the revolving belt or band 44 and the desired or required tension of such revolving belt or band 44. Extended press nip or clamping locations or zones 49 and 51 between the revolving belt or band 44 and the top or upper heatable rolls or rollers 24 and 26, respectively, are formed by the revolving belt or band 44.
In this embodiment, the tension of the revolving belt or band 44 is selected such that the fiber batt or web 17 in the press nip locations or clamping locations or zones 49 and 51 has a thickness of about 4 mm or less. The revolving belt or band 44 is preferably made of metal and is itself heated by the heatable rolls or rollers 23, 25 and 27 so that the heat input or transfer into the fiber batt or web 17 is accomplished from both sides.
FIG. 3 shows a further possibility of heating a fiber batt or web 17 in the clamped condition or state thereof. Four rotating heatable rolls or rollers 23.1, 24.1, 27.1 and 26.1 are provided. The revolving belt or band 44 passes over the first rotating heatable roll or roller 23.1, beneath the second rotating heatable roll or roller 24.1, over the third rotating heatable roll or roller 27.1 and then over two deflection rolls or rollers 45 and 46. Also in this case, there is provided a tension roll or roller 48. Above the second rotating heatable roll or roller 24.1 there is located the fourth rotating heatable roll or roller 26.1 which forms two press nip or clamping locations 28.1 and 32.1 with the surfaces of the two lower rotating heatable rolls or rollers 23.1 and 27.1 or with the surface of the revolving belt or band 44 wrapped around these two lower rotating heatable rolls or rollers 23.1 and 27.1, respectively. The fiber batt or web 17 runs over the guide plate 22, beneath a stationary guide or guide member 52 and through the press nip or clamping location 28.1, then along a further stationary guide or guide member 53, over the surface of the rotating heatable roll or roller 24.1 while being clamped by the revolving belt or band 44, past a stationary guide or guide element 54, through the press nip or clamping location 32.1 and finally beneath a further stationary guide or guide member 55 to the guide plate 39. The heated fiber batt or web 17 then passes to the opening roll or roller 41.
In this embodiment, the fiber batt or web 17 is heated over a considerable length in the clamped state or condition by means of just four rotating heatable rolls or rollers. The stationary guides or guide members 52 and 55 can also be replaced by rotatable guide rolls or rollers 57 and 58 or by a further revolving belt or band 59 which is guided or trained around the corresponding heatable rolls or rollers and guide rolls or rollers 57, 23.1, 24.1, 27.1, 58 and 26.1. The guide roll or roller 57 or the guide roll or roller 58 can be provided as a tension roll or roller.
It should be mentioned that the described apparatus or installations use heatable rolls which are heated to a temperature of about 220° C. Heating can be accomplished by means of oil, steam, electric current or any other heat source capable of supplying the required amount of heat in the required time. The fiber batt or web 17 moves through the plant or installation at a speed of between 0.02 m/sec and 0.1 m/sec. If the cotton being processed is not contaminated with honeydew, the heating can be simply turned off or the entire plant or installation can be by-passed.
FIG. 4 shows a variant of the apparatus of FIG. 1 inasmuch as a cooling zone or area 70 is provided between the chimney or flue 38 and the infeeding device 56, in order to cool the heated fiber batt or web 17 between two cooling conveyor belts or bands 71 and 72.
The cooling zone or area 70 is separated, by a separating or partition wall 60.1 and by a separating or partition wall 73 arranged opposite thereto, from the chimney 38 and from the region or area containing the infeeding device 56. The separating or partition walls 60.1 and 73 shown in FIG. 4 are of course closed by two end sides or walls to form a closed room or space.
On the other hand, these end sides or walls not particularly designated by reference characters in the drawing of FIG. 4 are provided with air inlet openings (not shown) to admit an air flow or current L which, for the purpose of cooling the fiber batt or web 17 located between the two cooling conveyor belts or bands 71 and 72, flows, for instance, substantially perpendicular through these two cooling conveyor belts or bands 71 and 72 which consist of lattice work or mesh structure. The air flow or current L is generated by a suitable suction fan (not shown), which is connected to a connection pipe or spigot or stud 74. The airflow or current L should have a relative air humidity which is able to absorb humidity from the fiber flocks.
The cooling conveyor belts or bands 71 and 72 are synchronously driven by a suitable single drive not particularly shown in the drawing of FIG. 4 and convey the fiber batt or web 17 at the outlet speed thereof prevailing in the press nip or clamping location 32 between the two last heated rolls or rollers 26 and 27.
It is readily conceivable that the fiber flocks can also be cooled in the next following unit for conveying or otherwise acting upon the fiber flocks, such unit being arranged downstream of the opening roll 56.
Finally, reference is made to the stripping or stripper knives 75 which are provided at the rolls or rollers or at the conveyor belts or bands for the purpose of removing or picking up any honeydew deposits. These stripping or stripper knives 75 can also be heated to effect a caramelization of the honeydew adhering thereto.
While there are shown and described present preferred embodiments of the invention, it is to be distinctly understood that the invention is not limited thereto, but may be otherwise variously embodied and practiced within the scope of the following claims. Accordingly, | The invention relates to a method of reducing the stickiness or tackiness of cotton flocks. For this purpose, cotton flocks delivered by any suitable conveyor mechanism are received in a flock chute and brought, by rolls or rollers, as a fiber batt between a number of heated rolls or rollers, in order to be heated such that the stickiness or tackiness of the honeydew on the cotton is thus reduced to an extend which no longer has an adverse effect on subsequent machinery. Downstream of the heated rolls or rollers the fiber batt is again opened into cotton flocks by an opening roll or roller and fed to a pneumatic conveyor line through which the cotton flocks are fed to the subsequent machine. | 3 |
TECHNICAL FIELD
[0001] The present invention relates to cellular communication devices. The invention has particular relevance to cellular devices that operate in accordance with the ETSI and 3GPP standards, such as the GSM standards, UTRAN standards and the Long Term Evolution (LTE) of UTRAN (called Evolved Universal Terrestrial Radio Access Network (E-UTRAN)) standards.
BACKGROUND ART
[0002] There are a number of different cellular telephone standards, such as GSM, UMTS, LTE that define different operating frequencies and protocols to allow user equipment (UE), such as a mobile telephone, to communicate with other user equipment via the telephone network. Many UEs are able to operate using a number of these different standards and typically will connect with the network node that provides the best signal strength and the best service level. However, as the UE moves, it has to handover to a different network node, which may operate using a different technology. For example, the UE may initially be connected with an LTE network node and may move out of coverage of that node into the cell coverage of a UMTS network node. Such handover is called “inter-RAT” handover as the UE changes the Radio Access Technology (RAT) during the handover. According to the current 3GPP standards, it is the responsibility of the network nodes to determine when a UE should handover to another network node. The network node makes this decision based on measurements provided by the UE for a number of candidate neighbouring cells (defined in a neighbour cell list) provided to the UE by the network node.
[0003] With the number of different technologies supported within a single phone on the increase (i.e. three or more), the task of managing inter-RAT measurements gets ever more complex. The current principle is that the network is all knowing (it knows the theoretical capabilities of the UE and its current state in sufficient detail). So the network should be able to manage traffic gaps (directly or indirectly, according to the technology) to allow inter-RAT measurements to be made by the UE. Moreover, the network assumes that the UE is able to act as planned and expects results within a certain timeframe.
[0004] Thus, when the network requires a UE to make inter-RAT measurements, it may define the measurements to be made and set up periodic reporting. In response, the UE makes the measurements during the managed gaps and then in due course, the UE sends measurement reports. It may:
report some measurements;
in which case the network might assume that more measurements will be coming, if the report is incomplete (i.e. some cells have not been measured yet).
report no measurements;
in which case the network might assume that the UE has completed all its measurements (i.e. any missing cell in the reports is invisible to the UE).
[0007] However, the inventors have realized that these assumptions made by the network are problematic and could be wrong and it may be a waste of effort to try and achieve absolute mastery of the UE's real-time state and capability. For instance the reporting interval provision might have been inappropriate for the UE's actual capabilities and circumstances on the current RAT and the UE might have been unable to do any measurements at all, without that implying that the measurements are complete (i.e. that it definitely cannot use any of the neighbouring cells). This problem could be solved by the network defining a relatively long reporting interval, but this is inefficient.
SUMMARY OF THE INVENTION
[0008] According to one aspect, a preferred embodiment provides new signalling in measurement reports, allowing the UE to indicate explicitly whether or not more measurements are to be expected (e.g. a continuation flag) or that network provisions are inadequate. That way, the network need not make assumptions one way or the other and, in the case where the UE is signalling that measurements are not complete, yet is not reporting any measurements, the network might then conclude that its gap scheduling policy or the defined measurement interval requires adjustment, at least with respect to that particular UE.
[0009] A cellular communications system is provided in which a mobile cellular device is configured to return status data to the network when instructed to obtain cell measurements. When used (the status data may not be needed, for example if the measurements can be completed and reported as requested), the status data may indicate that measurements are in hand and that further measurement reports may or will follow. The status data may also indicate if the reporting interval and/or the measurement gaps defined by the network are suitable to make the measurements given the current status of the mobile device. A network node is also provided that can receive the measurement reports and interpret the status data to decide to wait for further measurement results or to issue a new reporting interval or a new cell list or arrange a new configuration of idle gaps in which cell measurements may be made.
[0010] According to one aspect, the invention provides a cellular communications device comprising: means for receiving a measurement control command including a neighbour cell list; means for determining a suitability of network provisions for making the measurements in dependence upon a current status of the cellular communications device; and means for generating a measurement report including measurement status data indicative of the status of the requested measurements or indicative of the suitability of the network provisions.
[0011] The first measurement report may include cell measurements as well as the status data. However, the report may be sent before the first measurement opportunity defined by the reporting interval, especially if the status data indicates that the reporting interval is not suitable for the device.
[0012] The reported status data may include binary flags or enumerated values that indicate whether or not all cells that can be reported have been reported and whether or not more cells may or will be reported at a subsequent reporting opportunity. The status data may include data indicating that more cells may be reported but that the reporting interval makes for inefficient operation.
[0013] The status data may include data indicating whether or not the device can perform the requested measurements by a first reporting time defined by the reporting interval or data indicating whether or not measurement gaps are too short and/or too close to other reserved resources.
[0014] The status data may include data indicating an estimated time for completing the measurements or data indicating a minimum reporting interval required to enable efficient measurements.
[0015] According to another aspect, the invention provides a network communications node operable to communicate with one or more cellular communication devices, the network communications node comprising: means for outputting a measurement control command including a first neighbour cell list to a cellular communication device; means for receiving a measurement report from the mobile communications device, the measurement report including measurement status data indicative of the status of the requested measurements or indicative of the suitability of network provisions for the measurements; and means for determining whether to wait for one or more further measurement reports or to determine new network provisions in dependence upon said status data.
[0016] If the status data indicates that cell measurements may or will be reported at a subsequent reporting opportunity then the determining means determines to wait for one or more further measurement report. However, if the status data includes data indicating that more cells may be reported but that the measurement gap makes for inefficient operation or that the measurement gaps are too short and/or too close to other reserved resources, then the determining means is operable to determine a new measurement gap pattern for the cellular device.
[0017] If the status data includes data indicating a minimum measurement gap required to enable efficient measurements, then the network node may determine if a different measurement gap can be defined. The measurement gap can be signalled explicitly to the cellular device or it may be implicitly provisioned by the network node through defined idle times.
[0018] In response to receiving a measurement report known to be final (as indicated in the status data from the cellular device), the network node will determine whether or not to generate a new measurement command with a new cell list or whether to handover to another cell.
[0019] The innovation applies primarily when a UE supports handovers between two or more access technologies (RATs). It applies when handover from one or any of the access technologies is controlled by the network after obtaining neighbour cell measurements from the UE which may be specified in terms of cells to report on and when to report results. The invention therefore applies to, among others, GSM and its derivatives, UMTS and its derivatives and LTE and its derivatives.
[0020] In some embodiments, more values are defined so that the UE may provide more information with an empty report or even with non-empty reports (meaning with or without any measurement results). For example:
a flag may be provided that indicates whether or not the network provisions for the inter-RAT measurements are sufficient. Obviously such a flag is not needed in a non-empty report, as provisions are then clearly adequate. However, in an empty report, a negative value may be used to imply that the UE requires a different gap pattern to provide any measurement at all. There is still some ambiguity in this case since a positive value in an empty report can be interpreted in two ways: a) the UE did not manage any complete measurement by this reporting opportunity, but non-empty reports are to be expected eventually, however slowly, as the gap pattern is deemed acceptable by the UE; or b) the UE has indeed nothing to report. a flag may be provided that indicates whether or not measurements are complete. That is whether the network should expect any more, but not qualifying the scheduling policy. In a non-empty report, the flag is unambiguous: it signals the end of a measurement cycle (further reports will relate to cells already reported) even if not all the required cells could be measured. In an empty report, a positive value signals that there is nothing to report, but a negative value could be interpreted in two ways: a) further measurements will eventually be reported; or b) the UE cannot use the current gap pattern. A flag may be provided that has three states (resolving the ambiguities noted above): “all measurements done” (report may or may not be empty); “more measurements to be expected” (report may or may not be empty); and “please provide a different gap pattern” (the report should logically be empty).
[0024] Alternatively, the notions of measurement completeness and gap pattern adequateness could be reported via independent flags.
[0025] In a further embodiment, in addition to the options above, a further value may be provided indicating an estimate of how many more reporting opportunities will be required to complete the current cycle of measurements, including a value signifying that the UE cannot estimate the end of the current measurement cycle.
[0026] In one embodiment, the “all measurements done” value, or another value, could also be used by the UE to signify that it has decided not to measure any further cells.
[0027] Whilst such measurement reporting is typically carried out on a periodic basis, the concept could be extended to non-periodic reporting. For example, the UE might decide to report a partial set of measurements and indicate that it intends to send more. The UE can then send the other results at an appropriate time outside the normal periodic reporting interval and the network will wait for the next report.
[0028] The present invention also provides corresponding methods and a computer implementable instructions product comprising computer implementable instructions for causing a programmable computer device to become configured as the above mobile device or as the above network node. The product may include a computer readable medium or a signal that carries the instructions.
[0029] These and various other aspects of the invention will become apparent from the following detailed description of embodiments which are described, by way of example only, with reference to the accompanying Figures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] FIG. 1 schematically illustrates a mobile telecommunication system of a type to which the embodiment is applicable;
[0031] FIG. 2 is a block diagram illustrating components of a network base station forming part of the system shown in FIG. 1 ;
[0032] FIG. 3 is a block diagram illustrating components of a mobile communication device forming part of the system shown in FIG. 1 ;
[0033] FIG. 4 is a timing diagram illustrating the data flow between the mobile communication device and the base station shown in FIG. 1 .
DESCRIPTION OF EMBODIMENTS
(Overview)
[0034] FIG. 1 schematically illustrates part of a mobile (cellular) telecommunications system 1 having a mobile telephone 3 , three radio access networks 5 - 1 , 5 - 2 and 5 - 3 and corresponding core networks 7 - 1 , 7 - 2 and 7 - 3 . Each of the radio access networks 5 operates to communicate with mobile telephones 3 within a respective cell, which are illustrated in FIG. 1 by the dashed circles labelled C 1 , C 2 and C 3 respectively. In this embodiment, radio access network 5 - 1 is an E-UTRAN access network, radio access network 5 - 2 is a UMTS access network and radio access network 5 - 3 is a GSM access network. In this embodiment, the mobile telephone 3 is a multi-RAT device that can connect or communicate with E-UTRAN cells, UMTS cells and GSM cells. In the illustrated Figure, the mobile telephone 3 is within the all of the cells and so can therefore connect with any of the three radio access networks 5 to be able to communicate with other users (not shown) via the selected radio access network 5 , its associated core network 7 and the telephone network 9 .
(Radio Access Network)
[0035] Although each radio access network 5 may operate a number of different cells, each providing different services to the mobile telephone 3 , in this embodiment it will be assumed, for simplicity, that each radio access network 5 operates a single cell. In the case of E-UTRAN, the radio access network 5 - 1 is foamed by a base station (referred to as an eNodeB or just eNB) and it is the base station's responsibility to instruct the mobile telephone 3 to make the cell measurements so that it can make the appropriate handover decision. In other radio access networks the responsibility for instructing the mobile telephone 3 to perform the cell measurements may fall to some other network node in the radio access network or in the core network 7 . For ease of description, however, in this embodiment, it will be assumed that the mobile telephone 3 is associated with the E-UTRAN base station 5 - 1 and the main components of this base station 5 - 1 are illustrated in FIG. 2 . As shown, the base station 5 - 1 includes a transceiver circuit 21 which is operable to transmit signals to and to receive signals from the mobile telephone 3 via one or more antennae 22 and which is operable to transmit signals to and to receive signals from the core network 7 - 1 via a core network interface 23 . The base station 5 - 1 also includes a controller 25 which controls the operation of the base station 5 - 1 in accordance with software stored in memory 27 . The software includes, among other things, an operating system 31 , a handover module 32 and a report module 33 . The handover module 32 is operable to control the handover of the mobile telephone 3 to another cell. The report module 33 is operable to command the mobile telephone 3 to perform the desired inter-RAT measurements and to provide those measurements to the base station 5 - 1 within a defined time, so that this information can be used by the handover module 32 to identify the best target cell for the handover.
[0036] The memory 27 also stores various data including neighbour cell data 34 and mobile telephone (MT) capability data 35 . The report module 33 uses the neighbour cell data 34 to identify to the mobile telephone 3 the cells for which measurements are to be obtained. The report module 33 uses the MT capability data 35 to calculate an appropriate reporting interval by which the mobile telephone 3 is expected to provide a measurement report.
(Mobile Telephone)
[0037] FIG. 3 schematically illustrates the main components of the mobile telephone 3 shown in FIG. 1 . As shown, the mobile telephone 3 includes a transceiver circuit 71 that is operable to transmit signals to and to receive signals from a radio access network 5 via one or more antennae 73 . As shown, the mobile telephone 3 also includes a controller 75 which controls the operation of the mobile telephone 3 and which is connected to the transceiver circuit 71 and to a loudspeaker 77 , a microphone 79 , a display 81 , and a keypad 83 . The controller 75 operates in accordance with software modules stored within memory 85 . As shown, these software modules include, among other things, an operating system 87 , a measurement module 89 and a reporting module 91 . In response to receiving a command from the base station 5 - 1 , the reporting module 91 is operable to make the measurement module 89 obtain the desired measurements and to send the measurements to the radio access network 5 . The memory 85 also stores a neighbour cell list 93 that is received from the radio access network 5 . The measurement module 89 uses the neighbour cell list 93 to identify the cells for which measurements are to be obtained and the report module 91 sends one or more reports to the radio access network 5 to report the measurements that have been obtained. As will be described in more detail below, in this embodiment, the report module 91 also determines and sends feedback information to the radio access network 5 to help the radio access network 5 draw the correct conclusions when interpreting the measurement reports received from the mobile telephone 3 .
[0038] In the above description, both the base station 5 - 1 and the mobile telephone 3 are described, for ease of understanding, as having various discrete software modules. Whilst these software modules may be provided in this way for certain applications, for example where an existing system has been modified to implement the invention, in other applications, for example in systems designed with the inventive features in mind from the outset, the functionalities of these modules may be performed by a single module or they may be built into the overall operating system or code and so these modules may not be discernible as discrete entities.
(Operation)
[0039] The operation of the present embodiment will now be illustrated through a discussion of an example scenario that is given with reference to the timing diagram shown in FIG. 4 . As shown, the process starts when the base station 5 - 1 sends, in step s 1 , the mobile telephone 3 a measurement control command asking the mobile telephone 3 to report to it at one or more specified reporting times (specified in the command by a reporting interval—reporting_interval) with measurements for neighbouring cells (specified in the command—nc_list). The base station 5 - 1 determines the reporting interval based on the capability data 35 it has stored for the mobile telephone 3 and it determines the cells to include in the neighbour cell list based on its stored neighbour cell data 34 . In response to receiving this command, the mobile telephone 3 records the reporting interval and stores the neighbour cells as the current cell list 93 . In this example, as illustrated at step s 3 , at the time that this command is received by the mobile telephone 3 , the telephone 3 is busy (for example the base station 5 - 1 may have provided a reporting interval which is too close to a Multimedia Broadcast Multicast Service (MBMS) resource which the user of the mobile telephone 3 has unilaterally selected, so it cannot make full use of the reporting interval due to frequency switching delays) and so is unable to obtain all the desired measurements and report them to the base station 5 - 1 by the first reporting opportunity. Therefore, in this illustration at the first reporting opportunity the mobile telephone 3 sends, in step s 5 , a report with no measurements, but with a flag indicating that “more” measurements may follow. In step s 7 , the base station 5 - 1 identifies the “more” flag contained in the report and interprets it to mean that measurements may be sent. Therefore, the base station 5 - 1 decides to do nothing and to wait until the next reporting opportunity before making any further decisions for this mobile telephone 3 . At the next reporting opportunity, at step s 9 , the mobile telephone 3 has some (but not all) of the measurements to report and so prepares and sends another measurement report that includes the available cell measurements and another “more” flag, indicating that more measurements may still be reported.
[0040] At step s 11 , the base station 5 - 1 receives the second measurement report and stores the measurements contained therein. The base station 5 - 1 again identifies and interprets the “more” flag and again waits until the next reporting opportunity before making further decisions for this mobile telephone 3 . In step s 13 , the mobile telephone 3 sends a final measurement report to the base station 5 - 1 . The mobile telephone 3 identifies the report as being the final one in respect of the received command by including a “finished” flag in the report together with the final measurements. (If the command is a request for periodic reports, then this “final” report may not actually be final, just the last one for the current cycle.) In step s 15 , the base station 5 - 1 stores the final measurements and interprets the “finished” flag to mean that the mobile telephone 3 has finished sending (in the current cycle) measurement reports for the cells listed in the neighbour cell list sent by the base station in step s 1 . The base station 5 - 1 then processes the stored measurements and determines if it should wait for another measurement cycle; or if a new cell list should be sent to the mobile telephone 3 ; or if a handover should be performed and if so, with which target cell.
[0041] Thus the embodiment above allows the mobile telephone 3 to provide some feedback on the status of its measurements at measurement reporting opportunities, with or without any measurements, which may be incomplete.
(Advantages of the Embodiment)
[0042] Advantages of the embodiment include:
[0043] 1. The feedback should help the network to make the most appropriate decision, in particular when the measurements appear incomplete or missing altogether. Depending on the feedback, it might be best for the network to wait for the next measurement reporting opportunity, or it might be best for the network to offer a new set of cells to consider, or extend the measurement gaps, or arrange them differently, etc.
[0044] 2. With the proposed feedback information, the network can avoid having to make assumptions based on a statistical analysis, such as “When a mobile telephone 3 does not report measurements in time, it usually means it cannot detect the proposed cells” or some other heuristic the network implements.
[0045] 3. With mobile telephones that use this feedback mechanism, the network may choose to “sail close to the wind”: by not applying a conservative margin when deciding the reporting period, as the network can be confident that the mobile telephone 3 will immediately inform the network of its desire for a longer reporting period.
[0046] 4. Besides a possible reduction in handover time, the frequency of handover failures (or successful but with Quality of Service reduction) should be reduced as candidate cells are assessed better and thus chosen better.
[0047] Thus the present embodiment requires changes to be made to the existing standards. In particular, to implement the above embodiment, the existing standard must be adapted to allow the mobile telephone 3 to provide the feedback information to the network. Additionally, the standard must be adapted to allow the base station 5 - 1 (or other network node depending on the RAT involved) to accept and use the feedback information when deciding on whether to wait for further measurements or to issue a new cell list.
(Modifications and Alternatives)
[0048] A detailed embodiment has been described above. As those skilled in the art will appreciate, a number of modifications and alternatives can be made to the above embodiment whilst still benefiting from the invention embodied therein. By way of illustration only a number of these alternatives and modifications will now be described.
[0049] There is a range of feedback information the mobile telephone might return. Ideally, comprehensive feedback (such as a sensible combination of all the options mentioned below) would allow the network to make the optimal decision. However, the relevant standards bodies may prefer a more basic feedback to reduce the bit overhead involved. For example the feedback may be restricted to a simple flag indicating whether or not the measurements are possible under current conditions; or a simple flag indicating whether or not the measurement report is considered complete by the mobile telephone (confirming then that waiting for further reports would be wasteful as any non reported cells are either non detectable or anyway definitely worse than those that are reported); or, of course, a combination of both such flags. The mobile telephone 3 might also qualify any problems it has with the resources available for measurements (such as: measurement gaps are too short, or the measurement gaps are too close to a reserved resource (e.g. MBMS “slot”) by so much). The standards bodies may accept unused feedback codes for future use. The mobile telephone 3 might also return an estimate of the time required to complete the current round of measurements, under current conditions (given as a number of reporting opportunities). There could also be a value indicating the report is complete (e.g. zero more opportunities) and there could a value meaning never (this would be equivalent to an indication that measurement gaps are unsuitable). All these options are not mutually exclusive though some, of course, are.
[0050] Measurement reports in GSM and UMTS are very flexible. There would be no difficulty in adding a new optional Information Element (IE). The same flexibility will exist in succeeding standards, but in this case, the addition of an IE is even less problematic. Examples of IEs suggested by this proposal are defined below. Further IEs could be defined by combining fields from different examples. Any of the fields might be mandatory or optional. The decision on that is a matter for the standards bodies concerned.
[0051] A reasonable option consists in a single optional IE comprising a small set of fields, chosen from those given below. Note that some combinations of the examples below may be redundant and should not be selected within a solution.
[0000]
TABLE 1
Possible components of a Measurement Feedback IE
Name (arbitrary)
Size
Values
Meaning
More flag
1 bit
0
All cells that can be measured (or will be measured) have
been reported at least once.
1
Not all cells have been reported. The mobile telephone may
report some more at a further reporting opportunity.
Finished flag
1 bit
0
Not all cells have been reported. The mobile telephone will
report some more at a further reporting opportunity.
1
All cells that can be measured (or will be measured) have
been reported at least once.
Happy flag
1 bit
0
The mobile telephone cannot perform the requested
measurements as its capabilities and currently used services
do not allow them.
1
The mobile telephone can perform the requested
measurements in current conditions.
Feasibility.status
Suitable
0
No problem; measurements are complete or forthcoming.
for
(Other flags may complement this information.)
value
1
Measurement gaps are too short.
range
2
Measurement gaps are too close to other reserved resources.
3
Measurement gaps are too short and too close to other
reserved resources. (case 1 + 2).
?
Depending on the technology considered, other cases may be
relevant.
General status
2 bits or
0
All cells that can/will be measured have been reported at
more
least once.
1
More cells may be reported.
2
More cells may be reported, but the measurement gaps make
for inefficient operation.
3
No measurements reported because the measurement gaps
are unsuitable.
?
Depending on the technology considered, other cases may be
relevant.
Estimated Time of
Suitable
0
All cells that can/will be measured have been reported at
Delivery
for
least once.
value
1 to
Number of reporting intervals likely to be required to report
range
max-2
on all cells.
max-1
Never (measurement gaps unsuitable).
max
ETD unknown.
Gap requirement
?
?
Minimal interval configuration required to enable most
efficient measurements. This information may need to be
Access Technology specific. So no examples are given (gap
duration may not be the only relevant factor).
[0052] Fields can also be combined into enumerated types (rather than binary flags), as long as the different values are mutually exclusive. The actual numerical values used are arbitrary and need only be fixed by the standard.
[0053] Finally, it should be possible for the measurement feedback IE to be the only IE in a measurement report, or at least the only optional IE. In this case it is sent purely for feedback purposes and need not necessarily be sent after the designated interval. For example, if the mobile telephone 3 can determine that the measurement gaps are unsuitable, then it could send the feedback immediately without waiting for the first reporting opportunity.
[0054] It might be useful to enhance the mobile telephone's capability signalling, allowing the mobile telephone 3 to indicate to the network that it will use this measurement feedback.
[0055] In the above embodiment, the base station was responsible for issuing the measurement commands and for deciding on the handover. As those skilled in the art will appreciate, this functionality may be performed by some other network node in other radio access technologies.
[0056] In the above embodiments, a number of software modules were described. As those skilled will appreciate, the software modules may be provided in compiled or un-compiled form and may be supplied to the core network, radio access network or to the mobile telephone as a signal over a computer network, or on a recording medium. Further, the functionality performed by part or all of this software may be performed using one or more dedicated hardware circuits. However, the use of software modules is preferred as it facilitates the updating of radio access network 5 and the mobile telephone 3 in order to update their functionalities.
[0057] In the above embodiment, a mobile telephone was provided that communicated with a number of radio access networks. As those skilled in the art will appreciate, the invention is applicable to other types of user equipment (UE) such as laptop computers, Personal Digital Assistants or other hand held portable computer devices.
[0058] In the above embodiment, each radio access network was connected to its own core network 7 . As those skilled in the art will appreciate, a cell can be part of a network sharing architecture in which there may be several core networks 7 that use the same cell or there may be several cells (of different RATs) that operate in connection with the same core network. | A cellular communications system is described in which a mobile cellular device is configured to return status data to the network when instructed to obtain cell measurements. When used, the status data may indicate that measurements are in hand and that further measurement reports may or will follow. The status data may also indicate if the reporting interval and/or the measurement gaps defined by the network are suitable to make the measurements given the current status of the mobile device. A network node is also disclosed that can receive the measurement reports and interpret the status data to decide to wait for further measurement results or to issue a new reporting interval or a new cell list or arrange a new configuration of idle gaps in which cell measurements may be made. | 7 |
This is a continuation, of application Ser. No. 08/329,998, filed Oct. 27, 1994, now abandoned.
BACKGROUND OF THE INVENTION
1 . Field of the Invention
The present invention relates to, a method and apparatus for coating a board or paper web using an air knife as the doctoring means.
2 . Description of the Related Art
When using an air doctor, the coating mix applied to the web is smoothed by directing a high-velocity air jet via a slot-orifice nozzle of the air doctor toward the web. This air knife removes the excess coat from the web surface in the form of a coat mist which is collected into a specially designed blow-off hood and recycled back to the coating mix pan. With the help of the air doctor, a smooth coat is attained and the profile of the coated paper or paperboard web follows the contour of the base web. The opacifying power of the applied coat is good. However, this method is not suitable for applying high-solids coats.
The greatest drawback of air doctoring is its inherently weak blow-off capability of removing the excess coat, which capability is further impaired at higher web speed. Consequently, air doctoring must employ coating furnishes of low viscosity and solids content, and even so the usable web speed remains less than 500 m/min in even the fastest machines. For these reasons, air doctoring is used almost exclusively in board coating where good opacifying power is imperative and high web speeds are not as critical as in papermaking in general. If the viscosity or solids content of the coating mix is increased, the air doctor loses its ability to blow off the excess coat and, therefore, the finished coat weight becomes excessively heavy. Accordingly, the requirements set for air doctor coating are that the applied coat should be as smooth as possible and the weight of the applied coat should closely approximate the desired finished coat weight.
U.S. Pat. No. 3,235,401 to Fowells discloses an air doctor apparatus in which the web to be coated is directed, first to a metering roll of the applicator apparatus via a guide roll. The metering roll is placed in the coating mix pan so that the lower part of the roll is immersed in the pan, while the web runs over the upper part of the roll. The metering roll lifts an excess amount of the mix from the pan to the web which then passes over a rotating predoctoring rod that removes a portion of the excess coat from the web. The purpose of the predoctoring rod is to smooth the coat and remove so much of the excess coat that the air knife can then doctor the coat to the desired finished coat weight. After the predoctoring rod, the web travels onto a backing roll having a closely-disposed air knife so as to blow a narrow-slitted air jet in the reverse direction to the web travel and to thus doctor the coat to its finished weight.
Several variants of the above-described type of apparatus are known in the art, and they constitute the basic construction or use of air doctors. A drawback of these doctor apparatus is the rapid decrease of their doctoring performance in terms of coat quality and smoothness at higher web speeds.
Patent publication WO 91/17309 discloses an apparatus which is further developed from that described above in that the coat quality and maximum usable web speed during coating have been improved. The apparatus described in WO 91/17309 is otherwise similar to the apparatus described in U.S. Pat. No. 3,235,401, except that the applicator roll is complemented by a doctoring bar which performs both smoothing and metering of the coat transferred from the coating mix pan to the web. In this fashion, the coat applied to the web attains better smoothness and the coat weight is more accurately reduced to the desired finished coat weight. Such an arrangement has the advantage that the air knife need not remove a great amount of excess coat and the coat will have improved smoothness since the initially applied coat is already relatively smooth. Bar smoothing Of the coat applied to the web also improves the quality of the end product and permits a higher web speed owing to the reduced blow-off duty imposed on the air knife. In addition, bar smoothing obviates the need to use a rotating predoctoring/metering roll.
Though the above-described apparatus is capable of overcoming certain drawbacks of air doctor techniques, there remain several disadvantages mostly related to the applicator roll method. When running at a high web speed, the applicator roll causes vigorous splashing of the coating mix which then finds its way all over the machinery, including the web and the surroundings. As the rotational speed of the applicator roll is greatly increased at higher web speeds, splashing becomes particularly problematic at the highest web speeds. When using an applicator roll, uncoated spots will remain on the web. Further, the web tension profile has a significant effect on the thickness of the applied coat, and since the air doctor is incapable of smoothing away large variations in coat weights, changes in the web tension profile are directly evidenced by quality defects. Moreover, the roll applicator is characterized by a type of inherent quality defect, namely, the orange peel pattern caused by the splitting of the coat film at the outgoing side of the contact point between the web and the applicator roll; this orange peel pattern cannot be effectively removed by means of air doctoring, particularly if the web speed is high.
A roll applicator cannot be used for applying low coat weights on the web since it results in mottling of the web with uncoated spots. Furthermore, the control of the cross-machine profile of the applied coat becomes rather impossible.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a coating apparatus with an air doctor, which apparatus offers higher web speed and improved finished quality of the coated web.
The invention is based on applying a layer of coating mix of precise thickness onto the web by means of a narrow slot-orifice applicator operating with a counterflow in the reverse direction to the web travel and having precise control of the mass flow of the coat mix applied to the web so as to achieve a desired coat weight.
The present invention is capable of overcoming most of the drawbacks of the roll applicator method. Use of the slot-orifice applicator permits precise metering of the amount of coating mix applied to the web close to the desired coat weight, thereby minimizing the quantity of coating to be removed by an air doctor. Since the amount of coating mix removed is small, the web speed can be increased without compromising the quality of the end product. The machine-direction coat profile remains smooth irrespective of web tension variations, and the cross-machine direction coat profile can be kept smooth within a narrow tolerance, or alternatively, controlled in a desired manner to take into account the profile variations of the board base web. In accordance with another aspect of the invention, the apparatus provides good controllability and is suited for application of low-coat weights without the hazard of coat mottling.
The method in accordance with the present invention is free from splashing or the "orange peel effect", thereby reducing the need for subsequent cleaning, and thus offers direct improvement of availability and coat quality. The web surface is subjected to lower application pressure than that applied by roll applicators. The lower pressure reduces water penetration into the web and permits the machine to run at a reduced drying capacity and to use a coating mix with slightly higher solids content because of the reduced amount of water transferred from the coat to the web. The finished coat has excellent smoothness since the slot-orifice applicator, in accordance with the present invention, is capable of applying a high-smoothness coat with a weight that is extremely close to the desired finished coat weight. The runnability of the apparatus is good owing to the excellent control facilities offered by the method for optimizing the critical operating parameters of the air knife under widely varying process conditions including web speed variations.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings, wherein like reference characters denote similar elements throughout the several views:
FIG. 1 is a diagrammatic side view of an embodiment of the slot-orifice applicator apparatus in accordance with the present invention;
FIG. 2 is an enlarged cross-sectional view of the applicator apparatus as illustrated in FIG. 1;
FIG. 3 is a cross-sectional view of another embodiment of the applicator apparatus of FIG. 1;
FIG. 4 is a cross-sectional view of still another embodiment of the applicator apparatus of FIG. 1; and
FIG. 5 is a cross-sectional view of yet another embodiment of the applicator apparatus of FIG. 1.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The term "slot-orifice applicator apparatus" is used herein to refer to an applicator apparatus in which coating mix is transferred to the surface of a web by direct extrusion through a narrow slot orifice. Smooth spreading of the coating mix is ensured by, for example, a doctor blade, rod, grooved rod, or alternatively extruding the coating mix on the web at a high speed via a narrow slot orifice.
As seen in FIG. 1, the coater apparatus comprises a first backing roll 1, an applicator apparatus 2 adapted in conjunction therewith, a second backing roll 3 disposed following the applicator apparatus 2 in the travel direction of a web 5, and an air knife 4 disposed proximate the second backing roll 3. The web 5 passes partially around the first backing roll 1, then through the nip between the first backing roll 1 and the applicator apparatus 2 and then to the second backing roll 3, on which the web 5 further passes through the nip between the second backing roll 3 and the air knife 4. The diameter of the second backing roll 3 may be smaller than that of the first backing roll 1; when the web 5 bends over the backing roll 3 at a smaller radius of curvature, the efficiency of the air doctor in blowing off the excess coat from the surface of the web 5 is increased. However, such an arrangement is not required and the design criteria of the roll diameters can be based on different aspects or parameters as well. FIG. 1 shows that the coat removed from the web surface may be collected in a blow-off hood 25. The air knife 4 in the illustrated embodiment comprises an air chamber 6 that ejects air through a narrow slot orifice 7 which extends across the entire machine width. The slot orifice 7 and the air knife 4 are arranged or oriented to eject a stream of air in the reverse direction to the travel of the web 5. Since the coating mix dries and its solids content and viscosity increase after its application to the base web due to mechanisms such, for example, as moisture absorption by the web 5, it is desirable that the distance of the air knife 4 from the applicator apparatus 2 be adjustable so as to permit the adjustment of the air knife assembly 4 with its backing roll 3 to as close to the application zone as required.
Shown in FIG. 1 is an applicator apparatus provided with a smoothing/premetering blade 8. The applicator apparatus is adapted in conjunction with a rotating backing roll 1 around which the web 5 to be coated passes. Located at an underside of the backing roll 1 is an applicator that extends over the entire cross-machine width of the web 5 and has its framework formed by a support beam 9 having an approximately triangular cross-section. Through a feed channel, which extends over the entire cross-machine width of the web 5 along the support beam 9 on the incoming side of the web, the coating mix is guided into a chamber-like space 10, wherefrom the coating mix under pressure flows to the web via a narrow, flat slot-orifice channel 11. The channel extends over the entire web width and opens at the stem of the smoothing/premetering blade 8. Adapted to the orifice channel 11 is a comb-like flow-laminarizing element 18. Particularly at the orifice tip, the orifice channel 11 is very narrow with respect to conventional coating mix feed channels typically having the width of the exit slot 12 as narrow as 3-5 min. The smoothing/premetering blade 8 is supported at its stem by a blade holder 13. The blade 8 rests flexibly against the web 5 at a small angle, and during operation it is elevated away from the web by the applied coat. The angle of the blade 8 is typically smaller than 20° and most advantageously less than 10°. The blade support 13 is designed so that no step is formed between the exit slot 12 and the stem of the blade 8 so as to facilitate laminar flows. Particularly at the side of the orifice channel 11, the blade support 13 has a wedge-shaped cross-section tapering toward the tip of the blade 8. The purpose of such a support arrangement is to keep the flow of coating mix laminar from the orifice channel 11 up to the tip of the blade 8. The loading of the smoothing/premetering blade 8 can be adjusted by means of separate blade load control apparatus 16 (see FIG. 2). The load control apparatus 16 is divided into independent control zones over its cross-machine width so as to offer variable blade loading in that direction. The apparatus 16 thus permits the adjustment of the applied coat weight and thereby obtains a desired coat profile across the width of the web. Since several different blade loading arrangements are well known in the art, a more detailed description of such an apparatus is omitted herein.
The coating mix is fed at a high speed such, for example, as in excess of 1 m/s. In accordance with the present invention, an excess portion of the applied coating mix is guided in the reverse direction to the travel of the web 5 past an upper lip 17 of the orifice channel 11. This excess mix is particularly important to the successful outcome of the coating process since it plays a major role in assuring a smooth and homogeneous coat. The excess mix reverse flow (or return flow) 14 also permits an extremely accurate control of the amount of coating mix applied to the web 5 as well as the adjustment of the coat thickness including very thin coats. The coat thickness adjustment may be implemented by an ordinarily skilled artisan by either controlling the blade load or adjusting the feed rate of fresh coating mix; however, the best result is obtained by a combination of both of these control methods. The return flow 14 of the excess coating mix may be collected in an overflow trough 15. An apparatus of the above-described type is known in the art and a more detailed description thereof can be found in U.S. Pat. No. 5,104,697.
Alternative embodiments of the applicator apparatus are shown in FIGS. 3-5. The applicator illustrated in FIG. 3 is similar to that shown in FIG. 2 except that the upper lip 17 of the slot orifice 12 is complemented with a weir blade 19 resting against the backing roll 1. This weir blade 19 is preferably inclined at a small angle with respect to the web and
preferably made of a flexible material so that it conforms to the web contour. The weir blade 19 is advantageously provided with holes. The holes permit sufficient reverse flow against the web travel and thus feed some coating mix as a lubricant into the nip between the web and the weir blade 19. A function of the weir blade 19 is to elevate the coating mix pressure at the zone provided by the slot orifice 12, so that even a smaller amount of coating mix is sufficient for applying a high-solids coat. The applicator apparatus described herein is particularly suited for coating at a low web speed.
In another embodiment of the apparatus shown in FIG. 4, the smoothing/premetering blade is replaced by a doctor rod 20. The doctor rod 20 is mounted to a floating doctor rod holder 21 which is pushed toward the web by means of pneumatic tubes 22. The doctor rod 20 may be smooth or grooved. In comparison with the earlier described applicators, the doctor rod 20 has the same benefits and drawbacks as blade doctors, and when required, it may also be complemented by a weir blade. (not shown) so as to ensure sufficient application pressure at low web speeds.
With reference to FIG. 5, another embodiment of the slot-orifice applicator apparatus is shown therein, which applicator apparatus comprises an upper lip 17 and a lower lip 23. The slot orifice 12 of the applicator is formed by the rounded tip of the upper lip 17 and by the conformingly curved portion of the lower lip 23. The path of the coating mix flow starts from the narrow flat channel 11 and tapers toward the slot orifice 12. The width of the channel 11 at its entrance may be approximately 0.5-10 mm but is preferably in the range of 1.5-4 mm. Of course, the length of the channel 11 in the cross-machine direction must extend at least across the entire width of the web. The width of the orifice slot 12 may be in the range of 0.5-10 mm, however, so that at its exit the slot is slightly tapered relative to the inner width of the channel 11. The gap distance between the slot-orifice applicator apparatus and the backing roll 1 or surface of the web may be in the range of 1-20 mm, but preferably between 3-8 mm. The gap distance may be selectively adjusted by moving the lower lip using an adjustment apparatus 24. In addition, the upper lip may be made transferrable relative to the coater framework, whereby the width of the slot-orifice channel 11 may be made adjustable if desired. The rounded tip of the upper lip 17 induces a so-called Coanda effect, whereby the coating mix jet tends to follow the surface of the upper lip 17 at the exit of the orifice slot and thus directs the coating mix jet in the reverse direction to the web travel. The radius of curvature of the tip may vary in the range of 1-50 mm, and is preferably in the range of 3-10 mm.
A basic precondition to the formation of a suitable jet flow of the coating mix is that the surface of the lower lip 23 of the slot orifice 12 curves toward the direction reverse to the web travel, thereby achieving the desired aiming of the coating mix jet.
In accordance with the present invention, the amount of coating mix feed can be adjusted in many different ways, the most important of which is the control of the coating mix flow rate by adjusting the volume rate of fresh coating mix. Simultaneously or alternatively, the width of the slot orifice 12 or the jet direction may be varied. The jet direction may be altered by, for example, rotating the applicator apparatus with its support beam in the same manner that the angle of the doctor blades is adjusted. Such a slot-orifice coating apparatus is described in greater detail in Finnish patent application 924,841.
The above-described types of coater assemblies are operated as follows. The incoming web passes around the backing roll 1 of the applicator apparatus whereby to the top side of the web is applied a coat thickness closely corresponding to the desired coat weight using a slot-orifice applicator 2. The coat thickness having been so applied enables the air knife 4 to smooth the coat at the normally higher web speed; different coat solids and coat viscosity may be selectively employed to achieve the desired finished coat weight. Of course, when the coater-assembly is run at higher web speeds and employs higher coating mix viscosities, the applied coat thickness must be closer to the finished coat weight than when it operates at lower web speeds. The applied coat must however be thicker than the finished coat so as to leave the air knife 4 some excess coat to blow off in order to smooth or trim the applied coat to its finished weight. But if the initially applied coat is excessively thin, the quality of the coat may suffer since the air knife 4 may be rendered unusable, at least partially, and the finished coat weight may not meet specifications.
In the above description there are provided various embodiments of applicator apparatus in accordance with the present invention. It is demonstrated that the construction of the applicators can be varied provided that an applicator apparatus has a member that directs the coating mix to flow in the direction reverse to the web travel and that the slot orifice of the applicator apparatus applies to the web, in the travel direction of the web, only a coat thickness which closely approximates the desired finished coat weight. Of course, the present assembly and method are also suited for coating other similar materials besides board and paper.
Conceivably, the applicator apparatus and air doctor can be disposed around a single backing roll, although the construction of such an apparatus becomes extremely complicated because of difficulties such, for example, as the positioning of a fume hood between the applicator apparatus and the air doctor.
Thus, while there have been shown and described and pointed out fundamental novel features of the invention as applied to a preferred embodiment thereof, it will be understood that various omissions and substitutions and changes in the form and details of the devices illustrated, and in their operation, may be made by those skilled in the art without departing from the spirit of the invention. For example, it is expressly intended that all combinations of those elements and/or method steps which perform substantially the same function in substantially the same way to achieve the same results are within the scope of the invention. Substitutions of elements from one described embodiment to another are also fully intended and contemplated. It is also to be understood that the drawings are not necessarily drawn to scale but that they are merely conceptual in nature. It is the intention, therefore, to be limited only as indicated by the scope of the claims appended hereto. | A method and apparatus for applying a coat mix to a high-speed running board or paper web by accurately premetering and pre-smoothing the applied coal with an applicator apparatus and then minimally doctoring the applied coat with an air knife. The applicator apparatus has a narrow slot-orifice extending in a cross-machine direction for facilitating high-speed laminar flow of coating mix into a gap region defined by confronting surfaces of the applicator apparatus and the web. The applicator apparatus has a member for directing the ejected coating mix in tho gap region in a direction reverse to a travel direction of the web so that only a predetermined portion of the ejected coating mix is allowed to form an applied coat on the web. This accurate premetering of the coating mix by the applicator apparatus permits an operator to readily optimize the subsequent process of doctoring the applied coating with an air knife. | 3 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a circuit board and a method for manufacturing the same and, more particularly, to a circuit board with high thermal conductivity and a method for manufacturing the same.
[0003] 2. Description of Related Art
[0004] As the electronic industry develops rapidly, the demands for electronic products increase greatly. Additionally, the development in the electronics industry trends towards manufacturing electronic products with multifunction and high performance. Especially, as the growth and the utility in portable electronic products increase, the size of electronic products is reduced to meet the requirements of compactness and lightness. Hence, the size of circuit boards used in electronic products is also reduced. However, the reduced size of circuit boards makes heat dissipation more difficult.
[0005] For example, conventional light emitting diode devices (LEDs) can be applied in various electronic devices, such as backlight sources of display devices, mini-projectors, and lighting devices, due to its high brightness. However, 80 % input power of LEDs is converted into heat. If the heat cannot be dissipated appropriately, the junction temperature of the LEDs will rise which influences the brightness and the lifetime thereof.
[0006] A multilayer substrate disclosed in JP 2004-193283 is used for supporting electronic components, wherein the multilayer substrate is a laminate, which consists of a ceramic substrate, an insulating layer, and a diamond layer. Electrodes are formed on the bottom or top face of the supporting substrate, and electrically bonded to each other through via-holes filled up with metal. The aforementioned multilayer substrate comprises the ceramic substrate and the ceramic insulating layer. However, use of ceramic material as the multilayer substrate still has a disadvantage in poor heat dissipation. Hence, the heat generated by continuous operation of the electronic components cannot be dissipated efficiently, which will influence the stability and the lifetime of the electronic components.
[0007] Therefore, it is desirable to provide a circuit board for supporting electronic components to improve the thermal conductivity and the heat dissipation of the electronic components.
SUMMARY OF THE INVENTION
[0008] The object of the present invention is to provide a circuit board and a method for manufacturing the same to improve the thermal conductivity thereof, so that the heat generated by semiconductor devices can be dissipated rapidly.
[0009] To achieve the aforementioned object or other objects, the present invention provides a circuit board, comprising a substrate, a plurality of thermal conductive insulating layers, a patterned electrical conductive layer, a plurality of through-holes, and a solder layer. Herein, the substrate has an upper surface, and a lower surface; the thermal conductive insulating layers are respectively formed on the upper surface and the lower surface of the substrate; the patterned electrical conductive layer is disposed on the surfaces of the thermal conductive insulating layers; the through-holes are extended through the substrate, and electrically connected to the patterned electrical conductive layer; and the solder layer is partially formed on the patterned electrical conductive layer. Beside, the present invention also provides a method for manufacturing the aforementioned circuit board.
[0010] According to the circuit board of a preferable embodiment in the present invention, the through-holes are filled with a conductive material, which comprises Cu, Ag, or a combination thereof.
[0011] The circuit board of a preferable embodiment in the present invention may further comprise a plurality of ceramic layers formed on the upper surface and the lower surface of the substrate, and located between the substrate and the thermal conductive insulating layers, wherein the material of the ceramic layers is oxide, nitride, or boride.
[0012] According to the circuit board of a preferable embodiment in the present invention, the substrate comprises a metal substrate, a semiconductor substrate, or a substrate made from other applicable materials. Herein, the material of the metal substrate is Al, Cu., or a combination thereof, and the material of the semiconductor substrate is Si, Ge, GeAs, or a combination thereof.
[0013] According to the circuit board of a preferable embodiment in the present invention, the material of the thermal conductive insulating layers comprises diamond-like carbon. Additionally, the thermal conductive insulating layers have a dopant, which is F, Si, N, B, or a combination thereof. The thermal conductive insulating layers may have a thickness of 0.1-30 μm. Preferably, the thermal conductive insulating layers have a thickness of 2-5 μm.
[0014] The circuit board of a preferable embodiment in the present invention may further comprise an insulating layer formed on the sides of the through-holes, wherein the material of the insulating layer is insulating gel, or a ceramic material.
[0015] According to the circuit board of a preferable embodiment in the present invention, the material of the patterned electrical conductive layer is Cr, Cu, Ni, Au, Ag, or a combination thereof.
[0016] The circuit board of a preferable embodiment in the present invention may further comprise a metal layer disposed on the patterned electrical conductive layer to enhance the adhesive strength with the electronic component. Herein, the metal layer is Ni, Au, Ag, Sn or Sn alloy, and a combination thereof.
[0017] According to the circuit board of a preferable embodiment in the present invention, the circuit board is used to support an electronic component, which is disposed on the patterned electrical conductive layer of the circuit board through the solder layer, and the electronic component is a chip, or a semiconductor device.
[0018] To achieve the aforementioned object or other object, the present invention provides a method for manufacturing a circuit board (with high thermal conductivity), comprising the following steps: providing a substrate having an upper surface, and a lower surface; forming a plurality of thermal conductive insulating layers, which are respectively formed on the upper surface and the lower surface of the substrate; forming a plurality of through-holes, which are extended through the substrate, and the thermal conductive insulating layers; forming an electrode layer on the surfaces of the thermal conductive insulating layers; removing parts of the electrode layer to form a patterned electrical conductive layer; and forming a solder layer, which is partially formed on the patterned electrical conductive layer.
[0019] According to the method for manufacturing a circuit board with high thermal conductivity of a preferable embodiment in the present invention, the through-holes are formed by wet etching, or machine drilling.
[0020] According to the method for manufacturing a circuit board of a preferable embodiment in the present invention, the material of the thermal conductive insulating layers is diamond-like carbon.
[0021] The method for manufacturing a circuit board of a preferable embodiment in the present invention may further comprise: adding a dopant into the thermal conductive insulating layers. Herein, the dopant is F, Si, N, B, or a combination thereof.
[0022] The method for manufacturing a circuit board of a preferable embodiment in the present invention may further comprise: filling the through-holes with a conductive material, wherein the conductive material is Cu, Ag, or a combination thereof.
[0023] The method for manufacturing a circuit board of a preferable embodiment in the present invention may further comprise: forming an insulating layer on the sides of the through-holes, wherein the material of the insulating layer is insulating gel, or a ceramic material.
[0024] According to the method for manufacturing a circuit board of a preferable embodiment in the present invention, the electrode layer is formed by sputtering, electroplating, or electroless plating.
[0025] According to the method for manufacturing a circuit board of a preferable embodiment in the present invention, the electrode layer is removed by etching.
[0026] According to the method for manufacturing a circuit board of a preferable embodiment in the present invention, the electrode layer has a thickness of 0.1-100 μm, or 20-40 μm.
[0027] The method for manufacturing a circuit board of a preferable embodiment in the present invention may further comprise: forming a metal layer on the patterned electrical conductive layer after forming the patterned electrical conductive layer. Herein, the metal layer comprises Ni, Au, Ag, Sn or Sn alloy, and a combination thereof.
[0028] The method for manufacturing a circuit board of a preferable embodiment in the present invention may further comprise: forming a plurality of ceramic layers on the upper surface and the lower surface of the substrate.
[0029] According to the method for manufacturing a circuit board of a preferable embodiment in the present invention, the ceramic layers are located between the substrate and the thermal conductive insulating layers.
[0030] According to the method for manufacturing a circuit board of a preferable embodiment in the present invention, the ceramic layers are formed by anodizing, or thermal treatment.
[0031] According to the method for manufacturing a circuit board of a preferable embodiment in the present invention, the material of the ceramic layers is oxide, nitride, or boride.
[0032] In conclusion, in the circuit board and the method for manufacturing the same provided by the present invention, thermal conductive insulating layers and ceramic layers are formed on a substrate, and through-holes extended through the substrate are electrically connected to a patterned electrical conductive layer, which is disposed over an upper surface and a lower surface of the substrate. Hence, the heat generated by electronic components can be effectively dissipated by the circuit board of the present invention. Therefore, the efficiency and the lifetime of electronic components can be improved by use of the circuit board of the present invention.
[0033] Other objects, advantages, and novel features of the invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0034] FIG. 1 is a cross-sectional view of a circuit board according to an embodiment of the present invention;
[0035] FIGS. 2A to 2E are flow charts for illustrating a process for manufacturing a circuit board according to an embodiment of the present invention; and
[0036] FIG. 3 is a cross-sectional view of a circuit board according to another embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Embodiment 1
[0037] With reference to FIG. 1 , there is shown a cross-sectional view of a circuit board according to an embodiment of the present invention. The circuit board of the present invention comprises: a substrate 100 , a thermal conductive insulating layers 120 , and a patterned electrical conductive layer 135 . Herein, the thermal conductive insulating layers 120 are respectively formed on an upper surface 100 a and a lower surface 100 b of the substrate 100 , and the patterned electrical conductive layer 135 is disposed on the surfaces of the thermal conductive insulating layers 120 . The patterned electrical conductive layer 135 can be applied to electrically connect to other electronic components. For example, the patterned electrical conductive layer 135 is electrically connected to electronic components through wires. The material of the patterned electrical conductive layer 135 comprises materials with electrical conductivity, such as Cr, Cu, or Ag. Additionally, in the present embodiment, the substrate 100 is a substrate with thermal conductivity, which comprises a metal substrate, a semiconductor substrate, or a substrate made from other applicable material. It should be understood that any kinds of metal or semiconductor with the effect on heat dissipation can be used as the material of the substrate. Hence, in the present embodiment, the metal material comprises a metal or an alloy consisting of two or more metals, such as Al, Cu, an alloy thereof, or a compound thereof. The semiconductor material is, for example but not limited to, Si, Ge, GeAs, or a combination thereof.
[0038] In the present embodiment, the thermal conductive insulating layers 120 are formed on the upper surface 100 a and the lower surface 100 b of the substrate 100 . Here, the thermal conductive insulating layers 120 are used to dissipate the heat, which is generated from electronic components (not shown in the figure) disposed on the substrate. The material of the thermal conductive insulating layer 120 can be diamond-like carbon. If necessary, the diamond-like carbon film can be doped with elements, such as F, Si, N, or B, to reduce the inner stress of the thermal conductive insulating layer 120 . In the thermal conductive insulating layer 120 , which is formed by the diamond-like carbon film doped with elements, such as F, Si, N, or B, the content of these elements (atom %) is unlimited, as long as these elements will not cause any deterioration to the semiconductor effect. The content of F or Si in the diamond-like carbon film may be 1-40 atom %. Preferably, the content of F or Si in the diamond-like carbon film is 5-20 atom %. The content of N or B in the diamond-like carbon film may be 1-30 atom %. Preferably, the content of N or B in the diamond-like carbon film is 5-15 atom %. In the present invention, the thermal conductive insulating layers 120 are disposed on the surfaces of the substrate 100 , and made from diamond-like carbon with good thermal conductivity. Hence, when electronic components are operated, it is possible to dissipate heat to the environment effectively through the thermal conductive insulating layers 120 .
[0039] With reference to FIG. 1 , the circuit board of the present embodiment comprises a plurality of through-holes 130 vertically extended through the circuit board, wherein the through-holes 130 are filled with a conductive material 131 . It should be noted that any kinds of materials with electrical conductivity can be used as the conductive material 131 in the present embodiment. For example, the material used in the conductive material 131 can be metal, but should not be limited to Cu. Ag, or a combination thereof. Because the through-holes 130 are filled with the conductive material 131 , the patterned electrical conductive layer 135 disposed on the thermal conductive insulating layers 120 can be electrically connected through the through-holes 130 . Hence, the circuit board of the present invention can be electrically connected to other components. Besides, an insulating layer 132 is formed on the sides of the through-holes 130 , in order to electrically isolate the substrate 100 with the through-holes 130 . The material of the insulating layer 132 is an insulating gel or a ceramic material. The material of the insulating layer 132 is, for example but not limited to, oxides, nitrides, carbides, epoxides, silica gel, or polyimide (PI).
[0040] In addition, the circuit board of the present invention is used to support an electronic component 150 . As shown in FIG. 1 , a solder layer 140 is formed on the patterned electrical conductive layer 135 of the circuit board, and the electronic component 150 is disposed on the circuit board through the solder layer 140 . Herein, the electronic component 150 comprises a chip or a semiconductor device, such as a light emitting diode device (LED).
[0041] In the present invention, the thermal conductive insulating layers are formed on the upper surface and the lower surface of the substrate. Hence, not only the substrate but also the thermal conductive insulating layers of the present invention can dissipate the heat generated by electronic components, as compared with the conventional circuit board. Besides, the circuit board of the present invention includes the through-holes, so that the patterned electrical conductive layer disposed on the circuit board can be electrically connected. Hence, the circuit board of the present invention can be electrically connected to other components.
[0042] FIGS. 2A to 2E are flow charts for illustrating a process for manufacturing a circuit board of the present invention. First, with reference to FIG. 2A , a substrate 100 is provided, which has an upper surface 100 a and a lower surface 100 b . Then, as shown in FIG. 2B , thermal conductive insulating layers 120 are formed on the upper surface 100 a and the lower surface 100 b of the substrate 100 . The thermal conductive insulating layers 120 are formed by chemical vapor deposition (CVD), and the condition of the chemical vapor deposition can be modified by a person skilled in the art without changes of the main principle of the present invention. Hence, the examples of the vapor deposition include filament chemical vapor deposition (filament CVD), plasma enhanced chemical vapor deposition (PECVD), or microwave plasma chemical vapor deposition (MPCVD), and other like methods. Preferably, in the present embodiment, the thermal conductive insulating layers are formed on the upper surface 100 a and the lower surface 100 b of the substrate at 200° C. or lower by PECVD. Besides, the thickness of the thermal conductive insulating layers 120 is unlimited. Preferably, the thermal conductive insulating layers 120 have a thickness of 0.1-30 μm. In the present embodiment, the thermal conductive insulating layers 120 have a thickness of 2-5 μm.
[0043] With reference to FIG. 2C , a plurality of through-holes 130 is formed, and vertically extends through the substrate 100 and the thermal conductive insulating layers 120 . The through-holes 130 are formed by etching or machine drilling, for example. Besides, the through-holes 130 are filled with a conductive material 131 . Additionally, an insulating layer 132 is formed on the sides of the through-holes 130 . Then, as shown in FIG. 2D , an electrode layer 134 is formed on the surfaces of the thermal conductive insulating layers 120 . The electrode layer 134 is formed by sputtering, electroplating, or electroless plating, wherein the material of the electrode layer 134 is Cr, Cu, or Ag. The thickness of the electrode layer 134 is unlimited, and depends upon the density of current applied from the electronic components (not shown in the figures). Preferably, the electrode layer has a thickness of 0.1-100 μm. In the present embodiment, the electrode layer 134 has a thickness of 20-40 μm.
[0044] Finally, with reference to FIG. 2E , parts of the electrode layer 134 are removed to form a patterned electrical conductive layer 135 . The electrode layer 134 is removed by etching. After the patterned electrical conductive layer 135 is formed, the patterned electrical conductive layer 135 can be plated with Ni, Au, Ag , Sn or Sn alloy, and a combination thereof (not shown in the figures) if needed, in order to enhance the adhesive strength between the patterned electrical conductive layer 135 and electronic components.
Embodiment 2
[0045] With reference to FIG. 3 , there is shown a cross-sectional view of a circuit board according to another embodiment of the present invention. The circuit board and the method for manufacturing the same of the present embodiment are similar to those of the aforementioned embodiment. In comparison to the circuit board illustrated in the aforementioned embodiment, the circuit board of the present embodiment further comprises a plurality of ceramic layers 110 respectively formed on the upper surface and the lower surface of the substrate 100 , and thermal conductive insulating layers 120 are formed on the surface of the ceramic layers 110 . The material of the ceramic layers 110 is unlimited. Preferably, the material of the ceramic layers 110 is oxide, nitride, or boride. It should be noted that the method used for forming the ceramic layers 110 depends upon the material of the substrate 100 . In the present embodiment, when the substrate 100 is a metal substrate, the ceramic layers 110 are formed by anodizing. When the substrate 100 is a semiconductor substrate, the ceramic layers 110 are formed by thermal treatment. Additionally, in the present embodiment, the ceramic layers 110 are located between the substrate 100 and the thermal conductive insulating layers 120 , so it is possible to enhance the adhesive strength between the thermal conductive insulating layers 120 and the substrate 100 . On the other hand, the ceramic layers 110 are good thermal conductors, so it is possible to improve the efficiency of the heat 5 dissipation of the circuit board of the present invention.
[0046] In conclusion, the circuit board of the present invention has thermal conductive insulating layers, which can improve the efficiency of the heat dissipation of the circuit board of the present invention. Hence, the heat, which is generated by electronic components disposed on the circuit board 10 or electronic circuits, can be effectively dissipated through the thermal conductive substrate and the thermal conductive insulating layers.
[0047] Therefore, the efficiency of the heat dissipation can be improved, and the stability and the lifetime of electronic components can be improved greatly.
[0048] In addition, the circuit board of the present invention has the through-holes. 15 Hence, the patterned electrical conductive layer disposed on the circuit board can be electrically connected by the through-holes. Therefore, the circuit board of the present invention can be electrically connected to other components.
[0049] Although the present invention has been explained in relation to its 20 preferred embodiment, it is to be understood that many other possible modifications and variations can be made without departing from the scope of the invention as hereinafter claimed. | A circuit board having high thermal conductivity comprises a substrate, a plurality of thermal conductive insulating layers, a patterned electrical conductive layer, a plurality of through-holes and a soldering layer. The substrate has an upper surface and a lower surface; the thermal conductive insulating layers are respectively formed on the upper surface and the lower surface of the substrate. The patterned electrical conductive layer is disposed on the surfaces of the thermal conductive insulating layers. The plurality of through-holes are extended through the substrate and electrically connected to the patterned electrical conductive layer, and the soldering layer is partially formed on the patterned electric conductive layer. The present invention also discloses a method for manufacturing the circuit board as above-mentioned. | 7 |
This is a continuation of application Ser. No. 07,606,664 filed Oct. 31, 1990, now abandoned.
BACKGROUND OF THE INVENTION
This invention relates to fiber reinforced resin matrices and more particularly it relates to polyester fiber as the reinforcing fiber for a polyethylene terephthalate resin matrix. Plastic shells reinforced with fiber glass are used for certain applications such as automotive body parts or housings for tools or electronic equipment. The reinforcing fibers such as glass are cast or encapsulated in a matrix such as polyethylene terephthalate (PET) or polypropylene (PP).
There are several methods which are usually employed to form these structures. One such method uses injection molding of PET blended with a very short cut length of glass fibers. A second method uses a polyester in a solvent base which is sprayed into a mold, then laid up with glass, and then sprayed with another layer of polyester and a cross-linking agent to make this structure permanently solid. Yet in another method preform sheet is produced by consolidating (technically pre-consolidating) a mixture of glass fiber and PET or PP or by extruding PET or PP to a glass fiber mat. The sheet thus obtained is then vacuum formed or thermo-formed in a mold in a male female mold.
In all these techniques the PET has to be heated above its melting point to obtain conformance with the mold shape. Most homopolymer PET degrades very rapidly due to oxidation and hydrolytic degradation and looses it molecular weight and strength at this high temperature.
Hence, in all the above techniques, the moisture or oxygen has to be excluded from coming in contact with the hot polymer blend. This requires elaborate injection molding or blanketing or drying equipment or the use of antioxidants in the polymer.
SUMMARY OF THE INVENTION
This invention takes advantage of two fundamental properties of polyesters, namely, the degradation is most rapid at the melting point of PET (240° to 250° C.) in the absence of an inert media gas as is the case in most molding operations. It is also known that this degradation or strength loss is due to reduction in molecular weight caused by Chain Scission which declines rapidly with the reduction in temperature. The second property is the depression of the melting point of PET when copolymerized with isophthalates or glycols such as diethylene glycol (DEG). Surprisingly, this combination gives a copolymer PET matrix which can be reinforced with homopolymers PET fibers and neither the matrix nor the reinforcing fibers degrade significantly because the matrix can be melted and reconsolidated at lower temperatures. This invention involves a combination of matrix (binder) and reinforcing fibers such that the molding or the pre-consolidation temperature is low enough (220° C.) to accomplish molding without appreciable degradation of the matrix or the reinforcement. Specifically, when a composite of homopolymer PET matrix reinforced with glass fibers was molded, it had to be consolidated at 270° C. The glass remained intact but the polyester degraded from an intrinsic viscosity (I.V.) of 0.65 (20 LRV) to I.V. of 0.53 (13.5 LRV) and with this there was an unacceptable loss of molecular weight and strength. However, when PET was used as the reinforcing fiber and a copolymer of PET and 12.5 mole % DEG was used as the matrix and consolidated at 220° C., the matrix I.V. went from 0.667 to 0.627 retaining its strength and the PET reinforcing fiber I.V. went from 0.635 to 0.62 retaining its strength and giving a composite of very good strength (7.9×103 psi) and modulus (0.713×10 6 psi). Thus, the present invention specifies using copolymer PET fibers (with relatively low melt temperatures) as the matrix forming component so that molding could be carried out at temperatures below the temperature at which PET suffers significant molecular weight loss and accompanying loss of strength and stiffness.
Since both the binder matrix and the reinforcing polymers are both spinnable as fibers, they can be spun and blended, and air laid, carded, or wet laid as any other fibers and pre-consolidated into sheets which can then be heated and formed (molded) into useful shapes in a typical male/female press or a vacuum forming operation. The fiber blend as a mat can also be used, without preconsolidation, in a closed mold to form a useful article by subjecting the mold and its content to a complete heating and cooling cycle.
A further surprising advantage of this combination is that the surface finish of these composites is extremely smooth and it copies or surpasses the surface roughness of the mold. This is a result of the fact that unlike glass reinforcements PET conforms and retains the new configuration at low molding temperatures (about 220° C.).
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a photograph of the Tension Index for standard calibration surface.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The composite fiber mat is formed on a conventional card and then needle punched for structural integrity. The ratio of reinforcing fibers and matrix forming fibers in the mat to binder fibers in the mat could be adjusted by changing the feed rate of corresponding fibers. Though there is a preferred orientation in a carded mat, the extent of such orientation is not very significant and, for all practical purposes, the mat is considered as quasi-isotropic.
The reinforcing fibers used in the present invention consists of homopolymer staple fibers of 1.5 to 7 dpf (preferably 5.5 dpf) and cut length of 1" to 2.5" (preferably 1.5" long). These fibers usually have moderate crimp. Fibers of different geometry and differing number of holes (solid fibers to 4-hole fibers) were used in the present invention. These fibers are surface treated by a finish for better handling during carding or wet laying.
The binder (or matrix forming) fibers are lower melting copolymer fibers usually, but not exclusively crimped, of cut length 1" to 2.5" and 1.5 to 3.5 dpf. Binder fiber content in the mat is kept between 50% to 75% by weight. Better properties are observed when the binder fraction is 70%.
Several needle-punched pre-form mats are stacked to produce necessary thickness to make composite parts. It is found that better surface properties are obtained when a thin layer of binder fiber is placed on the outside of the fiber mat stack to be molded.
BLENDING PROCEDURE
For large quantities of fiber blend, the cutter blender technique is used in which blending is done along with cutting on a Lumnus cutter. The reinforcing fibers and binder fibers are passed through two cutter reels, each adjusted to produce staple fibers of required lengths, running at different speeds adjusted to obtain the required weight contribution of reinforcing and binder fibers in the blend. The cut fibers are collected in the same container. The blend thus obtained is reasonably uniform; however, by using a blender better uniformity is obtained.
GARNETING AND NEEDLE PUNCHING
Fiber blend obtained by the above-mentioned techniques are passed through a Garnet/Card and then through a needle puncher to form 22" wide 1/8" thick bats.
MOLDING PROCEDURE
About 80 grams of fiber mat (usually 5-7 layers) was stacked in a 7×7" picture frame mold coated with silicone. No attempt was made to dry the fiber blend prior to transferring fiber blend into the mold. The mold unit was then placed in a hydraulic press (Pasadena Hydraulic Press model B-230, 50 T capacity) whose plates were kept at a temperature 15° to 25° C. above the melting point of the binder fibers. The mold was kept between the plates under a 10 ton load for 15 minutes. The heat was then cut off and cold water was passed through the assembly and the mold was allowed to cool to a temperature below 100° C. The mold was then taken out of the press and the composite plaque was pushed out of the mold using a 3 ton Arbor press. Specimens were cut out from the plaques for tensile and blending measurements. These composites are extremely tough with high resilience and good surface characteristics. Average blending modulus and strength are calculated from several specimens.
TEST METHOD FOR SURFACE SMOOTHNESS
A tension meter, manufactured by PPG Industries, is used to characterize the surface smoothness (or roughness) of composites. The Tensio'n instrument is first calibrated on a smooth and even standard surface supplied by PPG. The instrument is placed over the surface and a Poloroid picture is taken by activating the flash. The picture thus obtained has 12 regions or rectangles. The rectangle designated by number 9 has widely spaced lines but the one corresponds to number 20 contain lines which are closely packed.
For the standard smooth surface, the lines in the rectangle 20 do not touch each other and are distinctly visible. These lines in the picture are images of a grid reflected on the surface of the composite, thus the finer the visible in the picture the better the surface. The Tensio'n index corresponds to the number assigned to the rectangle containing the closest packed which do not touch each other. Thus, the Tensio'n index for the calibration surface is 20.
After calibration, the instrument is placed over the composite sample and a picture is taken, and the Tensio'n Index is identified by reading the number assigned to the rectangle containing the finest and closest packed lines which do not touch each other.
TEST FOR DETERMINING BINDING MODULUS AND YIELD STRENGTH
ASTM D790-71 is the standard used to determine binding modulus and yield strength wherein a four point bending test is applied to evaluate bending modulus and yield strength of PET/PET composites. Samples used are of 1 inch width and usually about 1/8 inch thickness. The bending modulus is evaluated from the slope of the tangent of the initial part of the force-deflection curve. The yield strength is evaluated by finding the force required for a significant yield of the specimen under the four point bending condition and evaluating the maximum stress using the linear theory of bending.
TEST FOR DETERMINING INTRINSIC VISCOSITY (IV)
The intrinsic viscosity of PET or its copolymer derivatives were determined by measuring the solution efflux time in a calibrated Ostwald-Cannon-Fenske modified viscometer using a 0.32% solution of PET dissolved in a mixture of 25 parts of tri-fluroacetic acid and 75 parts of methylene chloride.
EXAMPLE 1
We obtained a uniform blend by carding crimped 5.5 dpf PET homopolymer fibers (T-374, 4-hole round) and crimped 3.75 dpf PET copolymer fibers (T-171, PET, DEG with 12.5% DEG) both 1.5" long, and needle-punching the nonwoven mat. The blend ratio (reinforcing fiber/binder fiber) was 30/70 by weight. The fibers had a standard textile lubricant antistat for processing on dry or wet laid equipment. The intake of reinforcing fibers and binder fibers is controlled to obtain the mat of required blend ratio. The dry mat weight was approximately 0.08 lbs./sq. ft. This mat was needle punched to a thickness of 1/8".
The nonwoven sheets are then stacked to form 7×7" batt of weight approximately 0.6 lbs./sq. ft. The mat is transferred to a 7×7 picture frame mold coated with standard mold release (silica) agent. The mold is closed and placed between the platens of a hydraulic press. The platens were kept at a temperature of 230° C. The mold and its contents are kept between the platens at a pressure of (15T/7×7") for approximately 15 minutes before water is allowed to circulate through the platens to cool the mold and its contents to a temperature to 80° C. Cooling process is started when the evidence of flash is sighted, if it happened earlier than 15 minutes. The composite plaque is then removed from the mold and is tested for its strength, modulus, and surface smoothness. The T-374/171 composite has a bending modulus of 720,000 psi and yield strength 5,400 psi in one direction and 75,000 psi in the other. The surface smoothness under (Tension index) was 16. By using "KAPTON" sheets on both sides of the mat before molding and removing these sheets after molding, the surface smoothness was improved. The Tension index for composites formed using a Class-A mold or by using "KAPTON" sheets was 18.
EXAMPLE 2
The procedure is identical to Example 1 using a composite preform layer composed of homopolymer PET reinforcing fibers and isothlate copolymer binder fibers (T-374 and D-262 fibers with 5.5 and 3 dpf, respectively; D-262 contains 30% of polyethylene isothalate). Molding temperature (235° C.) and molding time (20 minutes) are slightly higher compared to DEG copolymer binder fiber composites for 30/70 reinforcement/binder blend ratio. Isothalate composites provided a modulus of 700,000 psi and yield strength of 7,500 psi. Surface properties are excellent. The Tension Index for composites, without the use of "KAPTON" sheets was 15.
EXAMPLE 3
The procedure is identical to Example 1 using a composite preform layer composed of drawn PET as reinforcements (T-374) and undrawn PET (T-611, 6 dpf) as binder fibers (40/60 by weight). Molding is carried out at carefully controlled temperatures sufficient enough to melt the undrawn fibers while leaving the drawn fibers mostly intact. The Tension Index for the surface was 12, T-374/611 composites developed a bending modulus of 500,000 psi and having strength of 11,000 psi.
EXAMPLE 4
The procedure is identical to Example 1 using nonwoven sheets composed of PET reinforcing fibers (T-374) and isothalate (2GI) sheath-core copolymer binder fibers (D-269, PET/2GI/PET 50//50, dpf 4.0) in 30/70 ratio by weight. The molding temperature was slightly higher, 245° C. T-374/171 composites developed a modulus of 650,000 psi and strength 9,000 psi. The Tension Index for composites molded without using "KAPTON" sheets was 12.
EXAMPLE 5
The procedure is identical to Example 1 using a composite preform layer composed of PET fibers (T-372 solid round, dpf 1.5) and PET copolymer fibers (T-171) in 40/60 blend ratio. The bending modulus of resulting composite was 550,000 psi, and the bending strength was 11,000 psi. Tension Index of the surface Was 13.
EXAMPLE 6
The procedure is identical to Example 1 using a composite fiber batt composed of high IV 0.9, mid shrinkage, industrial PET yarn (uncrimped, 1.5" cut length) and a needle punched fiber blend of T-374 and 171 at 30/70 weight ratio. The preform fiber batt is obtained by stacking alternate layers of industrial yarn and T-374/171 fiber blend at 25/75 weight ratio so that both sides of the stack have T-171 fiber layer. The bending modulus of the resulting composite sheets was 900,000 psi and strength 9,500 psi. | Thermoplastic polyester fiber reinforced polyester panels which have extremely smooth and paintable surface and which can be deformed when hot to conform to a molded useful article without substantial loss in molecular weight or physical properties such as strength. | 3 |
This is a continuation of application Ser. No. 08/581,149 filed on Dec. 29, 1995, now U.S. Pat. No. 5,702,451.
FIELD OF THE INVENTION
The invention relates to a space holder for use with a vertebra or an intervertebral disk.
BACKGROUND OF THE INVENTION
Such a space holder is disclosed for example in document EP-B-O 268 115. This space holder comprises a stop formed by a ring on its inner side spaced from the corresponding free end of the jacket. The ring is connected with the jacket by means of bolts. In a particular embodiment a base plate comprising openings is mounted on the ring.
It is the object of the invention to simplify the space holder and make it more universally applicable.
SUMMARY OF THE INVENTION
In accord with the present invention, a space holder is provided, in particular, a vertebra or an intervertebral disk. The space holder comprises a jacket having apertures and a first and second edge. The edge has circumferentially adjacent recesses, each extending in a direction toward the opposite edge and a stop member is provided at least at one of the edges at a distance from that edge. The stop member is formed having an outer contour corresponding to the inner contour of the jacket. The stop member has nose-like projections at locations along its periphery corresponding to the recesses. Thus, the projections can engage the recesses.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of the jacket of the space holder;
FIG. 2 is a top view of a first embodiment of the member to be connected with the jacket;
FIG. 3 is a top view of a second embodiment of the member;
FIG. 3a is a sectional view along line IIIA--IIIA in FIG. 3;
FIG. 4 is a top view of a third embodiment of the member;
FIG. 5 is a sectioned lateral view along line V--V in FIG. 4;
FIG. 6 is a sectional view along line VI--VI in FIG. 7 through a further modified embodiment;
FIG. 7 is a top view of that embodiment;
FIG. 8 shows a section along line VIII--VIII in FIG. 9;
FIG. 9 is a top view of that further embodiment;
FIG. 10 shows a section along line X--X in FIG. 11; and
FIG. 11 is a top view of that further embodiment.
DESCRIPTION OF PREFERRED EMBODIMENTS
Further features and advantages of the invention will stand out from the description of embodiments with reference to the Figures.
As shown in particular in FIG. 1 the space holder comprises a closed jacket 1. The cross-section perpendicular to the longitudinal axis 2 of the jacket 1 is shaped in usual manner, in particular cylindrical, oval or kidneyshaped. In the manner shown in FIG. 1 the jacket 1 comprises diamond-shaped apertures 3, 4 having a longitudinal diagonal extending parallel to the jacket axis 2. Adjacent rows 3, 4 of such diamonds are mutually offset by half a diamond height. In this manner a grid is formed having webs 5, 6 intersecting at an acute angle and including equal angles with the longitudinal diagonal of the diamonds 3, 4. The upper edge 7 and the lower edge 8 both extend in a plane perpendicular to the longitudinal axis 2. The size of the diamonds 3, 4 and of the webs 5, 6 defining the diamonds is selected so that there is an integral number of diamonds in peripheral direction. The edges 7, 8 generate always an even number of V-shaped recesses 9, 10 or 9', 10', respectively, formed by the respective diamond base in peripheral direction. Owing to the above-described geometry the respective edge is quasi centrically symmetric to a point on the longitudinal axis 2 lying in the plane of the edge.
The first embodiment of a member 11 forming a stop shown in FIG. 2 is formed as a plate-shaped ring. The outer contour of the ring 12 corresponds to the inner contour of the jacket 1. Its dimensions are selected so that it can be pressed into the interior of the jacket but may also be pressed out again if desired, i.e. there is a frictional fit between the ring and the jacket 1. Equidistant projecting noses 15 are provided at the outer edge of the ring 12 in peripheral direction. The distance between two noses in peripheral direction equals the distance between two peripherally adjacent V-shaped recesses 9, 10. The cross-dimensions of the noses 15 in the plane of the plate are such that the noses fit smoothly into the base of the V-shaped recesses 9, 10. The length of the projecting noses corresponds to about the wall thickness of the associated jacket.
In use the jacket 1 is brought to the desired length by severing the upper edge 7 and the lower edge 8. Then one ring 12 is pressed into the interior of the jacket at the upper end and a second ring is pressed into the jacket interior at the lower end in such a manner that the noses 15 of the rings engage the corresponding basis of the associated V-shaped recesses 9, 10 and 9', 10', respectively.
Owing to the integral number of the V-shaped recesses and the central symmetry resulting therefrom one and the same member 11 may be used irrespective of the severing at the edge 7 or at the lowered edge 7' indicated in broken lines. If the edge is formed at the location 7' rather than at the location 7, then the ring 12 is inserted after rotation around its longitudinal axis, whereby using only one kind of rings the stock-keeping is reduced and the operation is simplified.
FIG. 3 shows a member 13 of a modified embodiment. Again it is a plate wherein the holes are formed by bore-shaped holes 14 distributed over the plate. All further features correspond to the member 11.
The FIGS. 4 and 5 show a member 16 according to a third embodiment. This member again comprises a plate which corresponds to the embodiment shown in FIG. 3 as regards the holes 14 and the noses 15. An outer ring 17 is arranged around the plate. As best shown in FIG. 5, the outer ring has a ring wall extending perpendicular to the plane of the plate and therefore parallel to the outer surface of the jacket 1. The length of the noses 15 is selected so as to be longer than the thickness of the jacket 1 just by an amount to form a clearance 18 between the plate, the noses and the ring which allows pushing the member onto the corresponding free end 7, 8 of the jacket 1 to fit the noses 15 into the base of the respective corresponding V-shaped recesses 9, 10, 9', 10'. The inner surface of the ring 17 then sits close to the outer surface of the jacket 1.
In the FIGS. 6 and 7 a member 19 according to a further embodiment is shown. It has a plate-shaped ring 12 which is identical with the ring shown in FIG. 2. As best shown in FIG. 6 an edge portion 20 having an outer contour which corresponds to the inner contour of the jacket 1 is provided on one surface of this ring and the free end of the edge portion 20 opposite to the plate 12 has equidistant prongs 21 in circumferential direction. The height of the prongs 21 above the plate 12 is so that when inserted the prongs extend beyond the edge 7 or 8, resp., of the jacket 1 almost to their base.
The embodiment of a member 22 shown in FIGS. 8 and 9 differs from the previously described embodiment only in that the base of the prongs is not in a plane parallel to the plate 12, but in a plane which is inclined with respect to the plate 12. The edge formed by the prongs lies also in a plane which is inclined with respect to the plate plane of the ring 12. The inclination is preferably between 8 and 10°.
The embodiment of the member 24 shown in FIGS. 10 and 11 differs from the embodiment according to FIGS. 8 and 9 in that the edge portion 20 is inclined with respect to the plane of the plate, i.e. with an angle other than 90° with respect to the plate plane of the ring 12.
In operation both embodiments, i.e. the members 19 and 22, respectively, are inserted into the jacket in the same manner as the previously described embodiments so that the projecting noses 15 of the ring 12 lie in the lowermost parts of the V-shaped recesses 9, 10 and the prongs extend outwardly beyond the edge of the jacket. In the embodiment shown in FIGS. 6 and 7 the prongs 21 or 21' may be cut to different lengths, for example along the broken line 23 to form a wedge-shaped insert. Similarly the edge of the member 22 can be cut so that the predetermined angle between the outer edge and the plate-shaped ring 12 is varied. In this manner it is possible to obtain, using few basic members, space holders having different wedge angles.
The outer contour of the respective rings 12 and 13 is, of course, determined as a function of the respective inner contour of the associated jacket.
According to modifications of the above-described particularly preferred embodiments the recesses of the edge may have other shapes in place of the V-shape, for example U-shaped or slit-shaped recesses. | A space holder in particular for a vertebra or an intervertebral disk is provided. The space holder comprises a jacket (1) having apertures (9, 10) and a first and second edge (7, 8). The edge has circumferentially adjacent recesses (9, 10; 9', 10') each extending in direction towards the other edge and a stop provided at at least one of the edges spaced from the outer edge. In order to provide for an easy manufacture and operation of the space holder the stop is formed by a member (11, 13, 16, 22) having an outer contour corresponding to the inner contour of the jacket (1) and nose-like projections (15) for engaging the recesses (9, 10) are provided at those locations of the periphery of the stop which correspond to the recesses (9, 10; 9', 10'). | 0 |
This is a continuation of application Ser. No. 08/201,363 filed Feb. 24, 1994, U.S. Pat. No. 5,453,022.
BACKGROUND OF THE INVENTION
The present invention generally relates to an actuating device.
More particularly, it relates to a device for an electrically controllable actuator, in particular a magnetic valve which is connected with at least one control conductor.
Electrically controllable magnetic valves connected with a conventional electric conductor which supplies the magnetic head with voltage for actuation of the valve are known in the art. Such valve controls are relatively expensive and require substantial installation expenses.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a device which avoids the disadvantages of the prior art.
More particularly, it is an object of the present invention to provide a device which with simple means provides a rationally installable control connection for a single conductor or a multi-conductor bus system.
In keeping with these objects and with others which will become apparent hereinafter, one feature of the present invention resides, briefly stated, in a arrangement for an electrically controllable actuator, especially a magnetic valve, connectable with at least one control conductor, wherein in accordance with the present invention an electric actuator is associated with a through connection useable without a tool and arranged so that the control conductor uninterruptibly contacts with the through connection.
When the device is designed in accordance with the present invention, it eliminates the disadvantages of the prior art and achieves the specified highly advantageous results.
The novel features which are considered as 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 specific embodiments when read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a view showing an inventive device with control conductors of a bus system provided in an upper housing part;
FIG. 2 is a plan view of the control conductor extending through the housing;
FIG. 3 is a front view of the inventive device with the control conductor extending through the housing in a section;
FIG. 4 is a sectioned side view of the of FIG. 3;
FIG. 5 is another sectioned view of the device of FIG. 3 with an open housing cover and an integrated mounting screw;
FIG. 6 is a general view of another device in accordance with the present invention;
FIG. 7 is a front view of the inventive device shown in FIG. 6;
FIG. 8 is a side view of the inventive device shown in FIG. 6;
FIG. 9 is a plan view of the inventive device shown in FIG. 1;
FIG. 10 is a general view of still a further device in accordance with the present invention;
FIG. 11 is a front view of the inventive device for FIG. 10;
FIG. 12 is a side view of the inventive device for FIG. 10;
FIG. 13 is a plan view of the inventive device for FIG. 10;
FIG. 14 is a partially sectioned view of the device of FIG. 12 on an enlarged scale;
FIG. 15 is a partially sectioned plan view of the inventive device of FIG. 14;
FIG. 16 is a front view of a housing connected with a device of FIG. 14;
FIG. 17 is a view showing the housing of the inventive device of FIG. 16 with a removed front cover wall; and
FIG. 18 is a general view of a device in accordance with a further embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A device shown in FIG. 1 is identified with reference numeral 1 and has a valve 2 and an electromagnetic actuator arranged in the valve. The actuator can be provided with a not shown electric coil and electromagnetically displaceable armature.
A coupling part 4 is formed on one side of the actuator 3 so that for example the wire ends of the electric coil contact in the coupling part. For example three electric contact tongues 5, 6, 7 extend from the coupling 4 and can be provided preferably with a flat rectangular cross-section.
A housing 8 composed for example of synthetic plastic material can be arranged on the coupling part 4 of the actuator 3. The housing 8 is mounted releasably and plugged with the projecting contact tongues 5, 6, 7. The housing 8 can be substantially rectangular and is provided with a front wall 9, a rear wall 10, two side walls 11, 12, a bottom 13 and a cover 14. The cover 14 closes an upper part 15 of the housing 8 so that no dust or water can penetrate into the housing 8. For preventing losing of the cover 14, it can be advantageous to mount the cover 14 turnably on the rear wall 10 of the housing by a hinge 16. In accordance with a preferable embodiment, the hinge 16 is formed of one piece with the cover 14 and the housing 8 as a so-called film hinge. The closing of the cover 14 can be performed preferably by means of an integrated snap connection 17 which for example includes a projection 18 provided on the cover 4 and engageable into an opening 19 of the housing 8. The snap connection 17 can be provided preferably at the front wall 9 of the housing 8 located opposite to the hinge 16, so as to enable an unobjectionable easy access to it.
The housing 8 is mounted on the coupling part 4 by a screw 20 which extends through the front wall 9, a printed board 21 arranged in the housing 8, and the rear wall 10 of the housing and is screwed with a threaded end 22 in a corresponding nut thread of the coupling part 4. The screw 20 can have a head 23 which is supported in a recess 24 of the front wall 9 in a countersunk fashion. The printed board 21 which is arranged in a chamber 25 of the housing 8 between the front wall 9 and the rear wall 10 is substantially parallel to the walls and can extend from the bottom 13 to the upper part 15. It is provided with contact passages 26 arranged so that they contact with conductor tracks of the printed board 21 and the contact tongues 5, 6, 7 engage in the contact passages.
In the region of the upper part 15 of the housing preferably three through connections 27, 28, 29 are provided for a single or a multiple conductor bus system and contacted with respective control conductors 30, 31, 32. Insulating webs 33 and 34 can be provided for spacing the control conductors 30, 31, 32 from one another. For this purpose it is advantageous when the through connections 27, 28, 29 are arranged in the upper part 15 of the housing in the longitudinal direction of the control conductors 30, 31, 32 with a distance one behind the other and with the lateral offset relative to one another.
Each of the through connections 27, 28, 29 can be substantially U-shaped and provided with contact slot 35 limited by two opposite knife blade contacts 36, 37. In the upper region of the contact slot 35 an insertion opening 38 for the control conductors 30, 31, 32 can be formed. It is limited by two insertion inclines 39, 40 formed on the knife blade contacts 36, 37. For connecting the control conductors 30, 31, 32 they are simply pressed from above through the insertion opening 38 into the contact slot 35. The insulation 41 of the electrical conductor 42 is cut through by the knife blade contacts 36, 37 so that the knife blade contacts 36, 37 contact with the electrical conductor 42. The control conductors 30, 31, 32 is however not separated and as well known is connected with clamp contacts while the control conductors 30, 31, 32 contact without interruption with the through connections 27, 28, 29.
Moreover, it can be advantageous when a sealing member 43, 44 is respectively arranged in the upper part 15 of the housing 8 on the opposite side walls 11, 12, so that the control conductors 30, 31, 32, can be tightly surrounded by the sealing members and no impurities can penetrate into the housing 8.
The conductor tracks of the printed conductor board 21 contact with the contact tongues 5, 6, 7 and the through connections 27, 28, 29. The chamber 25 which accommodates the printed board 21 can also contain a control module 45 provided between the contact tongues 5, 6, 7 of the actuator 3 and the through connections 27, 28, 29. The control module 45 can evaluate the signals received through the control conductors 30, 31, 32 and supply the signals to the actuator 3 or when needed through the control conductors 30, 31, 32 to one or more further actuating devices.
In the shown embodiment, the through connections 27, 28, 29 for the control conductors 30, 31, 32 and the control module 45 provided on the printed board 21 are assembled as a nut in the housing 8 which advantageously can be plugged on the contact tongues 5, 6, 7. This pluggable unit can be formed as an adaptor mountable later on the actuator 3, so that it can be equipped with such an adaptor at any time.
In accordance with another embodiment which is not shown in the drawings, it can be advantageous when the through connections 27, 28, 29 are already fixedly mounted on the actuator 3 or integrated in it in a factory. Moreover, it can be advantageous when the control module 45 is provided already on the actuator 3 so as to form a compact prefabricated unit.
An important advantage of the inventive arrangement is that a bus control is produced with a connection box for example for two-conductor technique, and the control conductors can be installed uninterruptingly with simple means manually.
The device in accordance with the embodiment shown in FIGS. 6-9 and identified with reference numeral 101 has a valve 102 with an electromagnetic actuator 103 having an actuator housing 104 which can accommodate a not shown electric coil and an electromagnetically displaceable armature.
A coupling part 105 can be arranged on one side of the actuator 103. It can be inserted into a recess of the actuator housing 104 and provided with contacts for wire ends of the electric coil and preferably with three projecting flat-rectangular contact tongues.
A housing 106 composed for example of a synthetic plastic material can be plugged on the coupling part 105 and has a substantially rectangular shape. It can have a rear wall 107, two side walls 108, 109, a bottom 110, an upper wall 111 and a releasable cover wall 112 which forms a front wall of the housing. The cover wall closes a housing opening 113 provided on a front side of the housing 106 which is remote from the actuator 103. The housing 106 can be releasably mounted on the coupling part 105 by a screw 114. The screw engages in a nut thread of the coupling part 105 and its head 115 preferably supported in a recess 116 of the cover wall 112 in a countersunk manner.
Opposite located recesses 117 can be formed preferably in the side walls 108, 109. They are substantially rectangular and adjoin the housing opening 113, so that the recesses 117 are limited at three sides and are open from the front in the plane of the housing opening 113 with the removable cover wall 112. When the cover wall 112 is removed, a control conductor 118 can be inserted in the recesses 113, It can be formed single-wire for a single conductor bus system or three-wire for a multi-conductor bus system as designed as a flat conductor cable. For the utilization of a multi-wire flat conductor cable the recess 117 can be formed so that it width is approximately equal to the width of the flat conductor cable. Troughs 119 can be formed on the base of the recesses 117 and the convex rounds of the control conductor 118 can be engaged in the troughs in a form-locking manner.
On the removable cover wall 112 on its opposite sides, preferably rectangular projections 120 can be formed an engage in the recesses 117. Preferably the end sides of the projections 112 which face the control conductor 118 can be also provided with such troughs 119. The convex rounds of the control conductor 118 form-lockingly engage in the troughs 119 so as to provide a tight closure and a reliable hold of the control conductor 118.
As can be seen from FIGS. 6, 7 and 9, an adjusting member 121 can be provided on the upper wall 111 of the housing 106. An addressing switch 140 supported in the housing 106 as shown in FIG. 12 can be adjusted by the adjusting member 121 from outside without removing of the cover wall 112.
The device in accordance with the embodiment shown in FIGS. 10-17 differs from the embodiment of FIGS. 6-9 substantially in that no coupling part 105 is provided between the actuator 103 and the housing 106 to form a distance therebetween. The housing 106 abuts directly against the actuator 103 so as to form a compact unit. The housing 106 can be integrated directly on the actuator housing 104 and will be removably connected with it. For this purpose, the housing 106 on its rear wall 107 can be provided with one or several holding webs 122 insertable in a recess 123 of the actuator housing 104 and engageable with the wall of the actuator housing 104 as shown in FIG. 9.
As can be seen from FIGS. 10, 11 and 16, the adjusting member 121 for the addressing switch 140 is provided in this case not on the upper wall 111 but instead of the removable cover wall 112. Therefore the adjustment of the addressing switch 140 can be performed from the front side.
As shown in FIGS. 11 and 12, for the use of several one-wire control conductors 118 it can be favorable when the recess 117 is formed for example by three small slots so that an individual conductor can be inserted in each slot. A trough 119 for receiving the convex round of the control conductor 118 can be formed in the bottom of the slot. Three web-shaped small projections 120 can be formed for example on the removable cover wall 112 at opposite sides and engage in the slot-shaped recesses 117. For this purpose it is advantageous when the end side of each projection 120 facing the control conductor 118 is provided with a trough 119, in which the convex round of the control conductor 118 engages in a form-locking member. Therefore for each individual bus conductor 118 a reliable holding and tight housing closure is provided.
As can be seen from FIGS. 14-17, three through connections 124, 125, 126 can be provided in the housing 106. A conductor of the control conductor 118 can electrically contact each throughgoing connection 124, 125, 126. For arranging the individual conductors of the control conductor 118 at a distance from one another, it can be favorable to arrange the through connections 124, 125, 126 which are preferably supported in the upper part of the housing 106 by the screw 114, with a lateral offset relative to one another in the longitudinal direction of the control conductor 118.
Each through connection 124, 125, 126 can be substantially U-shaped and provided with a contact slot 127 limited by two opposite knife blade contacts 128, 129. An insertion opening 130 can be formed at the free end of the contact slot 127 and limited by two insertion inclines formed on the knife blade contacts 128, 129. For connecting the control conductor 118 the respective conductor is pressed through the insertion opening 130 into the contact slot 127. The insulation of the conductor is cut through by the knife blade contact 128, 129 so that the latter contact with the electrical conductors. The control conductor 118 is however not separated, but instead contact without interruption with the through connections 124, 125, 126.
A printed board 131 can be provided in the housing 106. Preferably it is supported at a distance parallel to the plane of the rear wall 107 and limited by the side walls 108, 109 as well as by the bottom 108 and the upper wall 111. A pin 132 can be formed substantially in the center of the housing 106 on the rear wall 107 and a counter pin 133 can be formed on the cover wall 112 so that printed board 131 can be held between them. The through connections 124, 125, 126 can be mounted preferably on the printed board 131 so that the insertion opening 130 of the contact slot 127 faces the housing opening 113 or the cover wall 112 and is located in the plane of the recesses 117 or slots formed in the side walls 108, 109.
At least one contact 134 for a connection 135 of an electric coil 136 of the actuator 103 can be arranged on the printed board 131. Moreover, a magnetic closing disc 137 of the actuator 103 can be mounted under the bottom 110 of the housing 106 by a contact screw 138. Further, it can be favorable for the system control when an integrated circuit 139 and the address switch 140 are provided on the printed board 131 and supported preferably in the lower part of the housing 106.
As can be seen from FIG. 14 the screw 114 extends through an opening of a counter pin 133 formed on the cover wall 112 and has a free end engaging in a nut thread formed in the rear wall 107 or in the pin 132. During tightening of the screw 114 the housing opening 113 is tightly closed by the cover wall 112, and the latter abuts against projections 141 of the housing 106.
The inventive arrangement 201 shown in FIG. 18 has a substantially rectangular distributor 202 with preferably eight magnetic valves 203 arranged in series closely near one another on the front side of the distributor. Therefore a space saving integral compact module 204 is formed.
A plurality of medium-guiding passages can be provided in the distributor 202 and conductor connections 204 arranged at the upper end side of the distributor 202 can be associated with the passages. The conductor connections 105 serve for connection with not shown hose or tubular conduits in which the medium, for example air, is supplied. The valve body 206 of the magnetic valve 203 can be preferably removably mounted on a web-shaped projection 207 projecting from the front side of the distributor 202 and connected with the passages of the distributor 202.
Moreover, a contact rail 208 extending parallel to the projection 207 can be provided on the front side of the distributor 202. It has a contact web 209 which is arranged on a longitudinal side 210 of the distributor 202 and extends at the rear side opposite to the front side. The actuator 211 which is connected with the valve body 206 and formed for example as electromagnetic head, can be plugged on the contact rail 208 to provide an electrical contacting for a bus control.
It is preferable to provide an integrated switching circuit 212 and an addressing switch 213 which can be supported preferably on or in the contact rail 208 and permit an individual control of the magnetic valve 203 through the bus system. Moreover, a device plug 214 can be provided for the connection of the sensors. It is associated with the magnetic valves 203 and can be arranged at the front side of the distributor 202 on the rail 215 located at the side opposite to the contact rail 208 and parallel near the projection 207.
The compact module 204 can be mounted on a mounting rail 216 with the side of the distributor 202. The mounting rail 216 can have a substantially hat-shaped cross-section. For example a three-wire bus control conductor 217 can be supported inside the mounting rail 216 so as to be protected. Preferably it extends continuously uninterruptingly near the base wall 218 of the mounting rail 216 and preferably arranged on a supported wall 219 extending parallel to the base wall 218.
A part of the contact web 209 which extends over the distributor 202 can be provided with through connection 220. The connection contacts with the control conductor 217 uninterruptingly so that during mounting or plugging of the distributor 202 on the opening side opposite to the base wall 218, the mounting rail 216 provides automatically, without pressure manipulations, the contacting of the through connection 220 with the control conductor 217. For this purpose, two contact knife blades of the U-shaped through connection 220 surround the wire of the control conductor 217. The contacting is performed also inside the hatshaped profile of the mounting rail 216. Therefore a fast mounting of several magnetic valves 203 assembled to form a small contact module 204 and the reliable contacting of the bus control system are provided.
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 types described above.
While the invention has been illustrated and described as embodied in an actuating device, it is not intended to be limited to the details shown, since various modifications and structural changes may be made without departing in any way from the spirit of the present invention.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention. | An actuating device has an actuator, at least one control conductor conned with the actuator, and at least one through connection useable without a tool and associated with the electrical actuator, the control conductor uninterruptibly contacting with the through connection. | 8 |
BACKGROUND OF THE INVENTIONS
[0001] The inventions described herein relate to closure devices, and in particular, relate to a cap and liner (such as a tamper indicating seal or membrane) combination for bottles. The preferred cap of the present inventions is at least partially transparent or translucent to allow a customer to perceive a printed or colored liner or membrane through the cap at the point of purchase.
[0002] To identify the contents of a bottle, it is well known in the art to use opaque, colored caps, to apply adhesive backed labels to the top surface of a cap, and/or to print directly on the top of the cap. In the field of bottling and selling milk, bottlers use different colored caps to differentiate one kind of milk from another; i.e., red caps may be used to designate whole milk, light blue for skim milk, and yellow for 1%, etc. Colored caps are also used to designate different kinds of juices or different flavors of beverages.
[0003] To provide a liquid-tight seal on a bottle, it is well known in the art to use a seal, or liner, in combination with the cap. Cap suppliers often sell their colored caps with the liners placed on the inside of the cap. Because the liner is pre-installed on the inside of the cap, the liner is pressed against the bottle neck into intimate contact with the lip of the bottle opening when the cap is applied to the bottle. Two types of liners are generally in use today with blow molded bottles. The first type of liner is made of a soft pliable sealing material, such as a foam. The second type of liner, a foil liner, has a heat sensitive surface which can be heated into sealing engagement with the lip of a container neck by induction heating to form a membrane sealing the container closed.
[0004] In the bottling industry, it is well known to include tamper-evident features. With blow-molded bottles, bottlers often incorporate two levels of tamper evident features. A first level is incorporated into the design of the cap and a second level is incorporated underneath the cap. For a first level of tamper evidence, caps on bottles sold to consumers include an integrally formed (i.e., injection molded) feature such as a ratchet ring for threaded caps and a pull-tab for push-on caps. For a second level of tamper evidence, liners are often used. In particular, bottlers often use a liner that can be heat sealed around the opening of the bottle. The heat sealed liners are tamper evident in that, once the liner is removed from the lip of the bottle opening, the liner cannot be easily reattached to the bottle opening. Therefore, upon opening the bottle at home, the consumer can ascertain whether the product has been tampered with by visually verifying that the liner is present and sealed to the bottle opening.
[0005] While the combination of bottle caps and liners of the types currently in use provides for an acceptable means of product identification and sealing, these combinations do have their limitations. First, it is more costly to manufacture caps in an array of colors. This is because it takes time to change an injection molding machine over from one color to another, and because keeping inventory of various colors of caps means that more investment is required for that inventory and for the equipment and personnel to manage that inventory.
[0006] Second, the opaque caps of the prior art prevent consumers from ascertaining at the point of purchase whether the second level of tamper evidence—i.e. the heat seal label—has been tampered with. As discussed above, the prior art caps incorporate a first level tamper-evident feature into the cap that prevents the consumer from verifying the condition of the seal until after the purchase is made when the consumer removes the cap. Generally, consumers do not remove the cap until they have arrived at home, sometimes days after they have made the purchase. In the event that the consumer finds a broken seal, it will be very inconvenient for the consumer to return the product to the store.
[0007] Therefore, there is a need for a cap and liner combination which will provide a cost effective method of identifying the contents of a bottle. There is also a need for a cap and liner combination which will allow a consumer to ascertain, at the point of purchase, whether someone has tampered with the tamper-evident seal.
SUMMARY OF THE INVENTIONS
[0008] The present inventions relate to a clear cap and liner combination for bottles which solves the problems of the prior art. The preferred cap of the present inventions is at least partially transparent or translucent to allow a customer to perceive the liner through the cap at the point of purchase. In one embodiment, the liner serves as a label, wherein the customer can perceive, through the cap, information such as printing. The printing can be indicative of the product, such as the name of the manufacturer, the name of the bottle contents, ingredients, and/or nutritional data. Because the liner can be easily customized to identify the product contained in a bottle, only one version of a cap need be manufactured for use with many different products. In a second embodiment, the liner serves as a tamper evident seal, wherein the customer can perceive, through the cap, whether the seal has been breached. As such, the consumer will know, at the point of purchase, whether or not the product has been tampered with. In a third embodiment, the liner serves as both a label and a seal, wherein the liner creates a liquid resistant seal between the cap and the opening of the bottle. In a forth embodiment, the liner serves as both a label and a tamper evident seal.
[0009] Although not limited as such, the preferred application for the present inventions is as a closure device for blow-molded bottles. There are two types of caps which are generally in use today with blow-molded bottles: push-on caps and screw-on caps. These kinds of caps are often injection molded with polyethylene (both high and low density) or polypropylene, a common material used in injection molding. [polishing mold surfaces is important and/or reducing the thickness of the top wall, but need 0.025″ thickness]
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] These and other features, aspects, objects, and advantages of the inventions described and claimed herein will be become better understood upon consideration of the following detailed description, appended claims and accompanying drawings where:
[0011] FIG. 1 is an exploded perspective view of the bottle cap and liner of the present invention with a corresponding blow-molded bottle;
[0012] FIG. 2 is a top view of the present invention which is applied to a corresponding blow-molded bottle;
[0013] FIG. 3 is a cross-sectional view of a screw-on cap with a liner placed between the underside of the cap and the lip of a bottle neck;
[0014] FIG. 4 is a top view of a standard heat seal liner;
[0015] FIG. 5 is a perspective view of an improved heat seal liner; and,
[0016] FIG. 6 is a cross-sectional view of a push-on cap with a liner placed between the underside of the cap and the lip of a bottle neck.
[0017] It should be understood that the drawings are not necessarily to scale and that the embodiments are sometimes illustrated by graphic symbols, phantom lines, diagrammatic representations and fragmentary views. In certain instances, details which are not necessary for an understanding of the inventions described and claimed herein or which render other details difficult to perceive may have been omitted. It should be understood, of course, that the inventions described herein are not necessarily limited to the particular embodiments illustrated herein.
[0018] Like reference numerals will be used to refer to like or similar parts from Figure to Figure in the following description of the drawings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] FIG. 1 generally depicts one of the preferred embodiments of the present invention. An exploded perspective view of a container 14 , bottle cap 2 a , liner 4 , and bottle neck 6 a combination is shown. As demonstrated in FIGS. 1 and 2 , the cap 2 a is non-opaque such that printing on the liner 4 can be perceived through the cap 2 a.
[0020] The bottle cap 2 a shown in FIG. 1 is a screw-on type cap 2 a . Screw-on caps 2 a typically comprise a circular cover 20 a , a skirt 22 a depending from the peripheral edge of the circular cover 20 a , and a ratchet ring 24 which is frangibly attached below the skirt 22 a . On the inside surface 34 a of the skirt 22 a are threads 26 —preferably four—which are adapted to mate with corresponding threads 66 on the neck 6 a of the bottle. The ratchet ring 24 has internal teeth 28 for engagement with the bottle neck 6 a , which has external teeth 74 . Every other one of the internal teeth 28 are attached to a plurality of semi-circular outwardly directed tabs 30 which are equally spaced around the periphery of the skirt 22 a , forming the frangible connection between the ratchet ring 24 and the bottle cap 2 a . For further details regarding the screw-on cap 2 a , see U.S. Pat. No. 6,003,701 which is incorporated herein by reference.
[0021] Although the cap 2 a depicted in FIG. I is entirely non-opaque, the claims cover caps 2 a in which only a portion of the cap 2 a is non-opaque; i.e. the cap 2 a would have a window. Accordingly, at least a portion of the cap 2 a of the present invention is non-opaque such that the liner 4 can be perceived through the cap 2 a , preferably through the circular cover 20 a of the cap 2 a . The non-opaque cap 2 a may be translucent or transparent. However, it is preferable that at least the entire circular cover 20 a is transparent to prevent distortion of any printing which is present on the liner 4 . Distortion can minimized by careful resin selection/processing and mold polishing. The mold in the area that forms the top of the cap is preferably polished to SPI A-1, so that any surface diffraction of light passing through top or lid of the cap is minimized, making the top of the cap as transparent as possible. However, for certain applications, distortion may be a desired characteristic. For such an application, the cap 4 may be translucent so that the label 4 is at least still perceivable.
[0022] The cap 2 a is preferably colorless, but some applications may require a colored cap. Nevertheless, the colored caps are non-opaque and are simply characterized by a hue. Both colorless and colored, non-opaque caps are covered by the claims herein.
[0023] As shown in FIG. 1 , the liner 4 is displaced between the bottle cap 2 a and bottle neck 6 a . Two general types of liners 4 are preferred for the present invention: foam or foil. Foam liners 4 generally form a seal when compressed between the cap 2 a and the lip 68 of the bottle neck 6 a . Foil liners 4 are generally used when the bottler desires to form a heat seal on the lip 68 of the bottle neck 6 a . A material that is suitable for the foam liner 4 is a foamed sheet material made of styrene and having a thickness for some applications of about 0.040″ inches. However, a person of ordinary skill in the art would know that many other materials can be used as an acceptable substitute to form the foam liner 4 . Foil liners 4 are generally constructed of multiple layers. At a minimum, the foil liner must have a metal (preferably aluminum) layer with a plastic layer laminated on the underside of the metal layer to facilitate induction heat sealing to the lip 68 of the bottle neck 6 a . Some liners have a paper (or foam) backing adhered (via an adhesive) to the metal layer.
[0024] If an induction sealed liner (or other tamper indicating interior seal) is used, it may be possible to do any of the following: 1 ) completely eliminate a ratchet ring in the context of a screw cap 2 ) completely eliminate the pull tab in the context of a push-on cap, or 3 ) otherwise use simple non-tamper-indicating closure, and rely entirely on the inner tamper indicating seal, particularly when its condition (or presence) is readily visible through a transparent or translucent cap in accordance with the present invention. Among other things, the elimination of a ratchet ring or pull tab will reduce the amount of plastic used to make the cap, and will allow the shipment of more closures in a box, when the closure are shipped.
[0025] It is also contemplated that other liners 4 can be used that do not form a seal at the lip 68 of the bottle neck 6 a . Such a liner 4 may be used to provide an indication of the contents of the bottle 62 a and not for sealing purposes. Such a non-sealing liner 4 could be comprised of a laminated paper or a simple foam disc.
[0026] The preferred liner 4 of the present invention provides an indication of the contents of the bottle through printing or coloring. An example of such a liner 4 is shown in FIG. 2 , which is a top view of a bottle cap 2 a and liner 4 of the present invention placed on top of a bottle neck. The printing on the label 4 , “2%,” can be perceived through the cap 2 a , being that the cap 2 a is transparent. In some cases, depending on the thickness, softness and surface properties of the foam to which printing ink is applied, it may be useful to apply a covering layer, such as a lacquer or varnish or thin protective adhesive sheet to protect the printing from chipping or smearing.
[0027] The diameter of the liner 4 is generally sized to correspond to the diameter of the inside surface 34 a of the bottle cap 2 a such that the liner 4 fits snugly inside of the bottle cap 2 a . It is preferable that the liner 4 is held firmly against the underside of the circular cover 20 a to optimize printing clarity as seen through the circular cover 20 a . At a minimum, however, the bottle cap 2 a must hold the liner 4 near the underside of the circular cover 20 a such that the liner 4 does not fall out of the bottle cap during the bottling operations. This can be achieved through several means. First, the liner 4 can be held inside of the bottle cap 2 a by friction. Alternatively, holding means could be formed one the inside surface 34 a of the bottle cap 2 a to engage with the periphery of the liner 4 , such as an inwardly directed projection. As shown in FIG. 3 , the internal threads 26 of the preferred embodiment double as holding means, wherein the ends 32 of the threads 26 retain the liner 4 in place.
[0028] Referring back to FIG. 1 , the bottle neck 6 a , which is used with the present invention, is generally positioned at the top of the body 62 a of a blow-molded bottle and is formed of a generally cylindrical exterior surface 64 a . At the top edge of the exterior surface 64 a is a lip 68 which defines an opening 70 . The lip 68 is generally inwardly directed to form a sealing surface for sealing with the liner 4 and bottle cap 2 a . The exterior surface 64 a preferably includes four threads 66 which engage threads 26 on the inside surface of the cap skirt 6 .
[0029] Further, the bottle neck 6 a preferably includes two ratchet portions 72 having a plurality of ratchet teeth 74 . The two ratchet portions 72 are located diametrically opposite each other on the exterior surface 64 a below the threads 66 . The container 14 also includes a circumferential “bumper roll” or transfer ring 76 located below the ratchet portions 72 to facilitate gripping the bottle during the filling operation and grabbing the bottle during the loading of the bottle into a shipping container.
[0030] The liner 4 a in FIG. 3 is shown affixed to the lip 68 of the bottle neck 6 a by heat sealing. Heat sealing can be performed by conduction or induction; however, induction is the preferred method for heat sealing the liner 4 to the blow-molded bottle. As better shown in FIG. 4 , the liner 4 a is a standard liner having a semicircular tab 40 extending from the periphery of the liner 4 a . The tab 40 provides a gripping point to aid in the removal of the liner 4 a by the consumer. Even though a standard foil liner is depicted in FIG. 3 , the invention is not limited to this embodiment. For example, the liner 4 b may have a paper, foam or other backing. The liner 4 b of FIG. 5 also has a semicircular grip or tab 42 , although the tab is much larger than the grip or pull tab 40 . The diameter of the grip or tab 42 is preferably equal to the diameter of the liner 4 b . Furthermore, the tab 42 extends from a diameter of the liner 4 b instead of the periphery. To remove the liner 4 b , the consumer would grip the tab 42 , which is originally flush with the liner 4 b , and pull the tab upward until the tab 42 lies in a plane roughly perpendicular to the liner 4 b . Next, the consumer would apply upward force to the tab 42 to remove the liner 4 b from the lip 68 of the bottle neck 6 a . The liner 4 b is preferable to the liner 4 a , because the tab 40 of the liner 4 a could interfere with application of the bottle cap 4 a to the bottle neck 6 a ; the tab 40 is generally folded downward and is displaced between the threads 26 of the bottle cap 4 a and the threads 66 of the bottle neck 6 a . The liner 4 b is commercially available from Unipac (of Canada) under the trademark Lift ‘n’ Peel™.
[0031] Although described herein with particular reference to screw on caps, the present inventions can also be used with push on caps 2 b , as shown in FIG. 6 , and/or push-on—screw-off caps. Push-on caps 2 b typically comprise a circular cover 20 b , a skirt 22 b depending from the circular cover 20 b , and a pull-tab 23 which is frangibly connected to the bottom of the skirt 22 b . The circular cover 20 b typically has a greater diameter than the cross-section of the skirt 22 b whereby the cover 20 b extends beyond the periphery of the skirt 22 b to provide a gripping surface for removing the cap 2 b from the bottle 62 b . The pull-tab 23 is integrally molded with the cap 2 b . The pull-tab 23 is used to separate the lower part of skirt 22 b from the upper part of the skirt 22 b by tearing the skirt along a scored tear line 21 . A lower bead 25 on the inside surface of the lower part of the skirt 22 b engages with the corresponding lower rib 27 on the bottle neck 6 b . The lower bead 25 is located such that the cap 2 b cannot be removed by the customer without first tearing the lower part of the skirt it away from the cap 2 b along the tear line 21 . An upper bead 29 on the inside surface of the skirt 22 b engages with a corresponding rib upper rib 31 on the exterior of the bottle neck 6 b for retaining the cap 2 b on the bottle 62 b after the lower part of the skirt has been removed, such that the cap 2 b can be reapplied to and retained by the upper rib 31 .
[0032] The application has particularly beneficial application in the field of blow-molded containers, such as those typically used for milk and juice to which a foil liner is typically and preferably applied. However, closures made in accordance with the invention will also have beneficial application on other containers, such as fiberboard containers with fitments that include an internal tamper-indicating pull ring (or grip) and frangible membrane, such as those shown in U.S. Pat. No. 6,464,096. Using a transparent overcap as part of such a fitment will allow a consumer to easily see whether the membrane is intact without having to remove the overcap. As used herein, the term “tamper-indicating seal” is intended to include both a foil liner, as discussed above, and a removeable membrane with a grip to help remove the membrane as discussed in the '096 patent referred to above.
[0033] Although the inventions described and claimed herein (collectively sometimes referred to herein as the “invention”—singular) have been described in considerable detail with reference to certain preferred embodiments, one skilled in the art will appreciate that the inventions described and claimed herein can be practiced by other than the preferred embodiments, which have been presented for purposes of illustration and not of limitation. Therefore, the spirit and scope of the appended claims should not be limited to the description of the preferred embodiments contained herein. | The inventions disclosed herein include a clear cap and tamper-indicating seal combination for containers. The preferred cap is at least partially non-opaque to allow a customer to perceive the tamper-indicating seal through the cap at the point of purchase. In a first embodiment, the tamper-indicating seal serves as a label, wherein the customer can perceive, through the cap, information such as printing which is indicative of the contents of the container. In a second embodiment, the tamper-indicating seal serves as a tamper evident seal, wherein the customer can perceive, through the cap, at the point of purchase, whether the seal has been breached. In a third embodiment, the tamper-indicating seal serves as both a label and a seal, wherein the tamper-indicating seal creates a liquid resistant seal between the cap and the opening of the container. In a forth embodiment, the tamper-indicating seal serves as both a label and a tamper evident seal. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority from U.S. Provisional Patent Application No. 60/724,183 filed Oct. 6, 2005, which is hereby incorporated herein by reference.
TECHNICAL FIELD
The present invention is related to operating a four-stroke internal combustion engine.
BACKGROUND OF THE INVENTION
The automotive industry is continually researching new ways of improving the combustion process of the internal combustion engine in an effort to improve fuel economy, meet or exceed emission regulatory targets, and to meet or exceed consumer expectations regarding emissions, fuel economy and product differentiation.
Most modem conventional internal combustion engines attempt to operate around stoichiometric conditions. That is to say providing an optimal air/fuel ratio of substantially 14.6 to 1 that results in substantially complete consumption of the fuel and oxygen delivered to the engine. Such operation allows for exhaust gas aftertreatment by 3-way catalysts which clean up any unconsumed fuel (HC) and combustion byproducts such as nitrogen oxides (NOx) and carbon monoxide (CO). Most modern engines are fuel injected having either throttle body injection (TBI) or multi-port fuel injection (MPFI) wherein each of a plurality of injectors is located proximate an intake port at each cylinder of a multi-cylinder engine. Better air/fuel ratio control is achieved with a MPFI arrangement; however, conditions such as wall wetting and intake runner dynamics limit the precision with which such control is achieved. Fuel delivery precision can be improved by direct in-cylinder injection (DI). So called linear oxygen sensors provide a higher degree of control capability and, when coupled with DI, suggest an attractive system with improved cylinder-to-cylinder air/fuel ratio control capability. However, in-cylinder combustion dynamics then become more important and combustion quality plays an increasingly important role in controlling emissions. As such, engine manufacturers have concentrated on such things as injector spray patterns, intake swirl, and piston geometry to effect improved in-cylinder air/fuel mixing and homogeneity.
While stoichiometric gasoline four-stroke engine and 3-way catalyst systems have the potential to meet ultra-low emission targets, efficiency of such systems lags behind so-called lean-burn systems. Lean-burn systems also show promise in meeting emission targets for NOx through combustion controls, including high exhaust gas dilution and emerging NOx aftertreatment technologies. However, lean-burn systems still face other hurdles, for example, combustion quality and combustion stability particularly at part load operating points and high exhaust gas dilution.
Lean-bum engines, at a most basic level, include all internal combustion engines operated with air in excess of that required for the combustion of the fuel charge provided. A variety of fueling and ignition methodologies differentiate lean-bum topologies. Spark ignited systems (SI) initiate combustion by providing an electrical discharge in the combustion chamber. Compression ignition systems (CI) initiate combustion with combustion chamber conditions including combinations of air/fuel ratio, temperature and pressure among others. Fueling methods may include TBI, MPFI and DI. Homogeneous charge systems are characterized by very consistent and well vaporized fuel distribution within the air/fuel mixture as may be achieved by MPFI or direct injection early in the intake cycle. Stratified charge systems are characterized by less well vaporized and distributed fuel within the air/fuel mixture and are typically associated with direct injection of fuel late in the compression cycle.
Known gasoline DI engines may selectively be operated under homogeneous spark ignition or stratified spark ignition modes. A homogeneous spark ignited mode is generally selected for higher load conditions while a stratified spark ignition mode is generally selected for lower load conditions.
Certain DI compression ignition engines utilize a substantially homogeneous mixture of hot air and fuel and establish pressure and temperature conditions during engine compression cycles that cause ignition without the necessity for additional spark energy. This process is sometimes called controlled auto-ignition or homogeneous charge compression ignition (HCCI). Controlled auto-ignition and HCCI may be used interchangeably. Controlled auto-ignition is a predictable process and thus differs from undesirable pre-ignition events sometimes associated with spark-ignition engines. Controlled auto-ignition also differs from well-known compression ignition in diesel engines wherein fuel ignites substantially immediately upon injection into a highly pre-compressed, high temperature charge of air, whereas in the controlled auto-ignition process the hot air and fuel are mixed together prior to combustion during intake events and generally at compression profiles consistent with conventional spark ignited four-stroke engine systems.
Four-stroke internal combustion engines have been proposed which provide for auto-ignition by controlling the motion of the intake and exhaust valves associated with a combustion chamber to ensure that an air/fuel charge is mixed with combusted gases to generate conditions suitable for auto-ignition without the necessity for externally pre-heating intake air or cylinder charge or for high compression profiles. In this regard, certain engines have been proposed having a cam-actuated exhaust valve that is closed significantly later in the four-stroke cycle than is conventional in a spark-ignited four-stroke engine to allow for substantial overlap of the open exhaust valve with an open intake valve whereby previously expelled combusted gases are drawn back into the combustion chamber early during the intake cycle. Certain other engines have been proposed that have an exhaust valve that is closed significantly earlier in the exhaust cycle thereby trapping combusted gases for subsequent mixing with fuel and air during the intake cycle. In both such engines the exhaust and intake valves are opened only once in each four-stroke cycle. Certain other engines have been proposed having the exhaust valve opened twice during each four-stroke cycle—once to expel combusted gases from the combustion chamber into the exhaust passage during the exhaust cycle and once to draw back combusted gases from the exhaust passage into the combustion chamber late during the intake cycle. These engines variously utilize throttle body, port or direct combustion chamber fuel injection.
However advantageous such lean-bum engine systems appear to be, certain shortfalls with respect to combustion quality and combustion stability, particularly at part load operating points and high exhaust gas dilution, continue to exist. Such shortfalls lead to undesirable compromises including limitations on how much a fuel charge can effectively be reduced during part load operating points while still maintaining acceptable combustion quality and stability characteristics. As a further complicating factor, variations in commercially available fuels can also have pronounced effects upon combustion stability, particularly at low load operating regions.
SUMMARY OF THE INVENTION
A lean-bum, four-stroke, internal combustion engine is generally desirable. Furthermore, such an engine exhibiting high combustion stability at part load operating points is desirable. Moreover, such an engine capable of extended lean operation into heretofore unattained part load operating point regions is desirable.
The present invention relates to a method for robust homogeneous charge compression ignition control using commercially available fully-blended gasoline fuels with wide range of octane qualities. Using combinations of variable valve actuation and fuel injection, the controlled auto-ignition combustion is robust at all engine-operating conditions examined with the present invention.
The present invention provides these and other desirable aspects in a method of operating a four-stroke internal combustion engine with extended capability at low engine loads while maintaining or improving combustion quality, combustion stability and engine out emissions, particularly in light of variability of commercial fuels.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is a schematic illustration of a single-cylinder, direct-injection, four-stroke internal combustion engine;
FIG. 2 illustrates percent of samples as a function of OI with K=2.0 for regular, intermediate, and premium gasoline fuels in North America including summer and winter periods;
FIG. 3 illustrates crank angle position of 50% burned (CA 50 ) versus NVO for the test fuels at 8 mg/cycle during NVO sweep;
FIG. 4 illustrates a plot of crank angle position of 10% burned (CA 10 ) against crank angle position of 50% burned (CA 50 ) for the test fuels at 8 mg/cycle during NVO sweep;
FIG. 5 illustrates COV of IMEP versus crank angle position of 50% burned (CA 50 ) for the test fuels at 8 mg/cycle during NVO sweep;
FIG. 6 illustrates measured Net Mean Effective Pressure (NMEP) versus crank angle position of 50% burned (CA 50 ) for the test fuels at 8 mg/cycle during NVO sweep;
FIG. 7 illustrates NVO requirement for all the fuels tested at 8 mg/cycle such that CA 50 is maintained at 4 degrees after top dead center (aTDC) combustion;
FIG. 8 illustrates crank angle position of 50% burned (CA 50 ) versus NVO for the test fuels at 14 mg/cycle during NVO sweep;
FIG. 9 illustrates NVO requirement for optimal CA 50 of all the fuels tested at 8 and 14 mg/cycle;
FIG. 10 illustrates recompression burned fuel as a function of recompression injected mass for both Fuel A and Fuel E at hot idle—5.5 mg/cycle;
FIG. 11 illustrates CA 50 @ NVO=170 deg. as a function of octane index (OI) with K=2.1 for all the test fuels at 8.0 mg/cycle;
FIG. 12 illustrates CA 50 @ NVO=130 deg. as a function of OI with K=1.9 for all the test fuels at 14 mg/cycle;
FIG. 13 illustrates a schematic control diagram with which robust controlled auto-ignition combustion is maintained with variations in fuel octane qualities; and
FIG. 14 schematically illustrates a preferred embodiment of a control scheme utilizing valve control and fuel timing/quantity control to effect desired combustion phasing in the presence of fuel variability in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
With reference first to FIG. 1 , an exemplary single cylinder four-stroke internal combustion engine system (engine) 10 suited for implementation of the present invention is schematically illustrated. It is to be appreciated that the present invention is equally applicable to a multi-cylinder four-stroke internal combustion engine. The present exemplary engine 10 is shown configured for direct combustion chamber injection (direct injection) of fuel vis-à-vis fuel injector 41 . Alternative fueling strategies including port fuel injection or throttle body fuel injection may also be used in conjunction with certain controlled auto-ignition engines; however, the preferred approach is direct injection. Similarly, while widely available grades of gasoline and light ethanol blends thereof are preferred fuels, alternative liquid and gaseous fuels such as higher ethanol blends (e.g. E80, E85), neat ethanol (E99), neat methanol (M100), natural gas, hydrogen, biogas, various reformates, syngases etc. may also be used in such engines.
With respect to the base engine, a piston 11 is movable in a cylinder 13 and defines therein a variable volume combustion chamber 15 . Piston 11 is connected to crankshaft 35 through connecting rod 33 and reciprocally drives or is reciprocally driven by crankshaft 35 . Engine 10 also includes valve train 16 illustrated with a single intake valve 21 and a single exhaust valve 23 , though multiple intake and exhaust valve variations are equally applicable for utilization with the present invention. Valve train 16 also includes valve actuation apparatus 25 which may take any of a variety of forms including electrically controlled hydraulic or electromechanical actuation (a.k.a. fully flexible valve actuation, FFVA). Alternative valve actuation apparatus adaptable for implementation in conjunction with the present invention include multi-profile cams (a.k.a. multi-lobe, multi-step) and selection mechanisms, cam phasers and other mechanically variable valve actuation technologies implemented individually or in combination. A two-step with dual cam phasing valvetrain suitable for effecting the valve controls disclosed herein includes first exhaust and intake cams for effecting nominal duration and lift profiles, second exhaust and intake cams for effecting more limited duration and lift profiles and dual, independent cam phasers. Intake passage 17 supplies air into the combustion chamber 15 . The flow of the air into the combustion chamber 15 is controlled by intake valve 21 during intake events. Combusted gases are expelled from the combustion chamber 15 through exhaust passage 19 with flow controlled by exhaust valve 23 during exhaust events. Spark plug 29 is used to enhance the ignition timing control of the engine at certain conditions (e.g. during cold start and near the low load operation limit). Also, it has proven preferable to rely on spark ignition near the high part-load operation limit under controlled auto-ignition combustion and during high speed/load operating conditions with throttled or non-throttled SI operation.
Engine control is provided by computer based control 27 which may take the form of conventional hardware configurations and combinations including powertrain controllers, engine controllers and digital signal processors in integrated or distributed architectures. In general, control 27 includes at least one microprocessor, ROM, RAM, and various I/O devices including A/D and D/A converters and power drive circuitry. Control 27 also specifically includes controls for valve actuation apparatus 25 , fuel injector 41 and spark plug 29 . Controller 27 includes the monitoring of a plurality of engine related inputs from a plurality of transduced sources including engine coolant temperature, outside air temperature, manifold air temperature, operator torque requests, ambient pressure, manifold pressure in throttled applications, displacement and position sensors such as for valve train and engine crankshaft quantities, cylinder pressure, exhaust gas constituents and further includes the generation of control commands for a variety of actuators as well as the performance of general diagnostic functions. Known cylinder pressure sensors may sense combustion pressure directly, e.g. via intrusive or non-intrusive pressure sensors, or indirectly e.g. via ion sensing or crankshaft torque. While control and power electronics associated with valve actuation apparatus 25 , fuel injector 41 and spark plug 29 may be integral with control 27 , such may also be incorporated as part of distributed smart actuation scheme wherein certain monitoring and control functionality related to respective subsystems are implemented by programmable distributed controllers associated with such respective valve, fuel control and spark subsystems.
A total of 7 different fuels (designated as Fuel A to Fuel G) were tested using the exhaust recompression valve strategy at three different load conditions of 5.5, 8.0 and 14 mg/cycle. The three fueling/loads cover all three HCCI combustion modes: lean with split injection as disclosed for example in commonly assigned U.S. Pat. No. 6,971,365 B 1, lean with single injection as disclosed for example in commonly assigned U.S. Ser. No. 10/899,457 (2006/0016423), and stoichiometric with split injection as disclosed for example in commonly assigned U.S. Pat. No. 6,994,072 B2.
It is well known and accepted that Research and Motor Octane Numbers (RON and MON) alone do not adequately describe knocking (auto-ignition) behavior of commercial fuels in traditional spark-ignition engines. A combination of them, (RON+MON)/2, called octane number, however, was used in common practice to rank the anti-knock quality of a practical fuel.
In 2001, Kalghatgi of Shell Research proposed an octane index (OI) to better describe the fuels knocking behavior in accordance with the following relationships.
OI=RON−K*S where S (sensitivity)= RON−MON (1)
or
OI =(1 −K ) RON+K MON (2)
Kalghatgi showed good linear correlation between knock-limited spark advance and OI in a single cylinder engine, and acceleration times and OI in knock sensor equipped vehicles.
In 2003, Kalghatgi extended his K factor analysis to HCCI engines showing good correlation between CA 50 and OI at the following engine conditions.
CR=16.7 and 13.6,
PIVC=1 & 2 bar,
several TIVC,
several lambdas,
4 speeds,
11 different fuels, and
K values ranged from −1.90 to 0.41.
In 2003, Kalghatgi extended his K factor analysis further to include Shell's HCCI engine running at higher intake temperatures and included more “gasoline” like fuels. The following engine conditions correspond to this engine.
Single cylinder,
PFI,
fixed cams,
no EGR,
CR=14.0,
PIVC=1 bar,
3 TIVC,
several lambdas,
3 speeds, and
12 different fuels (4-PRF's, 3-toluene/hexane blends, 4-refinery blending components, one fully blended gasoline).
In summary, according to Kalghatgi's “K” factor analysis, the auto-ignition quality of a practical fuel can be correlated using the octane index, OI=RON−K*(RON−MON) where RON and MON are the Research and Motor Octane Numbers. K is a constant depending only on the pressure and temperature variation in the engine and varies with engine design parameter such as compression ratio. K decreases as the compression temperature in the unburned gas at a given pressure in the engine decreases and can be negative if this temperature is lower than in the RON test.
A four-stroke, single cylinder, 0.55 liter, controlled auto-ignition, gasoline direct injection internal combustion engine was utilized in implementing the valve and fueling controls and acquisition of the various data embodied herein. Unless specifically discussed otherwise, all such implementations and acquisitions are assumed to be carried out under standard conditions as understood by one having ordinary skill in the art.
Having thus described the environment and certain application hardware suitable for implementing the present invention, attention is now directed toward FIG. 2 . FIG. 2 shows the plot of percent of North America sampled fuels including during summer and winter periods against octane index (OI=RON−K*(RON−MON)) with K=2 (The reason for choosing 2 will be explained later). A total of 1870 samples were collected that includes regular, intermediate, and premium grade gasoline. Our test fuels, Fuel D, Fuel A, and Fuel E are indicated which covered wide OI range of the sampled fuels.
FIG. 3 shows the variations in CA 50 as a function of NVO for all the test fuels at 8 mg/cycle. It can be seen from the figure that CA 50 advances near linearly with increasing NVO. In particular, a 20-degree-increase in NVO resulted in 4-degree-advance in CA 50 . In addition, our base fuel, Fuel A, shows a CA 50 -NVO relationship representative of the average of all fuels tested.
Further, for fixed CA 50 , ±10 degrees spread in NVO is observed for all the fuels tested. In other words, a NVO authority of ±10 degrees centered at NVO=160 deg. is sufficient in maintaining the optimal combustion phasing at 8 mg/cycle independent of fuel.
When all the performance and emissions data are plotted against the crank angle position of 50% mass burned (CA 50 ), they collapsed into a single curve irrespective of the test fuels used. Typical examples are shown in FIGS. 4-6 for CA 10 , COV of IMEP, and NMEP, respectively. In particular, ±2 degrees variations in CA 50 centered about the optimal value at 4 degrees aTDC results in less than 1% reduction in NMEP. In other words, the change in NMEP with CA 50 is minimal for combustion phasings near the optimal value. Thus, for practical applications, a 10 degrees NVO spread (160±5 degrees) is sufficient in order to control NMEP within 1%
The required NVO for optimal combustion phasing at 4 degrees aTDC combustion is shown in FIG. 7 for all the test fuels. It can be seen from the figure that Fuel E has the most stringent NVO requirement.
FIG. 8 shows the variations in CA 50 as a function of NVO for all the test fuels at a fuel level of 14 mg/cycle. It can be seen from the figure that: 1) CA 50 advances near linearly with increasing NVO. In particular, 10 degrees increase in NVO resulted in 6 degrees advance in CA 50 . The sensitivity between CA 50 and NVO is higher for 14 mg/cycle than 8 mg/cycle. 2) For fixed CA 50 at 8 degrees aTDC, ±7 degrees spread in NVO is observed for all the fuels tested. 3) A NVO authority of ±7 degrees is needed to account for all the test fuel tested.
The required NVO for optimal CA 50 is shown in FIG. 9 for all the test fuels at 8 and 14 mg/cycle test points. In general, the fuels with higher required NVO at 8 mg/cycle demand higher NVO at 14 mg/cycle as well. Further, a consistent relationship exists between the NVO requirements at 8 and 14 mg/cycle in order to maintain best combustion phasing and hence engine performance. Knowing the required changes at one fueling level will be sufficient to make the necessary changes at all fueling levels. Among all the fuel tested at 8 mg/cycle, Fuel E requires the largest NVO to reach optimal combustion phasing at 4 degrees aTDC. It is about 175 degrees ( FIG. 7 ) which is very close to the upper limit of hydraulic cam phaser operation of 190 degrees. To mitigate the requirement on NVO for combustion phasing control, Fuels A and E were used for injection strategy study to demonstrate the effectiveness of using injection timing and quantity for combustion phasing control. To this end, both single and split injection strategies were evaluated. In particular, FIG. 10 shows that the recompression burned fuel increases with increasing recompression injected fuel, which resulted in higher mixture gas temperature during compression and hence combustion phasing advance. However, its effectiveness decreases with increasing recompression injected fuel beyond 2 mg.
The Applicants have resolved the above results to suggest the following procedure for steady-state HCCI engine combustion phasing control to account for fuel variations between 7 and 15 mg/cycle (180-450 kPa NMEP).
1. A nominal NVO is selected first depending on the load level ( FIG. 9 ). 2. Desired CA 50 is then specified. 3. Adjust NVO +/−5 deg. as required to maintain CA 50 within target range with different fuels. 4. At the NVO limits adjust reforming fueling level as required to maintain CA 50 within target window.
FIG. 11 shows the experimentally measured CA 50 @ NVO=170 for all test fuels at 8 mg/cycle versus OI using k=2.1. Good linear correlation between CA 50 and OI is demonstrated. The same is true for the 14 mg/cycle test point. FIG. 12 shows our measured CA 50 @ NVO=130 for all test fuels at 14 mg/cycle versus OI using k=1.9. By comparing FIG. 12 to FIG. 11 , it is clear from both figures that different correlations exist for different loads. However, it is also clear from both figures that our data are well correlated by a single Kalghatgi K factor (˜2) at different loads.
The CA 50 —OI correlations shown in FIG. 11 and FIG. 12 are useable to predict how commercially available, fully-blended gasoline fuels (with known RON and MON) will behave in our HCCI engine. For example, using RON and MON of the fuel and a K valve equals 2, the CA 50 can be calculated at 8 mg/cycle using the following relationship.
CA 50=0.44 OI −30.9 (3)
Eq. (3) differs slightly from the correlation shown in FIG. 11 due to the use of a slightly different K value. The NVO required in order to move the CA 50 back to its optimal location (4 degrees aTDC) is calculated using the following relationship at 8 mg/cycle which is derived based on Fuel A data shown in FIG. 3 .
NVO =182−4.35 CA 50 (4)
Since higher octane indices ( 01 ) equate to delayed HCCI combustion phasing, fuels with higher octane indices will be challenging. Further, since OI=RON−2*Sensitivity, fuels with high RON and low Sensitivity will be the most challenging.
FIG. 13 illustrates schematically a control methodology for HCCI engine combustion phasing control to compensate for fuel variations substantially as follows.
1. Primary load control parameter is NVO.
2. Lookup table for NVO as function of load at fully warmed-up condition.
3. Use combustion phasing (for example, LPP or CA 50 ) as closed loop feedback signal.
4. Compare CA 50 from each cylinder to target CA 50 value from lookup table.
5. If cylinders are randomly dispersed around target CA 50 , then use secondary control parameters (for example, injection timing/quantity during recompression, spark timing, etc.) to trim cylinders.
6. If ALL of the cylinders are displaced from target value then this indicates a shift in fuel “octane index”.
7. Use either NVO or secondary control parameters (for example, injection timing/quantity during recompression, spark timing, etc.) to adjust engine average CA 50 and update tables based on change in required NVO using relationship (4).
With reference to FIG. 14 , a more specific exemplary control schematic is illustrated. Engine 10 includes fuel injectors 41 and valve actuation apparatus 25 . An open-loop portion of the control including Valve Control Baseline Set-point Map 101 is preferably calibrated offline through known dynamometric techniques. This open-loop control may comprise, for example, tabulated intake and exhaust valve positions as stored in calibration tables referenced by engine speed and load data. It is these nominal valve positions that are used to establish baseline negative valve overlap NVO 102 . In accordance with an embodiment, engine 10 is additionally configured with one or more cylinder pressure sensors 103 . The control system is structured including a closed-loop portion to adjust the nominal valve positions based on combustion information 105 derived from cylinder pressure sensors 103 . NVO correction uses combustion phasing feedback information 105 (e.g. % burned angle, heat release rate, combustion duration, maximum rate of pressure rise, just to name a few) and compares it to a combustion phasing target 107 , e.g. from Baseline Combustion Phasing Map 109 . This comparison perturbs the nominal valve positions from Valve Control Baseline Set-point Map 101 to drive the combustion phasing error 106 input to Valve Control Set-point Optimizer 111 to zero. Limiter 113 limits the authority over valve adjustments in accordance with the particular hardware limitations of the engine including the valve actuation apparatus 25 . Hence, the control establishes negative valve overlap through intake and exhaust valve actuations that effect minimal error in predefined combustion phasings up to the limitations of the valve actuation apparatus.
Valve position targets and combustion phasing targets are referenced, for example, using engine speed and load data. Additional correction may be afforded in accordance with intake temperature, ambient pressure, fuel type, etc. Baseline Combustion Phasing Map 109 is preferably calibrated offline through known dynamometric techniques. Baseline combustion phasing targets represent desired combustion characteristics relative to a plurality of metrics (e.g. NOx emissions, combustion noise, fuel economy, and maximum MBT at dilution/knock limits for gasoline applications). The closed loop portion of the control maintains the desired combustion characteristics in the presence of variations and disturbances including variations in the fuel being provided to the engine. The Valve Control Set-point Optimizer 111 in one implementation is a slow integrator. In other words, the Valve Control Set-point Optimizer 111 slowly increases or decreases the valve set-points if the achieved NVO (combustion phasing feedback) 105 is less or more than expected.
Exemplary information 105 may correspond substantially to 50% fuel burned, e.g. crank angle of 50% fuel burned (CA 50 ). Information 105 may correspond, for example, to an average across all cylinders, to a single cylinder, or to a bank of cylinders in accordance with the available engine cylinder pressure sensing hardware configuration and cost considerations. And, with respect to valve actuation hardware which is limited in its individual cylinder-to-cylinder adjustment capability (i.e. cam phasers), the NVO is necessarily established consistently for each of the individual cylinders. For this reason, other cylinder-to-cylinder combustion variability factors may result in cylinder-to-cylinder variability in the combustion phasings. Generally, therefore, it is with respect to a single NVO setting applicable to all cylinders that the average combustion phasing across all cylinders results in a minimal average deviation from the desired phasing. Independently actuatable valves (i.e. fully flexible valve actuation) may allow for individual cylinder-to-cylinder adjustments of NVO in accordance with respective cylinder pressure sensing. Still, deviation of the average combustion phasing across all cylinders from desired combustion phasing is minimized. As mentioned earlier, all of this is accomplished within the boundaries of the valve actuation apparatus authority.
At the limits of valve actuation apparatus authority, a secondary combustion phasing control more particularly adaptable to individual cylinder-to-cylinder variations is preferably implemented. For example, fuel injection timing in a direct injection fuel apparatus may be controlled on a cylinder to cylinder basis. In FIG. 14 , another open-loop portion of the control including Fuel Injection Control Baseline Set-point Map 115 is preferably calibrated offline through known dynamometric techniques. This open-loop control may comprise, for example, tabulated fuel injection timing as stored in calibration tables referenced by engine speed and load data. It is these nominal fuel injection timings that are used to establish baseline fuel injection timings 117 . In accordance with the secondary combustion phasing control, and preferably in accordance with limits in the valve actuation authority of the valve position control as illustrated (or alternatively in accordance with minimal combustion phasing having been satisfied by the valve control), a closed-loop control portion adjusts the timings or the mass of reforming fuel based on combustion information 105 derived from cylinder pressure sensors 103 . Fuel injection timing correction uses combustion phasing feedback information 105 and compares it to the combustion phasing target 107 . This comparison perturbs the nominal fuel injection timings from Fuel Injection Control Baseline Set-point Map 115 to drive the error input to Fuel Injection Control Set-point Optimizer 119 to zero. Hence, the secondary combustion phasing control establishes fuel injection timing that further trims the combustion phasing error 106 . An alternative secondary combustion phasing control may be implemented in similar fashion utilizing spark timing controls at least in operating regions wherein spark assist is utilized and normal spark authority ranges can effect the desired combustion phasing shifts. Combustion phasing of all cylinders may be adjusted, for example via a shift of all injection timings, or each individual cylinder's combustion phasing may be adjusted, for example via cylinder-to-cylinder fuel injection optimizations. The latter implementation may benefit from the utilization of individual or per-cylinder combustion sensing.
NVO has been shown an effective parameter for HCCI engine combustion phasing control from 7 mg/cycle to 15 mg/cycle to account for fuel variations. Below 7 mg/cycle, the NVO is preferably changed for combustion stability and emissions considerations and the combustion phasing is controlled primarily by recompression injected fuel mass and timing. Octane index (OI) correlations ( FIGS. 11 and 12 ) can be used to predict how commercially available, fully-blended gasoline fuels will behave under HCCI operation within a wide load range. In particular, with known RON and MON, OI can be calculated using K=2. The CA 50 can then be calculated using the relationship (3) herein above. The NVO requirement to move CA 50 back to its optimal location (substantially about 4 degrees aTDC) is calculated using the relationship (4) herein above.
The present invention has been described with respect to certain preferred embodiments and variations herein. Other alternative embodiments, variations ad implementations may be implemented and practiced without departing from the scope of the invention which is to be limited only by the claims as follow: | Operation of a homogeneous charge compression ignition engine is adapted to fuel variations. A variable valve actuating system is employed to effect conditions conducive to homogeneous charge compression ignition operation. Nominal valve timing is selected and adjustments thereto are made based on deviations in combustion phasing from a desired combustion phasing. Fuel delivery timing and quantity are adjusted once valve timing authority limits are reached to achieve further combustion phasing improvement. | 5 |
DESCRIPTION
This application is a continuation-in-part of our application, Ser. No. 08/439,063 filed May 8, 1995 now matured as U.S. Pat. No. 5,611,281 issued Mar. 18, 1997.
The present invention relates to systems (apparatus and methods) for removing contaminants from process rollers and more particularly to apparatus and methods for washing and scrubbing contaminants from process rollers, and most particularly to apparatus and methods for removing accumulated particles from contact cleaning rollers.
Process rollers are well known in the manufacturing arts for conveying and transforming substrates, especially flexible linear substrates such as film and paper supports known generically as webs. Rollers may be used, for example, to convey, steer, tension, smooth, compress, print, and clean substrates in, for example, film and paper coating machines, rotary printing presses, and high-pressure calendaring machines.
A common problem with all such rollers is that they eventually accumulate contaminants, especially foreign particles, on their surfaces, which can cause unwanted physical and/or chemical anomalies in the substrates and in coatings thereupon. All such process rollers, therefore, require cleaning of their surfaces from time to time. The problem is particularly acute for contact cleaning rollers (CCRs) which are intended by their very nature to become clogged on their surfaces as they remove particles from the surfaces of substrates over which the CCRs have been rolled, and which must be renewed by cleaning in order to restore their particle-removing effectiveness.
In the process roller cleaning apparatus of the above referenced parent application Ser. No. 08/439,063 a stationary cleaning pad is brought into rubbing contact with the contaminated surface of a roller being driven. The pad may be dry or, typically, it may be moistened with a suitable liquid to aid in dislodging or dissolving the contaminants on the roller surface. Such apparatus is shown in FIGS. 1 and 2 and discussed more fully hereinafter. Rubbing or scrubbing of the cleaning pad against the roller causes contaminants to be transferred to the cleaning pad. The pad may consist of a cleaning web in contact with the roller surface, supported by a backing element such as a sponge to urge the cleaning web against the roller. The cleaning web may be intermittently or continuously dispensed from an unsoiled source to present clean web to the roller, the soiled web being accumulated out of contact with the roller. The pad also may move axially of the roller during cleaning so that a pad substantially narrower than the roller can progressively clean the entire roller surface. See U.S. Pat. Nos. 4,982,469 to Nishiwaki and 5,251,348 to Corrado for other apparatus for cleaning process rollers.
At least two problems can arise in existing apparatus for cleaning process rollers. First, the force with which the cleaning pad is urged against the roller is distributed over the entire surface area of the pad, so that the unit pressure at any point on the pad may be quite low, which can result in slow and incomplete cleaning of the roller surface. Thus, a need exists for means for increasing locally the force exerted on a portion of a cleaning pad. Second, cleaning systems employing liquids typically rely for cooling and lubrication on the liquids themselves, and if flow of liquid to the cleaning pad is lost, the dry pad can rapidly damage or destroy the delicate surface of the roller being cleaned. Thus, a need exists for means for monitoring and controlling the proper rubbing action of a cleaning pad against a roller and for providing an out-of-control alarm.
It is a principal object of the invention to provide improved systems for cleaning process rollers which increase locally, selectively, and automatically the force exerted on a cleaning pad in rubbing contact with a roller surface.
It is a further object of the invention to provide such systems which also serves to monitor and control the force being exerted by a cleaning pad against a roller surface.
It is a still further object of the invention to provide such systems and which also operates alarm the system when the frictional resistance of a cleaning pad against a roller surface exceeds predetermined control limits.
Briefly described, a roller cleaning system embodying the invention comprises a cleaning pad which may be urged selectively against the surface of a rotating roller to be cleaned. The roller may be rotated by any convenient drive means from which a drive signal may be extracted, including an electric motor, an internal combustion engine, an hydraulic motor, and an air motor. The cleaning pad may include a backing sponge and a cleaning web between the sponge and the roller surface. The system may include a reservoir or other source of cleaning fluid, such as water or solvent, to moisten, cool, and lubricate the pad during rubbing or scrubbing against the roller, and to loosen or dissolve the contaminants being removed. The unsoiled cleaning web may be dispensed as from a feed roll of material, and the soiled web may be wound on a takeup roll. The components are mounted on a suitable frame or housing, which may be translatable axially of the roller during cleaning.
To initiate rubbing contact between the cleaning pad and the roller surface, either the roller is urged with a first force against the cleaning pad, as in the references cited previously, or the pad may be urged against the roller.
An actuator is disposed between the frame and a portion of the back side of the cleaning pad to selectively exert a second and higher force against the portion of the cleaning pad and hence against the roller in a localized area of higher pad pressure to accelerate removal of more firmly adhered contaminants.
In a preferred embodiment of the invention, a control loop is included between the roller drive and the actuator. A controller senses continuously a drive signal from the roller drive indicative of the magnitude of frictional resistance between the roller and the cleaning pad and adjusts continuously the force exerted by the actuator on the cleaning pad to maintain a constant frictional resistance. The system alarms when predetermined control limits are exceeded. Other values of frictional resistance can be achieved if desired by programming the controller to vary the second force exerted by the actuator.
A roller cleaning system in accordance with the invention is especially useful in "renewing" (cleaning) contaminant-loaded contact cleaning rollers, known in abbreviation as CCRs.
The foregoing and other objects, features, and advantages of the invention, as well as presently preferred embodiments thereof, will become more apparent from a reading of the following description in connection with the accompanying drawings in which:
FIG. 1 is an elevational view in cross-section of an existing roller cleaning system, taken along line 1--1 in FIG. 2;
FIG. 2 is an elevational view of the existing roller cleaning system shown in FIG. 1;
FIG. 3 is a view like that of FIG. 1, showing a roller cleaning system having a cleaning pad high-pressure actuator in accordance with the subject invention; and
FIG. 4 is a view like that of FIG. 3, showing a roller cleaning system having a schematic control loop for controlling the pressure exerted by a cleaning pad high-pressure actuator.
Referring to FIGS. 1 and 2, existing roller cleaning apparatus 10 is shown in position to clean, or "renew," by rubbing a first contact cleaning roller 12, which roller has been pivoted out of cleaning contact with surface 14 of web 15 being conveyed around process conveyance roller 16. Second contact cleaning roller 18 is in position to clean surface 14. Roller cleaning apparatus 14 includes a cleaning pad 19 supported on a frame 21 preferably having a backing element 20 and a cleaning web 22 although other cleaning pad configurations may be used. Backing element 20 may be any suitable resilient material, preferably a sponge or sponge cartridge, and operates to urge cleaning web 22 against roller 12 at a substantially uniform pressure over the entire surface of element 20. Cleaning web 22 may be any suitable web, preferably a non-shedding cloth material impregnated with an agent to aid in removing particulates from contact cleaning rollers 12 and 18. Preferably, cleaning web 22 is continuously wetted at the contact point with roller 12 with liquid from a reservoir (not shown) included in apparatus 10. Cleaning web 22 is dispensed intermittently or continuously from a feed roll 24 of material and is accumulated on a take-up roller 26 when soiled.
Contact cleaning roller 12 is driven in rubbing contact past cleaning pad 19 by friction drive wheel 28 which is mounted on a shaft of drive motor 30. Preferably, roller 12 is driven at a fixed speed experimentally predetermined to yield adequate cleaning of roller 12 in a desired length of time. Apparatus 10 is mounted on a horizontal track and rails 32 and preferably is driven axially of roller 12 in an oscillatory or reciprocating motion so that pad 19 progressively cleans the entire surface of roller 12. Apparatus 10 also includes vertical rails 33 to permit the cleaning apparatus to be elevated to a second position appropriate for renewing roller 18 when it is pivoted into its renewal position.
In some applications, the existing apparatus can remove deposits from the cleaning roller only very slowly and incompletely. We have found that an unexpected and dramatic improvement in cleaning rate and thoroughness can be achieved if a portion, preferably a central portion, of cleaning pad 19 is urged selectively against the cleaning roller with a second rubbing force substantially greater than the first force existing over the rest of the pad. FIG. 3 shows roller cleaning system 34 in accordance with the invention. An actuator 36 is disposed between the back side of backing element 20 and housing 38 and between feed and take-up rollers 24 and 26, respectively. Actuator 36, shown as preferred, is a pneumatic cylinder supplied with pressurized air from a high-pressure source 39 through supply line 40 and a reducing valve 42, by which the selectively greater force on backing element 20 can be set. Alternatively, actuator 36 may be any convenient, variable source of selectively increased force against a portion of pad 22, for example, a hydraulic cylinder or a stepper motor. Other means of variable actuation which may come to mind are within the scope of the invention.
In general, it is most desirable to clean a roller in the shortest time possible, consistent with thorough cleaning and without damage to the roller surface. This may require that the second force be quite large, and cleaning liquid generally is necessary in the contact area to cool and lubricate the roller surface and the cleaning web, as well as to loosen and dissolve particles on the dirty roller and to aid in their transfer to the cleaning web. If flow of liquid to the contact area is lost, for example, if the reservoir is not timely replenished, increasing friction from dry rubbing can lead rapidly to damage and destruction of the roller surface and even to combustion of the cleaning web. Thus, it is also highly desirable to have control means in the roller cleaning system for sensing an out-of-control condition, for preventing damage to the roller and the system, and for alarming any potentially dangerous condition.
FIG. 4 shows a control loop 44 added to the novel roller cleaning system 34 of FIG. 3. An electronic controller 46 senses a signal from a conventional electronic drive package 48 which controls roller drive motor 30. The current 47 drawn by motor 30 is a useful signal indicative of the magnitude of frictional resistance between roller 12 and cleaning web 22, the level of which current is desirably held constant during a roller cleaning cycle. The correct controller set point for this desired current level is determined experimentally. Controller 46 outputs through a conventional current/pressure transformer 50 to vary the opening of reducing valve 42 to increase or decrease the force exerted by actuator 36 on backing element 20 and thereby to maintain as constant the amperage drawn by drive motor 30. Of course, the controller may be programmed to increase or decrease the force as desired, for example, additional force may be beneficial in areas of the roller known to be more heavily loaded with particles.
If the cleaning area becomes dry and frictional resistance begins to increase, the motor load begins to increase, and the controller instantly and automatically reduces the second force on the cleaning pad. If the motor load continues to increase, the controller will continue to decrease the second force. Preferably, an alarm limit is established within or at the limit of controller action, at which point the system presents an alarm condition and activates alarm 52. Preferably, cleaning of the roller is automatically terminated at the alarm, either by separating the roller from the cleaning pad or by shutting down the roller drive, or both.
In an alternative embodiment, drive motor 30 may be such that increased frictional load results in a decrease in motor speed, for example, an air motor or an hydraulic motor. In such case, the control scheme can utilize the rotational speed of the motor as the set point for the controller. The action of the controller and the alarm is the same as above.
From the foregoing description it will be apparent that there has been provided an improved apparatus and method for cleaning rollers, wherein a programmed higher cleaning force is locally exerted on a cleaning pad to improve the effectiveness of cleaning. Variations and modifications of the herein described roller cleaning system, in accordance with the invention, will undoubtedly suggest themselves to those skilled in this art. Accordingly, the foregoing description should be taken as illustrative and not in a limiting sense. | A cleaning system for removing contaminants from the surface of a roller. A stationary cleaning pad is forced at a first urging force against a roller to be cleaned, and the roller is driven in rubbing contact with the pad. Preferably, the pad is supplied continuously with a cleaning liquid. An actuator disposed against a portion of the back of the pad urges that portion against the roller at a second, greater urging force to accelerate the rate of cleaning. A control loop between the roller motor drive and the actuator responds to a signal from the drive indicative of the magnitude of frictional resistance between the roller and the pad and increases or decreases the second force furnished by the actuator to provide a predetermined constant frictional resistance during cleaning. If flow of cleaning liquid to the pad is lost, friction can build up quickly and the roller surface can become damaged. The system safeguards the roller surface by reducing the actuator force to counter frictional increase and by terminating the cleaning cycle and alarming the condition when the limit of controller action is reached. | 1 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to safety devices, and in particular to devices useful in heightening the visibility of hazards to on-lookers.
[0003] 2. Background Information
[0004] Many circumstances require that items, locations, or even persons be rendered more highly visible, if safety is to be optimized. Such circumstances are particularly prevalent in conditions of darkness, with disabled vehicles at a roadside being a classic example of the need for heightened visibility.
[0005] Incendiary flares have long been an item of choice when illuminating the location or a disabled vehicle, an accident site, or of persons working in a dangerous location vis a vis moving traffic, or in other conditions where siting things or individuals is for some reason of paramount importance. Battery operated flashlights are the most common alternatives.
[0006] The conventional approach to light-marking items or individuals as just described are not without limitations. Incendiary flares are rather quickly exhausted, represent something of a hazard when transported in a vehicle, and present a serious fire hazzard when used in certain areas with a high fire potential. Battery operated flashlights tend to be highly directional, not particularly noticeable when viewed by others at a distance, and are also rather short-lived.
SUMMARY OF THE INVENTION
[0007] In view of the foregoing, it is an object of the present invention to provide an improved visualization aid in light-marking objects or individuals.
[0008] It is another object of the present invention to provide a visualization aid in light-marking objects or individuals which, vis a vis existing incendiary flares, flashlights, and the like, present a more highly visible light-marking effect.
[0009] It is another object of the present invention to provide a visualization aid in light-marking objects or individuals which, vis a vis existing incendiary flares, flashlights, and the like, provide an improved, re-usable item which, even on a single use basis, provides longer service life than most presently available alternatives.
[0010] It is another object of the present invention to provide a visualization aid in light-marking objects or individuals which, vis a vis existing incendiary flares, flashlights, and the like, provides a far greater breadth of contexts in which the device is safely and effectively useable.
[0011] In satisfaction of these and related objects, the present invention provides an LED-based light emitting system. The system in its preferred embodiment includes a fabric pouch-like assembly upon which two LED panels are externally mounted. A battery pack, control circuitry, and a switch for powering and actuating the LED panels resides in accessible, internal pockets. VELCRO-fastenable flaps are provides to reversibly attach the pouch-like assembly to various support structures, including several choices of stand members which are described in the specification. The flexibility of the pouch-like member, together with the flaps affords great flexibility in positioning and orienting the system for light-marking locations or individuals.
[0012] By utilizing LED-based lighting (flashing LEDs being the preferred choice), the present system has a very long service life on any given set of batteries, very high light output over almost the entire life of the batteries.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a perspective view of the preferred embodiment of an electronic safety flare system of the present invention.
[0014] FIG. 2 depicts the electronic safety flare system of the present invention mounted on a sawhorse type traffic barrier.
[0015] FIG. 3 depicts the electronic safety flare system of the present invention mounted on a stand specifically designed for use in the present system.
[0016] FIG. 4 depicts the electronic safety flare system of the present invention positioned over an edge of an automobile enclosure.
[0017] FIG. 5 depicts the electronic safety flare system of the present invention attached to the belt of a runner.
[0018] FIG. 6 is a perspective view of the safety flare systems of the present invention inclusive of a rigid stand for use as a roadside flare.
[0019] FIG. 7 is a perspective view of the safety flare systems of the present invention inclusive of a foldable stand for use as a roadside flare.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0020] Referring to FIG. 1 , the electronic safety flare system (absent any stands, which are to be discussed later) is identified generally by the reference number 10 .
[0021] System 10 includes a flexible support member 12 . Flexible support member 12 is, in the preferred embodiment, made of water-resistant fabric. While flexible support member 12 is primarily a unitary structure, with but a pocket 20 and light panels 22 appended, it is best to describe functional portions thereof.
[0022] Flexible support member 12 includes, in its preferred embodiment, two light support faces 14 which are surfaces areas on one side of member 12 and positioned on either side of a substantial line of symmetry A of member 12 , about which flexible support member 12 can be readily bent to configure and orient member 12 as desired for any particular use (to be discussed in more detail later).
[0023] The preferred embodiment of the present invention includes two LED light panels 22 which are positioned within the areas of flexible support member 12 which are identified as light support faces 14 as depicted in FIG. 1 . The preferred embodiment of the present invention utilizes arrays of flashing LEDs (together, or in combinations) with luminosity as follows: Red-500 mcd, Yellow-800 mcd, Blue-1500 mcd and/or other colors of a particular user's or designer's choice. When LEDs are used, a CMOS tyle LED driver is used to flash the LEDs at a twice per second rate in the preferred embodiment, and the unit is powered by conventional AA batteries (in the preferred embodiment) in a conventional AA battery case 24 (which resides in pocket 20 appended to flexible support member 12 ). It should be noted that alternative lighting options might include such things are conventional “strobe” lights, halogen lights with flashing circuitry, and other light emitting choices. However, because of the high efficiency of present LEDs when compared to present alternative lighting choices, it is believed that the LED represents the best choice at present.
[0024] In one embodiment of the present invention, either a portion of member 12 , or an additional panel added thereto over the light support faces 14 portion, will be fabricated of retro-reflective material (such as is often used in night-reflected safety vests, cyclists clothing striping, etc.) and serves as a reflective supplement to the lights themselves in enhancing visibility.
[0025] While a number of options are available which would fall within the scope of the present invention, exemplary LED components and circuitry, all or a portion of which may be useful in constructing alternative embodiments of the present invention, are shown in U.S. Pat. Nos. 4,345,305, 5,149,190 and 6,515,584, the disclosures of which are here incorporated by reference.
[0026] Referring still principally to FIG. 1 , “flexible envelopment tethers” 26 (essentially fabric flaps in the preferred embodiment) extend from the central portion of flexible support member 12 . Envelopment tethers 26 are paired, with each having a respective pairing of hook 28 and eye 30 fastening materials (VELCRO) attached to their distal margins.
[0027] As is clear from an examination of FIGS. 2, 3 , 4 and 5 , the structure and constitution of system 10 affords considerable utility in a wide variety of contexts, without any additional components. System 10 can easily be adapted to attach to existing structures or items (see particularly FIGS. 2, 4 and 5 ), but can be supported by stands 32 , 34 or 36 which are made specifically for incorporation into the present system (see particularly FIGS. 3, 6 and 7 ). These stands, or course, can be made of metal or plastic, depending on the intended user's preferences for weight, durability, etc.
[0028] Referring in particular to FIGS. 3, 6 and 7 , stands made specifically for incorporation into the present system 10 can fulfill many needs. Stand 36 shown in FIG. 3 , for example, can be used by police, fire and other public servants where particularly high visibility in a street or highway context is desirable, and consumption of trunk space and the like is not as much of a concern as might be the case with a private vehicle. On the other hand, variants of “flare stand” 32 and 34 (collapsible version) shown in FIGS. 6 and 7 would well serve any one looking to replace the conventional incendiary flares, while conserving car trunk space.
[0029] Notably, system 10 is easily attached and removed from any of the depicted mounting structures or devices, and is easily convertible between any of the depicted uses.
[0030] Because of the use of LED-based lighting as described, system 10 emits highly visible light pulses, yet consumes very little battery power per unit time, while avoiding any of the hazzards associated with incendiary flares, nor limited visibility and battery life associated with conventional flashlights. Embodiments of the present invention are light, compact, and easily stored and transported.
[0031] Although the invention has been described with reference to specific embodiments, this description is not meant to be construed in a limited sense. Various modifications of the disclosed embodiments, as well as alternative embodiments of the inventions will become apparent to persons skilled in the art upon the reference to the description of the invention. It is, therefore, contemplated that the appended claims will cover such modifications that fall within the scope of the invention. | A flexible electronic safe flare system which includes two LED flashing light arrays mounted on a flexible base member with attachment straps for attaching in any of a number of different orientations and configurations. Stands are described for supporting the flare system in positions and orientations for various uses, such as highway light-marking of objects or positions. | 6 |
CROSS REFERENCE TO RELATED APPLICATIONS
The present invention claims priority to provisional patent application Ser. No. 60/520,658, filed Nov. 18, 2003, which is herein incorporated by reference.
BACKGROUND OF THE INVENTION
The present invention relates to the field of mail processing and more particularly to a system and method for resolving non-address attributes on an address face of a postal item.
Non-address attributes as used herein include: stamps, pictorial representations, alpha numeric characters, stylized and non-formatted textual fields, postal endorsements, logos, and markings and the like whose resolution is desired and/or necessary for effective sorting of the respective mail piece and for associated applications such as Mail Forwarding and Return to Sender functions.
Current and prior attribute resolution systems perform automatic address reading via optical character recognition software (OCR). An example system is set out in German Patent DE 195 31 392 C1. Ideally, current mail handling automation would include some form of non-address attribute recognition. However, non-address attributes defy current automation rules including a lack of redundancy and standardization among the many non-address attribute candidates. Accordingly, with current resolution techniques, reject and error rates are higher than with address attribute resolution. As with address attributes, when an unresolveable non-address attribute is encountered with current automatic resolutions means, the image containing the unresolvable attribute is forwarded to a video coder for manual resolution. Per standard encoder techniques, a video encoder, sitting at a video encoding station, receives an image on a display (typically a computer monitor), analyzes the image for the missing/unresolvable attributes and manually keys in or enters information which could not have otherwise been obtained automatically. Thresholds of confidence are used to determine when an attribute has not been resolved and the entire image must be manually encoded.
To assist encoders, methods have been proposed wherein the encoder's attention is brought to a particular portion of the image (area of interest) where it is believed (by the method) that the non-resolvable attribute is present. Additionally, encoder communication of information has been reduced, in some circumstances to a single key stroke. However, despite such aids, manual encoding remains an inefficient solution because oftentimes, zooming and other manually scanning is required and information is not always communicatable with a single key stroke. Attempts have been made in making manual encoding more efficient by reducing the number of steps required by an encoder to arrive at a non-address attribute image location as well as the number of key strokes required for resolution. One solution, proposed by U.S. Pat. No. 5,455,875, includes the use of truthing tables. In truthing tables, portions of images are presented in matrix format. The truthing matrix per the above patent contains non-resolvable attributes clustered by what the recognition logic believed them to be. The belief is based on a partial resolution of the unresolvable attribute, wherein the partial resolution fell below a confidence threshold. A prior art matrix from the '875 patent is depicted in FIG. 1 (with reference numbers added for clarity). The matrix entries include different backgrounds to denote where the operator flagged non-matches.
As depicted in FIG. 1 , a matrix 10 is presented to a viewer on computer screen 22 . The matrix comprises a plurality of boxes 12 having or depicting a “O” therein. Exceptions flagged by the operator are depicted as having a hatched background and depict a “ 6 ” (element 14 ), “L” (element 20 ) and “ 5 ” (element 18 ). The matrix of FIG. 1 is limited in application to distinguishing single, well recognizable to the operator, alpha-numeric characters. Likewise, non-address attributes comprise more than the single digits analyzed by the '875 reference and complex ad hoc classes of patterns are not effectively handle by the method. Accordingly, a need exists for increasing mail sorting throughput via recognition of complex, non-address attributes.
SUMMARY OF THE INVENTION
An objective of the present invention is to provide a system and method for more effective video coding of non-address attributes as required for automation of mail processing and, in particular, to increase productivity while at the same time decrease operator error rate from existing methods of video coding non-address attributes. An additional objective is that the basic system and method to be described can be application-wise extended beyond the previously mentioned examples of non-address attributes (i.e. stamp classification and endorsement) to include filtering of patterns whether they are structured, such as conventional alphabets, or are an arbitrary grouping of shapes. Yet another objective is to increase the level of work satisfaction of coding operators through exposure to non-keying intensive tasks and ones that use aspects of the operators' cognitive intellect. These and other advantages are made available by the present invention.
The present system comprises means for executing the above described inventive method. The present system includes a feeding mechanism for handling the mail pieces, the feeding mechanism comprising means for running mail pieces past a high resolution scanner or similar image lift device. An image, created by the scanner, is forwarded to at least one processor for resolution. In the event the non-address attributes are unresolveable, a second processor and database are consulted for creation of the aforementioned matrix, however, the present matrix includes a Cognitive Zone. The cognitive zone includes example non-address attributes which may match the unresolved non-address attributes. The Cognitive Zone is centrally located and may comprise a single or column entry or row entry. The matrix is then forwarded via appropriate means to one of a plurality of video coding stations for decoding.
The present invention also comprises a method for performing non-address attribute resolution using the above mentioned system. According to the present method, an image is created and non-address attributes therein are resolved by automatic means. A determination as to whether Automatic resolution was successful is performed. A successful determination is one that rises above a particular threshold. Unsuccessfully resolved attributes that have a recognition affinity to a given attribute class but where below the successful recognition threshold are assigned to a matrix designated for said attribute class. A cognitive zone made up of example attribute(s) is inserted into the matrix and the matrix forwarded to an encoder for manual encoding. The example attributes in the cognition zone are arrived at by matching the non-resolved attributes with example attributes believed to be a match, the matching rated by level of confidence. Because the confidence level of the initial resolution is not high, it is not always a guarantee that the example attribute displayed in the cognitive zone will match the non-resolved attribute. If the encoder indicates that the non-resolved attribute does not match the example attribute in the cognitive zone, the subject reject attribute is reassessed according to its next highest likelihood recognition and inserted as one of the candidates in a second matrix with a cognitive zone composed of examples related to this new recognition alternative. The present method includes other steps detailed below.
When an non-match is indicated, a second matrix is created using example attributes having a next highest match confidence level. The second matrix is presented to the encoder for manual matching. This occurs for additional matrices until the match confidence level falls below a preset threshold; at which time the entire image is presented to encoder for manual encoding.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
The novel features and method steps believed characteristic of the invention are set out in the claims below. The invention itself, however, as well as other features and advantages thereof, are best understood by reference to the detailed description, which follows, when read in conjunction with the accompanying drawings, wherein:
FIG. 1 depicts a prior art matrix without a cognitive zone;
FIG. 2 depicts the present system in schematic form;
FIGS. 3 , 3 a and 3 b depict a flow chart of the present method; FIG. 4 depicts a 3×3 matrix with a cognitive zone comprising a single central entry;
FIG. 5 depicts a 5×5 matrix with a cognitive zone comprising a central column;
FIG. 6 depicts 5×4 matrix with a cognitive zone comprising a central column;
FIG. 7 depicts a 5×4 with two non-matching non-address attributes;
FIG. 8 depicts a 5×4 matrix with one non-matching non-address attribute;
FIG. 9 depicts a 5×4 matrix with another example attribute from FIG. 8 in the cognitive zone; and
FIG. 10 depicts an image containing an example non-resolvable non-address attribute.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 2 depicts a schematic of a non-address attribute resolution system according to the present invention. As shown, the present system includes a mail sorter 100 for removing and sorting mail pieces or items 102 . The mail sorter is able to sort mail when the non-address attributes are automatically resolved or resolved by coding.
Mail sorter 100 includes a feeding mechanism 104 which pulls successive mail pieces 102 from magazine 106 . The mail pieces 102 are transported to a high-resolution video scanner 108 for automatic scanning of a mail piece address surface 110 and generating an image 112 thereof. The mail pieces 102 may be transported at a rate of approximately 10 mail pieces per second by means known in the art. Although the scanning of the mail piece address face is discussed herein, such should be understood as an embodiment of the present invention with another embodiment including the scanning of a non-address face of the mail piece.
The image 112 is directed to OCR and pattern matching element 114 . Element 114 includes at least one microprocessor 122 , memory 124 , and address register or database 126 interconnected so as to be to automatically resolve and decode image 122 with a high degree of confidence. The actual level considered “high” is set by application as known to one skilled in the art. High confidence degree resolution includes resolution of both address and non-address attributes. Address attributes include alphanumeric characters indicative of a postal or destination address. Non-address attributes include stamps, pictorial representations, alpha numeric characters (i.e. endorsements), markings and the like.
Prior to and concurrent with image resolution at element 114 , the mail piece 102 is held in a delay loop a delay loop 116 . Should the image be resolvable with the high degree of confidence, a bar code is made to be printed on the mail piece at printer 118 and the mail piece is forwarded to sorting bins 120 where further sorting with the aid of the bar code ensues. Unsuccessfully read images are stored in database 127 .
Processor 128 is arranged in communication with database 127 and processors 114 . Processor 128 as with processors 114 , receives an image and resolves it. However, with processor 128 , the image is taken or received from database 127 and the resolution is to a lower or functional degree of confidence. In an alternative embodiment, the lower or functional degree resolution may be effected by processors 114 . A functional degree of confidence is one where it is likely or possible to identify the general nature of the non-address attribute to a degree so as to find possible matches in the form of example non-address attributes. Once obtained, the functional degree is then compared with example attributes stored in database 127 for a possible match. To facilitate this, a search is made of database 127 for best possible matches ranked upon their degree of match confidence. Typically, more than one possible match is determined given the lower degree of confidence from which the process begins. Alternatively, database 126 may substitute for database 127 . Typically, the search will produced Confidence for the match may be at least at the functional level. Finally, processor 128 includes appropriate programming for the creation of a matrix including the cognitive zone. The functional non-address attributes occupy the matrix but for the cognitive zone which is made to be occupied by the example attributes. The newly created matrix is then forwarded to an order sorting element 130 for further communication to one of a plurality of video coding stations 132 . By way of example, four video coding stations 132 are depicted. The video coding stations 132 may be networked via a local area network 134 . The bar code printer 136 is included and arranged in communication with sorting device 130 . In operation, when an image is unsuccessfully read, the printer 136 is made to print a tracking (TID) bar code on the respective mail piece which is then directed to a suitably long delay loop to enable manual/on-line resolving or specially held to enable off-line resolving. As is known in the art, the TID bar code enables the mail piece to later rejoin the successfully read mail pieces in sorting via, e.g. bins 120 . As an alternative to the TID printer actually printing the bar code, bar code printer 118 can be made to print the bar code as is depicted in FIG. 2 . Should the video encoder indicate that a non-match occurred between the resolved non-address attribute and the example non-address attribute in the cognitive zone, the processor 128 is made to create a second matrix with another attribute having a lower degree of confidence. Should another non-match occurs, another matrix is created an so on until no more example attributes are available. At this point, the entire image is shown to the encoder for manual encoding.
FIG. 3 depicts a flowchart of the present method for resolving unsuccessfully read non-address attributes. The unsuccessfully read image 112 is stored in database 127 and it is with this image that the method starts (step 200 ).
In step 202 , an analysis of the unresolvable non-address attribute is made. Given that the information was not automatically readable, a lower recognition level is herein employed.
In step 204 , the now somewhat resolved non-address attribute is matched or associated with an appropriate attribute category. This step is effected by the substeps of searching the various available categories and determining which category and/or attribute that best matches what is known about the functionally resolved attribute. The categories and example attributes (resolution permitting) are ranked by degree of matching confidence. In step 206 , a validation matrix is created comprising a plurality of attributes from an appropriate matching attribute category arranged in the cognitive zone. The matrix and cognitive zone may vary in size by application. In step 208 , the matrix is stored in one of the above mentioned databases, i.e. database 127 .
In step 210 , the matrix is forwarded to at least one of the video coding stations 132 via means described above.
In step 212 , the matrix is displayed for the coding station operator. The operator then indicates where a match exists or non-match by application. Should all the unresolved non-address attributes match the example attributes, it would be at the coders option to indicate this via a single key stroke. Such indication may be effected by known man-machine interfaces. In step 214 , acceptance or non-acceptance are indicated by the operator and transmitted to processor 128 .
In step 216 , a determination is made whether a non-match was indicated. If a match was indicated 218 , the method via connector D, 252 , to step 240 set out below. If a match was not indicated 220 , the method continues, via connector A 222 / 224 .
In step 224 , the method continues to a determination. In step 226 , a determination is made whether there are untried example attributes available for a matrix. If there are no more example attributes 230 , the image containing the non-resolved non-address attribute is forwarded to the encoder in step 234 .
In step 238 , the encoder's match indication is transmitted to database 128 .
In step 240 , a bar code is printed or a TID is updated to reflect the final decision arrived at using the resolution of the non-address attribute by the encoder. The mail piece may be sorted accordingly.
In step 242 , a determination is made whether there are other mail piece images to be resolved. If no more are present, 248 , the method ends 250 . If additional images are present 244 , the method loops back via connector C, 246 , to start 200 .
Returning to step 226 , if it is determined that additional example attributes are available, a new matrix comprising the new example attributes in the cognitive zone is created and, via connector B, 236 , the method loops back to step 208 whereby the new matrix is considered as was the previous one.
FIG. 4 depicts a 3×3 matrix 300 with a cognitive zone 302 being a single example attribute located at the center thereof. The non-address attribute is an American flag. Herein, the encoder would depress a single key indicating the entire matrix 300 matches the cognitive zone 302 attribute.
FIG. 5 depicts a 5×5 matrix 500 of American flags with a cognitive zone 502 being a column running the center of the matrix. Again, the encoder would indicate an overall match via a single key stroke. Alternatively, the encoder may highlight a match or non-match with a pointer and a mouse click. Other such indication methods may be employed as envisioned by one skilled in the art.
FIG. 6 depicts a 5×4 matrix 600 as would be displayed on a computer monitor 602 . The cognitive zone 604 runs the center of the matrix. The matrix 600 comprises American flags with all matches which again could be so indicated with a single key stroke.
FIG. 7 depicts a 5×4 matrix 700 of stamps depicting George Washington. The matrix is depicted as it would appear on a computer monitor 702 . The cognitive zone 704 is a column running the center of the matrix. Herein there are two non-matching attributes 706 . The encoder would indicate the non-match via man-machine interface, such as a key stroke or mouse pointer.
FIG. 8 depicts a 5×4 matrix 800 of American flags as would be depicted on a computer monitor 802 with cognitive zone 804 running down the center. Herein a single attribute 806 is non-matching. In operation, another matrix would be created with another example attribute that may match attribute 806 . The current example attribute of an American flag was initially considered because the cancellation of the non-matching attribute 806 included wavy lines akin to the flag.
FIG. 9 depicts a 5×4 matrix 900 of Madonna and Child as would be depicted on a computer monitor 902 with cognitive zone 904 running down the center. Herein a match is exhibited and the present invention would print an appropriate bar code based on the match indication, sort the mail piece and return to start. FIG. 10 depicts a whole image of a non-resolvable non-address attribute that would be depicted to the encoder in the event all the example attributes were exhausted.
The present invention having been presented above will be further set out in the appending claims. The above description is one embodiment of the invention leaving open the possibility for other embodiments and uses which would not depart from the spirit of the invention. For example, the present application may be used for the resolution of stamps, various groupings of letters and/or numbers and/or pictures, signatures, markings and so forth. | The present invention relates to a system and method for resolving non-address attributes on a mail piece. The present system uses a mail sorter for sorting and facilitating the obtaining of a scan of the mail piece. The image is then scanned by automatic means to determine whether the non-address attributes can be automatically resolved. In the event of an unsuccessful scan, the image is forwarded to a processor which makes a functional resolution of the non-address attribute, locates example attributes and ranks them, and creates a matrix with the example attribute in the cognitive zone. The matrix is displayed to a coder who then quickly identifies whether or not the attribute and example attribute match. In the event of a non-match, a matrix with a next highest rank example attribute is created and forwarded to the encoder until no more example attributes remain, wherein the entire image is forwarded to the encoder. | 6 |
[0001] The present application claims priority to U.S. Provisional Patent Application No. 61/411,273, filed Nov. 8, 2010, the entire disclosure of which is incorporated by reference herein.
[0002] The present invention generally relates to implantable devices which can be infused with fluid in order to cause tissue expansion.
[0003] In the case of a mastectomy, much of the mammary glands and surrounding tissue is removed, which creates a void, which can thereafter be filled with an implantable prosthesis.
[0004] Often before the implantation of a permanent prosthesis, it is desirable to utilize what is referred to as a tissue expander, in order to enlarge, or grow, a skin flap over the cavity for accommodation of the permanent prosthesis.
[0005] After implantation, the tissue expander is gradually enlarged by the infusion of fluid. This may be accomplished with an infusion needle. After gradual inflation over periods of weeks or months, the skin and subcutaneous tissue expands in order to accommodate a permanent prosthesis.
[0006] Since a tissue expander shell may leak if punctured by a needle, it is common practice to infuse fluid at a location that is remote from the tissue expander shell. A tissue expander system thus generally includes a remote needle penetrable septum which is inserted through a remote port connected to the tissue expander by means of a conduit. Known tissue expansion systems often require that the septum and the conduit that connects the septum to the tissue expander prosthesis be implanted with the tissue expander prosthesis. The surgery for implanting a tissue expansion system normally includes an incision or incisions through which the implant and conduit and septum are directed. It can be appreciated that a tissue expander with a remote septum requires a greater amount of surgery to implant than a tissue expander without a septum.
[0007] Bark, et al. describes a self-sealing tissue expander which includes a closed flexible shell that defines an internal chamber having no fluid entry port and is noncommunicable with any septum or conduit. The shell is puncturable with a needle and is self-sealing. Fluid infusion is accomplished directly through the shell.
[0008] A self-healing tissue expander is desirable, however, the thickness of self-healing expandable walls can prevent compact folding of the expander prior to insertion into a tissue pocket.
[0009] Accordingly, it is desirable to provide an improved tissue expander for preparing a breast for a more permanent mammary prosthesis, or a prosthesis in another area of the body.
SUMMARY
[0010] A tissue expander, hereinafter sometimes referred to as an implant, is provided. The expander generally includes an elastomeric shell having an anterior inside surface and a posterior inside surface, and a fluid fillable, expandable chamber therebetween.
[0011] The expander further comprises a self-sealing layer, hereinafter sometimes referred to as “self-healing layer”. The self-healing layer abuts at least a portion of the anterior inside surface. In one aspect of the invention, the self-healing layer extends only as far as the posterior inside surface. In another aspect of the invention, the self-healing layer does not extend as far as the posterior inside surface and includes boundaries which are spaced apart from the posterior inside surface. The entire shell is foldable which facilitates surgical introduction of the implant insertion into a tissue pocket and further enables inflation of the shell subsequent to insertion by fluid injected between the self-healing layer and the posterior surface.
[0012] A self-healing layer may be formed from a suitable silicone gel. The self-healing layer may be adhered to the anterior inside surface with an adhesive, for example, a silicone-based adhesive.
[0013] In some embodiments, the self-healing layer comprises a silicone gel which is located between the anterior inside surface and a partition. The partition forms a pocket, which is fixed to the anterior inside surface to form a gel pocket. The partition may be fixed to the anterior inside surface by an adhesive and a silicone gel may be disposed in the pocket.
[0014] In another aspect, a folded tissue expander is provided. The folded tissue expander is formed of an elastomeric shell with an anterior inside surface and a posterior inside surface along with a self-healing layer adhered to at least a portion of the anterior inside surface. The self-healing layer may abut the posterior inside surface or may be spaced apart therefrom. In the folded configuration, the elastomeric shell may be inserted into a surgically-created breast pocket and then expanded by injection of fluid between the posterior inside surface and the self-healing layer. After infusing the cavity with saline, the needle is withdrawn without the occurrence of leaking.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] The advantages and features of the present invention may be better understood and/or appreciated by the following description when considered in conjunction with the accompanying drawings in which:
[0016] FIG. 1 is a cross-sectional view of a tissue expander in accordance with an embodiment of present invention, generally showing an elastomeric shell having a self-healing layer abutting only a a portion of an anterior inside surface.
[0017] FIG. 2 is an alternative configuration of a tissue expander in accordance with the present invention similar to that shown in FIG. 1 wherein the self-healing layer includes a partition fixed along a perimeter thereof to an anterior surface to form a gel pocket with a silicone disposed therein; and
[0018] FIG. 3 is a folded configuration of a tissue expander in accordance with the present invention illustrating a compact folded expander facilitated by a use of a self-healing layer disposed only on one anterior surface of the tissue expander.
DETAILED DESCRIPTION
[0019] With reference to FIG. 1 , there is shown a tissue expander 10 in accordance with an embodiment of the present invention. The expander 10 is generally formed in the shape of a breast implant, with a rounded anterior portion 11 and a generally planar posterior portion 12 , forming a shell 14 of the expander 10 . It can be appreciated by those of skill in the art that the expander can take on other shapes as well, depending upon the part of the body in which the expander is to be placed, and the specific needs of the patient requiring the expander.
[0020] In the shown embodiment, generally defined between the anterior portion 11 and the posterior portion 12 is a fluid-fillable cavity 16 which, when infused with fluid, for example saline or other biologically inert fluid, enlarges the volume of expander. The expander 10 , once positioned in a breast pocket created by a mastectomy, for example, can therefore be gradually inflated to allow tissue such as skin, to grow slowly, for example, to accommodate the tissue expander 10 without causing unnecessary trauma to the patient's body. Once the breast pocket is appropriately sized, the tissue expander 10 is removed from the breast and a more permanent breast implant may be surgically implanted into the pocket that is left after removal of the expander 10 .
[0021] The anterior and posterior portions 11 , 12 forming the shell 14 of the expander 10 , may form a single unitary construction which has been formed by traditional dip molding techniques, on a mold surface, for example, a mandrel, as is well known in the art. The shell 14 may be formed of any suitable elastomeric material, for example, a silicone elastomer, for example, a silicone elastomer manufactured under the tradename PN-3206-1, available from Nusil, Inc., or other suitable, biocompatible elastomer.
[0022] The elastomeric shell 14 includes an anterior inside surface 18 and a posterior inside surface 22 .
[0023] As shown in FIG. 1 , a self-healing layer 26 covers or abuts only a portion of the anterior inside surface 18 . As also shown in FIG. 1 , the self-healing layer 26 may be disposed in a spaced apart relationship with the posterior inside surface 22 . For example, as in the shown embodiment, the self-healing layer 26 does not extend as far as to contact the curved surface region 28 that generally defines the widest perimeter of the expander located between the dome-shaped anterior portion and the generally planar posterior portion forming the shell. A perimeter portion 24 of the anterior inside surface 18 is left uncovered by the self-healing layer.
[0024] The structure of the self healing layer 26 may be selected in order to enable healing of any hole created by a infusion needle, for example, a 21 gauge or finer diameter hypodermic needle 34 . The self-healing layer prevents any leakage of saline solution when the needle 34 is removed from the expander 10 .
[0025] In one embodiment, the self-healing layer comprises a soft silicone material such as
[0026] Turning briefly to FIG. 3 , the structure of the presently described tissue expanders may significantly facilitate folding thereof prior to insertion into a breast pocket (not shown). Further, the structure may facilitate inflation of the shell 14 , as shown in FIG. 1 , with a fluid 30 , for example, a saline solution, by a hypodermic needle 34 .
[0027] The self-healing layer 26 may be cast separately from a soft silicone, for example, any suitable silicone gel, for example, a clear, tacky silicone gel, for example, a medium penetration soft silicone gel known to those of skill in the silicone gel art, such as, but not limited to MED 6350, available from Nusil Technologies, Inc. The layer 26 may be cast in a sheet form and thereafter cut and attached to the anterior inner surface 18 . Attachment to the inner surface 18 may be accomplished using a silicone adhesive 38 . This may be done after molding of the shell 14 by turning the molded shell inside-out, applying the adhesive 38 and then applying the layer 26 .
[0028] An alternative embodiment tissue expander 42 is shown in FIG. 2 with common numerical references referring to identical or substantially equivalent elements illustrated in FIG. 1 in the description of the tissue expander 10 .
[0029] Tissue expander 42 includes a self-healing layer 46 which includes a separate partition 50 fixed along a perimeter 54 thereof to the anterior inside surface 18 of the shell 14 to form a gel pocket (shown filled with a gel 62 in FIG. 2 ). Any suitable cohesive gel 62 may be utilized and the pocket 58 is of sufficient thickness, empirically determined, to enable self-healing after penetration by a 21 G or smaller hypodermic needle 34 as shown in FIG. 2 .
[0030] The tissue expander 42 may further include a needle guard (not shown) forming or covering a posterior side of the expander 42 . Such a needle guard can be provided to prevent a needle from undesirably puncturing entirely through the expander 42 .
EXAMPLE 1
Method of Making a Self-Healing Tissue Expander
[0031] A silicone gel dispersion, PN-3206-1 (Nusil Technologies) was used for constructing a flexible silicone shell. A different soft silicone gel, Nusil MED 6350 was used to form the self healing layer shown such as shown in FIG. 1 .
[0032] The shell is created by mandrel dipping process known to those of skill in the art.
[0033] Soft silicone MED 6350 was casted separately in the form of gel sheet and cured at about 150 C for about 30 min.
[0034] When fully cured, a patch of appropriate dimension was cut from the silicone gel sheet and is then attached on the inner surface of anterior side of the shell, the cut gel sheet forming the self-healing layer of a tissue expander such as shown in FIG. 1 .
EXAMPLE 2
Method of Making a Self-Healing Tissue Expander
[0035] A silicone gel dispersion, PN-3206-1 (Nusil Technologies) was used for constructing the shell.
[0036] A portion of an identical shell was cut and secured to the inside surface of the shell using a silicone adhesive to form a pocket. The pocket was filled with a cohesive silicone gel and the pocket is sealed around the cohesive silicone gel using silicone adhesive. The pocket and cohesive gel form a self-healing layer of the tissue expander such as shown in FIG. 2 .
[0037] Although there has been hereinabove described a specific tissue expander with self-healing anterior side in accordance with the present invention for the purpose of illustrating the manner in which the invention may be used to advantage, it should be appreciated that the invention is not limited thereto. That is, the present invention may suitably comprise, consist of, or consist essentially of the recited elements. Further, the invention illustratively disclosed herein suitably may be practiced in the absence of any element, which is not specifically disclosed herein. Accordingly, any and all modifications, variations or equivalent arrangements which may occur to those skilled in the art, should be considered to be within the scope of the present invention as defined in the appended claims. | A tissue expander includes an elastomeric shell having an anterior inside surface and a posterior inside surface with a self-healing layer abutting only a portion of the anterior inside surface. The layer is spaced apart from the posterior inside surface while facilitating folding of the shell prior to insertion into a tissue pocket and also enabling inflation of the shell subsequent to insertion by a fluid injected between the self healing layer and posterior surface. | 0 |
BACKGROUND OF THE INVENTION
Inflatable structures, sold by applicant under the trademark AIRBEAM are characterized by low mass, low stowed volume for on-site deployment, overload tolerance and tailored strength and stiffness. Current applications use multiple deploy-strike cycles with inflation pressure maintained while in use.
The known inflatable structures are limited in size and load carrying by both manufacturing limitations and by material properties. This invention overcomes size limitations and improves strength and stiffness of very large inflatable structures.
The known inflatable structures are described in U.S. Pat. Nos. 5,421,128 and 5,735,083. A high bias angle that elongates under pressure provides high bending strength in these structures. This invention, having added external tension elements, provides an increased moment of inertia for even greater strength and stiffness for a given inflatable structure. This invention is applicable to, but not limited to structures for shelters, bridges, deployable wings, and space structures.
SUMMARY OF THE INVENTION
This invention uses external bracing tensioned by inflatable structures. The external tensile members are made of high modulus fibers and are spaced away from the central inflatable structure by transverse frames. The structure can be made rigid after deployment by unidirectional bundles of fibers to maximize compression performance after deployment. A truss can be made up of a central inflatable structure or member that is strengthened with external braces made of high modulus fibers spaced away from the central member by transverse frames. A structural member arch can be strengthened using a cable below the member and parallel to it at some distance with spoke-like linear attachments holding the member shape under loads that would tend to collapse the arch. A deployable wing with an inflatable member spar that also relies on span-wise tension in the skin of the wing for maintenance of shape, would operate under the same principle as the other externally braced inflatable structures of this invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows an inflatable structure with three external tension cables.
FIG. 2 shows a cross section of the inflatable structure of FIG. 1 .
FIG. 3 shows an arch with an inside strengthening cable.
FIG. 4 shows a cross-section of FIG. 3 .
FIG. 5 shows an inflated wing.
FIG. 6 shows the inflatable structure with diagonal cables.
DETAILED DESCRIPTION
A truss-like structure is illustrated in FIG. 1 and in FIG. 2 , a cross section. The inflatable beam or member 1 comprises a bladder 4 , a braided restraint layer 5 and axial reinforcement straps 6 . The bladder 4 holds inflation gas, but has no structural function. The braided restraint layer 5 retains the gas pressure and provides shear and torsion resistance. The axial reinforcement straps 6 govern the inflatable structure's bending strength and stiffness. Transverse frames 2 restrain and align the bracing cables 3 at a distance from, and parallel to the central inflatable structure 1 . The end transverse frames 2 A provide tension to the bracing cables 3 at a distance from and parallel to the central inflatable structure 1 . The end transverse frames 2 A provide tension to the bracing cables 3 at a distance from and parallel to the central inflatable structure 1 .
The end transverse frames 2 A provide tension to the bracing cables 3 by the action of the central inflatable structure 1 tending to elongate when pressured. The axial reinforcement straps 6 are also tensioned by this action. A designer, by choosing materials with a particular elastic modulus, and by determining the amount of weight per unit length of each material, determines how much tension is carried in the bracing cables 3 compared to the tension carried in the axial reinforcement straps 6 , and, thus, tailors the structural properties of the truss-like externally braced structure.
Variations of this embodiment include trusses and beams, similar structures with more than three external cables and optional diagonal cables between transverse frames to increase shear and torsion stiffness and strength.
The various flexible elements of the truss example may be infused with a resin that is controllably hardened to create a permanently rigid structure that does not depend on the maintaining of the inflation pressure. This may be advantageous for very large structures for use in space that can be initially stowed in a small volume for launch.
An arched beam structure is illustrated in FIGS. 3 and 4 . The inflatable component 7 is an inflatable beam comprising a gas-impermeable bladder 10 , a braided restraint layer 11 and one axial reinforcement strap 12 . The bladder 10 retains inflation gas, but has no structural function. The braided restraint layer 11 lends the structure the capability to retain high pressure, provides shear and torsion resistance, and can be curved during the manufacturing process without wrinkling. Transverse frames 9 restrain and align the bracing cable 8 at a distance from the central inflatable component 7 . Pivots 13 can be provided as part of the transverse frames 9 to reduce the size of the transverse frames 9 when the arched beam structure is deflated and folded for storage.
Inflating the inflatable component causes the axial reinforcement strap 12 and the bracing cable 8 to be tensioned. Tension is provided to the axial reinforcement strap 12 and to the bracing cable 8 by the action of the central inflatable structure 7 that elongates and straightens when pressurized. Such action, which the designer controls by choice of the various materials, material weight per unit length, inflatable component 7 diameter, and the offset distance of the bracing cable 8 from the inflatable component 7 , determines the strength and stiffness of the arched beam.
Compared to an un-braced inflatable structure, the arched beam of FIG. 3 will have increased strength for downward loads, and little or no advantage for upward loads. Therefore, it would be beneficial for supporting structures subject to high snow loads, or for buried shelters as may be needed for lunar habitation.
Variations of the arched beam of FIG. 3 include designs with multiple axial reinforcement straps 12 and/or multiple bracing cables for increasing strength in the direction perpendicular to the plane of the arch.
In FIG. 6 the structure of FIG. 1 ( 20 ) is reinforced with diagonal cables 21 . Such diagonal cables enhance the structure when the shear stiffness of the inflated member is not sufficient.
Another example of an externally braced inflatable structure is the membrane wing shown in FIG. 5 . The inflatable spar 14 comprises a gas-impermeable bladder, a braided restraint layer, and axial reinforcement straps 15 previously described. The wing skin membrane 18 encloses the spar 14 and ribs 17 and provides the aerodynamic surface of the wing. The membrane 18 is attached to the tip rib 16 such that the action of the inflatable spar tending to elongate when pressurized creates tension in the membrane. A chord 19 , forming the trailing edge of the wing, is also tensioned by said action of the inflatable spar 14 , “span-wise”, which is necessary for controlling the aerodynamic shape of the membrane 18 between 16 and 17 .
In the wing example, the benefit of external bracing is not improved structural performance; it is the ability to control the distribution of tension into the wing skin membrane 18 for an aerodynamic benefit.
Variations of the inflatable wing example include additional inflatable elements to further improve membrane shape, the addition of cords or fibers to the membrane in order to tailor its modulus, and ribs that bend or have pivoting means in order to fold the wing flat for storage. | An inflatable structure is augmented with transverse frames and bracing cables to make a truss-like structure. This feature is adaptable for adding strength to a plain inflatable structure and to an inflatable structure forming a structural arch. It can also be incorporated into an inflatable wing. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to an automatic sewing machine.
2. Background Art
U.S. Pat. No. 4,312,282 teaches an automatic sewing machine in which a cross slide is mounted on a stand, the x carriage of which is guided displaceably on the stand, while a y carriage is displaceable on the x carriage perpendicularly thereto on a horizontal plane. The y carriage is provided with a guide arrangement, by means of which at least one workpiece can be displaced for sewing on a workpiece-receiving plate and under the sewing head. The motor driving the x carriage is mounted on the stand. The motor driving the y carriage is likewise mounted on the stand. For the y carriage to be driven on the x carriage, a shaft that is coupled with the y drive is rotatably arranged on the stand and carries a rotatable pinion that lodges on it displaceably. This pinion meshes with a rack mounted on the y carriage and serves simultaneously for stabilizing the y carriage that is guided only on a single guide. Displacement of the x carriage that is likewise guided only on a single guide and of the y carriage is to take place on the sewing plane only formed by the workpiece receiving plate. The shaft is suspended and extends only over a comparatively short guide length, on which the workpiece is guided for sewing under the sewing head. This known design has the advantage that the cross slide exhibits little mass, since the motors that serve for driving are stationary on the stand, i.e. they need not be moved together with the cross slide. However, this known design is not suitable to be used in automatic sewing machines in which the workpiece is not only guided under the sewing head, but moved over prolonged feed distances from an auxiliary station to the sewing head and vice versa. Automatic sewing machines of this type are known for instance from U.S. Pat. No. 4,809,627.
SUMMARY OF THE INVENTION
It is the object of the invention to embody an automatic sewing machine which exhibits motors stationary on the stand for driving a first and a second carriage, while ensuring the transport of a workpiece holder between the sewing head and an auxiliary station over a comparatively long feed length.
According to the invention, this object is solved by an automatic sewing machine comprising the following features:
a stand,
a workpiece receiving plate disposed on the stand,
an auxiliary station, which is allocated to the workpiece receiving plate and serves for handling at least one workpiece,
a sewing head comprising an upper arm disposed above the workpiece receiving plate and a base plate allocated to the workpiece receiving plate,
a guide and feed device,
comprising a first carriage supported on the stand to be straightly displaceable in a first direction that is parallel to the workpiece receiving plate,
comprising a second carriage guided on the first carriage to be straightly displaceable in a second direction that is perpendicular to the first direction and parallel to the workpiece receiving plate,
comprising a workpiece holder supported on the second carriage,
comprising a first drive for displacement of the first carriage on the stand in the first direction,
comprising a first motor stationary in relation to the stand, and
a first drive transmission device coupled with the first motor and the first carriage,
comprising a second drive for displacement of the second carriage on the first carriage in the second direction,
comprising a second motor stationary in relation to the stand,
comprising a shaft (44) which is stationary in relation to the stand and extends in the first direction, and which has a first end and a second end, the second end being in closer vicinity to the auxiliary station than the first end,
comprising a first bearing which is stationary in relation to the stand and adjacent to the sewing head, and which rotatably lodges the first end of the shaft,
comprising a drive connection which is coupled with the second motor on the one hand and on the other hand with the shaft in vicinity to the latter's first end,
comprising a torque/linear beating rotatably supported on the first carriage to be displaceable on the shaft in the first direction, but non-rotatable relative to the shaft, and
comprising a second drive transmission device coupled with the torque/linear bearing and with the second carriage.
Since the shaft is driven in the proximity of the sewing head, only a very short section of the shaft is exposed to torque during sewing when the first carriage is in vicinity to the sewing head, guiding the workpiece holder with the workpiece under the sewing head. Consequently, the accuracy of guidance of the workpiece holder in the second direction is very high. When the workpiece holder is situated at the auxiliary station the section subject to torque of the shaft is comparatively long, which is, however, no drawback. When the workpiece holder is moved at the auxiliary station, no substantial motions of the dynamic type occur in the second direction so that any tolerances regarding the positioning of the workpiece holder in the second direction keep within very close limits. When the at least one workpiece is sewn, only a comparatively short length of the shaft is strained by torque so that, referred to a desired position, any undesired deviation of position of the workpiece holder relative to the needle of the sewing head is minimized, which deviation may occur as a result of elastic torsion of the shaft.
Advantageous embodiments of the invention involve the arrangement, positioning and length of the shaft.
The arrangement of the guide of the first carriage underneath the workpiece receiving plate permits a compact structure with small components of little mass.
Further features, advantages and details of the invention will become apparent from the ensuing description of an exemplary embodiment, taken in conjunction with the drawing.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a plan view of an automatic sewing machine,
FIG. 2 is a vertical cross-section through the automatic sewing machine corresponding to the section line II--II of FIG. 1,
FIG. 3 is a partial rear view of the automatic sewing machine corresponding to the arrow III of FIG. 1,
FIG. 4 is a partial plan view of the automatic sewing machine corresponding to the arrow IV of FIG. 2,
FIG. 5 is a vertical partial section through the automatic sewing machine corresponding to the section line V--V of FIG. 1, and
FIG. 6 is a partial plan view of the automatic sewing machine corresponding to the arrow VI of FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The automatic sewing machine of the drawing comprises a stand 1, on which a sewing head 2 is disposed stationarily. Customarily, it comprises a base plate 3, a standard 4 and an upper arm 5. As is usual, an arm shaft 6 to be driven by an electric sewing machine drive motor 7 is lodged in the arm 5 of the sewing head 2. Conventionally, the drive of a needle bar with a needle 8 and of a hook located in the base plate 3 derives from the arm shaft 6.
A workpiece receiving plate 9 is disposed on the stand 1, its upper side defining a sewing plane 10. This workpiece receiving plate 9 is disposed above the base plate 3 and has a stitch hole that permitts the needle 8 to pass through to the hook. Designs of this type are familiar and general practice.
A guide and feed device 11 is mounted on the stand 1, by means of which workpieces 12, 13 are fed from an auxiliary station, for instance a preparatory station 14, to the sewing head 2, where they are guided during the sewing job, subsequent to which they are conveyed to another auxiliary station (not shown), for instance a piler. In the embodiment shown, a pocket section that constitutes the second workpiece 13 is folded in the preparatory station 14 and positioned on a trouser cut that constitutes the first workpiece 12 and held by a workpiece holder 15 which is part of the device 11. Both workpieces 12, 13 are held by the workpiece holder 15 on the workpiece receiving plate 9 and displaced on the latter by means of the device 11. Numerous preparatory stations 14 of this type are known, for instance from U.S. Pat. Nos. 4,819,572, 4,793,272, and 4,785,749.
The guide and feed device 11 comprises an x carriage 16 which moves on the horizontal line in the x direction, i.e. from the preparatory station 14 to the sewing head 2 and at least partially back again, consequently from the left to the right and from the right to the left--referred to viewing direction from the operator's side 17. A y carriage 18 is disposed on the x carriage 16, moving on the horizontal line in the y direction, i.e. from the operator's side 17 in the direction to the back 19 of the automatic sewing machine and vice versa.
As seen in particular in FIG. 2--the x carriage 16 is angular and comprises a bearing arm 20 which extends horizontally in the y direction and a support arm 21 which extends vertically downwards from the latter, i.e. in the z direction. The z direction corresponds to the direction of motion of the needle 8 of the sewing head 2. The support arm 21 of the x carriage 16 is supported on the stand 1 by way of an upper guide 22 and a lower guide 23. Guides of this type are generally known, for instance from Japanese patent 1 405 187, and they are commercial, for instance under the designation THK LM SYSTEM of THK CO., LTD. of Tokyo, Japan.
Between the two guides 22, 23, which are supported on a part of the stand 1 formed as a pillow block 24, an x drive 25 engages with the support arm 21 of the x carriage 16. It has an electric motor 26, which is mounted on the stand 1 underneath the pillow block 24 and which chives a timing belt pinion 27 lodged in the stand, as seen in particular in FIGS. 2 and 3. In vicinity to the preparatory station 14, a deflection pulley 28 that is allocated to the timing belt pinion 27 is lodged in the stand 1. An endless timing belt 29 is fixed to the support arm 21 of the x carriage by fastening means 30 and guided around the pinion 27 and the deflection pulley 28. This x drive 25 serves to displace the x carriage 16 in the x direction between two end positions that are roughly outlined by dot-dashed lines in FIG. 1.
The y carriage 18 is supported on the bearing arm 20, for instance in the form of a rectangular robe, of the x carriage 16 by way of two guides 31, 32 which, in the embodiment shown, are both on a common horizontal plane, i.e. an x-y plane, and extend in the y direction. A y drive 33 is provided for the y carriage 18 to be displaced on the x carriage 16. This drive 33 has an electric motor 34 which is fastened to a support 36 of the stand 1 by means of a support plate 35. A timing belt pinion 37, which has an axis of rotation 38 that extends in the x direction, is coupled with the motor 34. A timing belt pulley 39 is disposed in parallel thereto--as seen in particular in FIGS. 2, 3 and 4--and has an axis of rotation 40 that is parallel to the axis of rotation 38, i.e. it extends likewise in the x direction. The timing belt pinion 37 lodges in the support plate 35 and in a bearing plate 41 that is parallel thereto and mounted on the stand 1. The timing belt pulley 39 lodges rotatably in a pillow block 42, part of which is formed by the bearing plate 41. An endless timing belt 43, by means of which the motor 34 drives the timing belt pulley 39, is slung around the pinion 37 and the pulley 39. A shaft 44 likewise extending in the x direction is tightly united with the timing belt pulley 39, its axis of rotation being identical with the axis of rotation 40. This shaft 44 rims as far as into the proximity of the preparatory station 14, where it is supported in relation to the stand 1 by means of a bearing 45. As seen in particular in FIG. 2, the shaft 44 is disposed underneath the workpiece receiving plate 9.
At the point of intersection of the bearing arm 20 and the support arm 21 of the y carriage 18, the latter is provided with a bearing and guide housing 46 that is passed through by the shaft 44. Concentrically of the shaft 44 and thus concentrically of the axis of rotation 40, a timing belt pulley 48 is supported freely rotatably by means of rolling beatings 49 in the housing 46, this timing belt pulley 48 again being non-rotatably joined to a torque/linear bearing 50. By way of balls 51, this torque/linear bearing 50 is joined to the shaft 44 to be non-rotatable, but displaceable in the x direction. These balls 51 engage with grooves 52 of the shaft 44 and with grooves 53 of a bearing bush 54 that encloses the shaft 44, as seen in detail in FIG. 6. This bearing bush 54 is non-rotatably connected with the timing belt pulley 48. So, the grooves 52, 53 extend also in the x direction. Torque/linear bearings 50 of this type are generally known and commercial.
In the vicinity of the free end of the x carriage 16, i.e. the end turned towards the back 19 of the automatic sewing machine, a deflection pulley 55 is lodged freely rotatably in a beating 56 that is connected with the x carriage 16. An endless timing belt 57, which is fastened to the y carriage 18 by fastening means 58, is slung around the timing belt pulley 48 and the deflection pulley 55 so that, as a result, the y carriage 18 can be displaced in the y direction by the electric motor 34 that is stationary on the stand. Consequently, the y drive 33 is formed by the motor 34, by the timing belt pinion 37, by the timing belt pulley 39 and the timing belt 43, by the shaft 44 which is driven by the timing belt pulley 39, by the torque/linear bearing 50 and the timing belt pulley 48 comprising the deflection pulley 55 and the timing belt 57.
The workpiece holder 15 is fixed to a double-armed, cranked lever 59, namely at the free end of the latter's cranked lever arm 60 of greater length. The lever 59 is arranged on the y carriage 18 in a pivot bearing 61 pivotably about a pivot axis 62 that extends in the x direction. The lever 59 has a--as compared with the lever arm 60--short lever arm 63, which extends in a direction towards the back 19 of the automatic sewing machine and with which engages a lift and press drive 64 that is supported on the y carriage 18. The lift and press drive 64 is a linear drive, i.e. a pneumatically actuated piston-cylinder drive.
The lever arm 60 extends in the y direction and is cranked in the direction towards the preparatory station 14. As seen in FIG. 2, it extends substantially horizontally and is disposed directly above the workpiece receiving plate 9.
Operation takes place as follows:
The first workpiece 12, in the present case the trouser cut, is placed on the workpiece receiving plate 9 under the preparatory station 14 which is formed as a folding device. Then the second workpiece 13, i.e. the pocket section, is folded in the preparatory station 14 and placed on the first workpiece 12. By the motors 26 and 34 being correspondingly triggered by a central computer control unit 65, the workpiece holder 15 is moved into a position shown by dot-dashed lines on the left of FIG. 1. By corresponding actuation of the lift and press drive 64 which is also triggered by the control unit 65, the workpiece holder 15, which had previously been in a position lifted off the workpiece receiving plate 9 and shown by dot-dashed lines in FIG. 2, is lowered onto the workpieces 12, 13 and pressed on the workpiece receiving plate 9. When all the the parts that are between the first workpiece 12 and the second workpiece 13 have been pulled out of the preparatory station 14, the workpiece holder 15 and the workpieces 12, 13 are moved on the workpiece receiving plate 9 substantially in the x direction into a position under the sewing head 2 shown in solid lines in FIG. 1. This feed motion again takes place by the motors 26 and 34 being correspondingly triggered. It reaches over a feed length a in the x direction.
By the sewing machine drive motor 7 of the sewing head 2 and the motors 26 and 34 being correspondingly triggered, a sewing job is then carried out, the workpiece holder 15 and the workpieces 12, 13 being guided under the needle 8 along the course of a seam 66 to be produced; this seam 66 is sewn through a corresponding recess 67 in the workpiece holder 15.
During this job, the workpiece holder 15 still covers a guide length b in the x direction, 5 b>a>2 b applying to the ratio of a relative to b. The maximum length of total motion c, to which applies c=a+b, corresponds to the length by which the x carriage can be displaced maximally in the x direction and consequently on the shaft 44. Between the bearing 45 and the pillow block 42, the shaft 44 must have a length d to which d=a+b+e applies, e being the maximum extension of the x carriage in the x direction in the vicinity of the guides 47 for the shaft 44. In practice, dimensions of d=1500 mm are conceivable. Referred to the x direction--the pillow block 42 with the timing belt pulley 39 is close to the sewing head 2 so that, during the entire sewing job, there is only a small distance of the timing belt pulley 48 and the torque/linear bearing 50 from the pillow block 42. Consequently, it is a minor portion of the shaft 44 that may be exposed to torque by reason of displacements of the workpiece holder 15 in the y direction during the sewing job. Correspondingly, errors in guidance of the workpiece holder 15 during the sewing job are negligible. | An automatic sewing machine comprises a stand, on which a workpiece guide and feed device is mounted. This device substantially comprises an x carriage, a y carriage displaceable thereon and a lever with a workpiece holder for the displacement of workpieces on a workpiece receiving plate. The y carriage is drivable by a drive stationary on the stand by way of a shaft which is likewise stationary on the stand and passes though the x carriage. A drive for the y carriage is supported on the shaft by means of a torque/linear bearing. Driving the shaft takes place in proximity to the sewing head and at a distance from an auxiliary station so that inaccuracies of guidance occasioned by torsion of the shaft are minimized during the sewing operation. | 3 |
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application No. 60/786,640 filed Mar. 28, 2006.
STATEMENT REGARDING FEDERALLY-SPONSORED RESEARCH AND DEVELOPMENT
[0002] This invention was made with Government support under contract awarded by the United States Department of Energy. The Government has certain rights in the invention.
REFERENCE TO AN APPENDIX
[0003] (Not Applicable)
BACKGROUND OF THE INVENTION
[0004] 1. Field of the Invention
[0005] This invention relates generally to fuel cells and more particularly to fuel cell systems that can be used in sulfur environments.
[0006] 2. Description of the Related Art
[0007] Fuel cells liberate electrochemical energy from fuel streams containing hydrogen and/or other gases. A particular type of fuel cell, known as a solid oxide fuel cell (SOFC), has the ability to produce energy from hydrocarbon fuels at efficiencies far greater than traditional combustion engines, potentially as high as 80% for integrated systems. The discovery of a feasible energy production process is very important, given that natural gas and oil reserves are at low levels and continue to diminish. Though coal is also a limited resource, very large quantities still exist in many countries, including the USA. Coal can be used as a fuel for SOFCs if it is gasified to form a fuel known as “coal syngas”.
[0008] A diagram demonstrating how a typical SOFC works is shown in FIG. 1 . Another simple diagram of a basic SOFC is shown in FIG. 2 . Since SOFC are electrochemical devices, they consist of three main components: an anode, a cathode and an electrolyte. As shown in FIG. 1 , available CO and H 2 in the fuel stream are utilized at the SOFC anode. H 2 oxidizes more readily than CO due to the faster diffusion rate of H 2 into the porous anode. The fuel stream reacts in the triple phase boundary (the area where the fuel, oxygen ions, and electrons produced by the oxidation are present) of the anode. The electrons produced by oxidation constitute the electrical power produced by the fuel cell. After reaching a power load, the electrons travel to the cathode of the SOFC where oxygen from air is reduced to oxygen ions (O 2− ). The oxygen ions then travel across an electrolyte, such as yttria stabilized zirconia (YSZ), that only allows the passage of oxygen ions. The ions then complete the circuit when they reach the anode.
[0009] During operation, a fuel stream containing H 2 and/or CO flows over the anode, while the cathode is exposed to either oxygen or air. When a load is applied to the system, oxygen reduces at the cathode to form oxide ions as noted above and according to the following:
[0000] O 2 +4 e − →2O 2− (1)
[0000] These ions migrate through the electrolyte to the anode, where they react with the fuel stream components to produce an electrical charge according to the following:
[0000] 2CO+2O 2− →2CO 2 +3 e − (2)
[0000] 2H 2 +2O 2− →2H 2 O+4 e − (3)
[0010] H 2 S is a colorless, poisonous gas that is present in gasified coal and can cause many problems throughout SOFC systems, most notably to the anode. The SOFC shown in FIG. 1 shows little to no resistance in H 2 S-containing environments. The activity of a typical SOFC anode drops considerably after exposure to H 2 S concentrations as small as 2 ppm. In the presence of larger concentrations of H 2 S, this effect can be irreversible.
[0011] Therefore, in order to use gasified coal as a fuel source for SOFCs, either the anodes in the SOFC must be tolerant to H 2 S, or there must be no H 2 S present in the inlet fuel stream. The removal of H 2 S from fuel streams is expensive. Such costly fuel treatments to remove impurities as H 2 S prevent SOFC from competing with more traditional power generation methods. State-of-the-art sulfur tolerant anodes effectively react H 2 S, but show poor results when attempting to oxidize H 2 , making them inappropriate for power production.
[0012] H 2 S is typically removed during coal gasification by the Claus process, where a partial oxidation with air produces elemental sulfur and water. This process consists of two consecutive steps:
[0000] 2H 2 S+3O 2 →2SO 2 +2H 2 O (4)
[0000] 2H 2 S+SO 2 →3S+2H 2 O (5)
[0000] The former reaction is carried out at temperatures nearing 1400 K as a non-catalytic combustion, while the latter reaction is a reversible catalytic process taking place over an equilibrium reactor train. The efficiency of this reaction scheme is limited by multiple side reactions, including the oxidation of sulfur:
[0000] S+O 2 →SO 2 (6)
[0000] and a reverse Claus process:
[0000] 3S+H 2 O SO 2 +H 2 S (7)
[0013] The largest contemporary obstacles to industrial or distributed use of SOFC are their susceptibility to poisoning by H 2 S impurities and the necessary costs of fuel treatment to remove H 2 S from syngas. While SOFC have shown encouraging stability and performance in systems containing only H 2 and H 2 O, it is costly and difficult to locate and/or produce large quantities of pure elemental hydrogen. The damage to SOFCs if the H 2 S is not removed is unacceptable.
[0014] Due to the high operating temperature of the SOFC, H 2 S can also thermally decompose:
[0000] H 2 S→½S 2 +H 2 (8)
[0000] The elemental sulfur and hydrogen produced by this chemical reaction may further react in the electrochemical reactions
[0000] H 2 +O 2− →H 2 O+2 e − (9)
[0000] ½S 2 +2O 2− →SO 2 +4 e− (10)
[0000] where E 0 for the reactions described by Equations (11) and (12) are 1.185 and 0.883 V, respectively. The simultaneous presence of H 2 S along with SO 2 produced by the reaction described by Equation 12 at the SOFC anode may lead to their consumption via the reverse Claus process.
[0015] The contemporary standard for SOFC anodes is a metal such as Ni or Pt. These metals possess excellent catalytic activity toward H 2 and CO oxidation at the temperatures (˜1000° C.) reached during SOFC operation. However, conventional SOFC anodes such as Ni or Pt are poisoned by H 2 S present in syngas, causing poor electrochemical performance and even irreversible system failure. For example, platinum catalyzes the oxidation of H 2 S to sulfur oxides at temperatures above 300° C. Researchers have examined the use of Pt as an anode in a SOFC utilizing an H 2 S-containing fuel stream, but Pt anodes have poor longevity when used with H 2 S-containing fuel streams due to the formation of PtS, which increases the interfacial resistance between the Pt anode and the YSZ electrolyte leading to detachment of Pt from YSZ. Fuel streams containing both 5% H 2 S (balance H 2 ) and pure H 2 S have been tested, and it was found that longer anode lifetimes were achieved when using the dilute H 2 S feed.
[0016] Prior studies utilizing Pt as a SOFC anode in H 2 S-containing systems predominantly tested systems containing YSZ as the electrolyte. Such studies utilized ceria-based electrolytes in an effort to reduce the SOFC operating temperature. While low overpotentials and high current exchange densities were observed in such systems as in other Pt anode SOFC systems, the ceria electrolyte has been found to develop electronic conductivities in reducing environments and demonstrate poor long-term stability in a H 2 S environments. Corroborating the results of the previous researchers mentioned, the Pt anode demonstrated a steady loss in activity with time due to the formation of PtS.
[0017] Given that Pt anodes proved to be inappropriate for SOFC systems utilizing H 2 S-containing feeds, attention was given to contemporary Ni/YSZ anode SOFCs. A study using impedance analysis and DC polarization showed extensive sulfur poisoning due to the formation of NiS during operation. Since NiS has a melting point below the operating temperature of SOFCs, Ni-based anodes are susceptible to melting during operation with H 2 S-containing fuels. Differences in thermal expansion between Ni/YSZ and NiS can also prove problematic. Analogous to the results found for Pt anodes, it was found that the degree of sulfur poisoning on Ni/YSZ anodes is proportional to the total H 2 S content in the incoming fuel stream. Another study found that the polarization resistance for Ni/YSZ anodes doubled when a H 2 fuel stream containing 5% H 2 S was utilized, while yet another study found that sulfur poisoning on Ni/YSZ anodes became irreversible after exposure to 105 ppm H 2 S at 1273 K.
[0018] Due to the infeasibility of Pt and Ni-based SOFC anodes in H 2 S environments, researchers have turned their attention to anodes made of perovskite oxides, which is a term for compounds having the generic composition ABO 3 . One study examined the properties of a wide range of perovskites based on lanthanum chromite (La 1-x A x Cr 1-y B y O 3 ). While most of the materials tested somewhat fulfilled the requirements of an SOFC anode, none of the materials were found to have a combination of properties superior to Ni/YSZ. Poor conductivity, lacking activity toward hydrogen oxidation, and thermal expansions not matching those of YSZ or ceria-based electrolytes were among the disadvantages associated with using these materials as SOFC anodes.
[0019] Conventional studies of the properties of La x Sr 1-x TiO 3 (LST) found it to meet all requirements for SOFC anodes, and others successfully tested SOFCs utilizing LST anodes using fuel streams with concentrations of H 2 S ranging from 10 to 5000 ppm. These anodes showed little degradation over time and even showed an increase in activity when 5000 ppm H 2 S was present. This phenomenon was attributed to the SOFC oxidizing ˜12% of the available H 2 S, producing additional electricity.
[0020] LST anodes also oxidize other fuel gas species present in the fuel stream, such as H 2 , along with H 2 S, although the literature shows that LST does not have high electrocatalytic activity toward any fuel species. The overall electrocatalytic performance of LST anodes was noted in the literature to be far below that found using existing anode materials, such as Ni/YSZ. The maximum power density found using LST anodes is 175 mW/cm 2 , while power densities of up to 1.8 W/cm 2 have been demonstrated by other contemporary systems.
[0021] More recent studies have shown that a perovskite known as lanthanum strontium vanadate (La x Sr y VO 3 or LSV) is not only resilient to H 2 S when used as a SOFC anode in 0-10% H 2 S environments, but further shows excellent activity toward H 2 S oxidation. LSV, however, does not show strong activity toward oxidation of other fuel gas species.
[0022] Studies using a Pt anode were also carried out for comparison. Performance of SOFCs utilizing LSV anodes showed no significant deterioration during a 48 hour period of operation in H 2 S environments. Moreover, the performance of the LSV anode appeared to increase as H 2 S concentration increased.
BRIEF SUMMARY OF THE INVENTION
[0023] The invention is a solution to the problem of damage to conventional SOFC by H 2 S without the added cost of fuel treatment by taking advantage of the strengths of certain anode materials rather than attempting to overcome their known weaknesses. Thus, coal syngas can be used as a fuel for SOFCs if the levels of H 2 S present in coal can be accommodated by the SOFCs. The invention shows promise in making reformed fuel containing sulfur species a viable fuel source for energy production via SOFCs.
[0024] Though low grade thermal energy may be recovered from the Claus process, it is more desirable to replace the combustion furnace of the first step in fuel treatment with a H 2 S/Air SOFC with a LSV anode, which oxidizes H 2 S electrochemically. This allows direct conversion of the energy released to electricity at efficiencies as high as 80% for integrated systems.
[0025] The electrochemical oxidation of H 2 S in a SOFC begins with the reaction of migrated oxide ions and H 2 S, forming either elemental sulfur:
[0000] H 2 S+O 2− →½S 2 +H 2 O+2 e− (11)
or SO 2 :
[0026] H 2 S+3O 2− →SO 2 +H 2 O+6 e− (12)
[0000] where E 0 for the reactions described by Equations 11 and 12 are 0.801 and 0.855 V, respectively. It has been found that the reaction of Equation 12 predominates in the sulfur-tolerant SOFC, especially at high levels of fuel utilization.
[0027] Although LSV anodes realize power densities of only 140 mW/cm 2 , comparing poorly with contemporary, sulfur-intolerant SOFC anodes, numerous observations suggest that the LSV anode preferentially oxidizes H 2 S, even in the presence of a large amount of orthodox SOFC fuel gases such as H 2 . The ability of the LSV anode preferentially to oxidize H 2 S while leaving behind benign fuel gas constituents makes it a seemingly excellent choice for “scrubbing” H 2 S from a fuel gas stream while recovering electricity from the process. The gas constituents remaining in the fuel stream, such as H 2 , CO, CH 4 , etc. are then more efficiently oxidized by contemporary sulfur-intolerant SOFCs downstream from the LSV anode SOFC.
[0028] The process includes conveying gas containing sulfur (as harmful sulfur species) through a sulfur tolerant planar solid oxide fuel cell (PSOFC) stack for sulfur scrubbing, followed by sending the gas through a non-sulfur tolerant PSOFC stack. The sulfur tolerant PSOFC stack utilizes anode materials, such as LSV, that selectively convert H 2 S present in the fuel stream to other non-poisoning sulfur compounds. The remaining balance of gases remaining in the completely or near H 2 S-free exhaust fuel stream is then used as the fuel for the conventional PSOFC stack that is downstream of the sulfur-tolerant PSOFC. In this manner, a broad range of fuels such as gasified coal, natural gas and reformed hydrocarbons are used to produce electricity.
[0029] Utilizing the invention rather than conventional coal combustion will effectively reduce the total amount of CO 2 emitted to the environment while reducing fuel costs. The process produces only negligible amounts of NO, since combustion reactions are not used, while the capture efficiency of other pollutants such as SOX and particulate matter are greatly increased when a laminar flow electrostatic precipitator is used for the capture of these pollutants.
[0030] The invention thus includes a process for using a fuel derived from “coal syngas” which contains H 2 S. Syngas is an attractive option for SOFC fuel due to the abundance of coal in the US. Current estimates place the amount of coal produced in the US at 1.1 billion short tons each year. Moreover, the production, storage and transportation of conventional SOFC fuels such as hydrogen are both inefficient and dangerous. Coal, conversely, has been mined, stored and shipped worldwide for centuries.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0031] FIG. 1 is a schematic illustration of a conventional solid oxide fuel cell.
[0032] FIG. 2 is a schematic illustration of a conventional solid oxide fuel cell.
[0033] FIG. 3 is a graphical illustration of the relative performances of SOFCs, one with a platinum anode and the other with a LSV anode, in an H 2 S containing fuel blend with V cell =0.44V; T=1273K; fuel flow rate=14 sccm.
[0034] FIG. 4 is a graphical illustration of the impedance spectra for a LSV SOFC in 100% H 2 and 10% H 2 S/90% H 2 fuel gas.
[0035] FIG. 5 is a schematic illustration of a SOFC with a sulfur-tolerant anode, where A is LSV, LST or other such sulfur-tolerant anode materials; B is the combination of the material used in layer A along with an electrolyte such as YSZ or GDC; and C is YSZ or GDC.
[0036] FIG. 6 is a schematic illustration of a SOFC with a sulfur-intolerant anode, where D is a catalyst such as nickel (Ni); E is the combination of the catalyst used in layer D along with an electrolyte such as YSZ or GDC; and F is YSZ or GDC.
[0037] FIG. 7 is a schematic illustration of a system according to the present invention in which the first stage is a sulfur-tolerant SOFC and the second stage is a sulfur-intolerant SOFC.
[0038] FIG. 8 is another schematic illustration of a system according to the present invention in which the first stage is a sulfur-tolerant SOFC and the second stage is a sulfur-intolerant SOFC.
[0039] In describing the preferred embodiment of the invention which is illustrated in the drawings, specific terminology will be resorted to for the sake of clarity. However, it is not intended that the invention be limited to the specific term so selected and it is to be understood that each specific term includes all technical equivalents which operate in a similar manner to accomplish a similar purpose. For example, the word connected or term similar thereto are often used. They are not limited to direct connection, but include connection through other elements where such connection is recognized as being equivalent by those skilled in the art.
DETAILED DESCRIPTION OF THE INVENTION
[0040] A solution to the problem of sulfur in the gas stream of SOFCs has been developed utilizing a two-stage reaction process, which is shown in FIGS. 7 and 8 . The first stage includes a fuel cell stack utilizing sulfur tolerant anodes, while the second stage includes conventional fuel cells. The fuel gas flows first through the first stage SOFC, which preferably oxidizes at least the sulfur-containing species. The gas then exhausts from the first stage and flows downstream into the second stage, which has higher energy production levels, but cannot tolerate any substantial amount of sulfur in the fuel gas stream. Thus, after the fuel gas has been “scrubbed” of sulfur by the first stage, it flows downstream to the second stage, which produces a substantial amount of energy.
[0041] Diagrams of the cells used in each stack are shown in FIGS. 5 and 6 . The anode in the sulfur-tolerant stack utilizes a catalytic material with high activity toward the electrochemical oxidation of H 2 S, such as, but not limited to, lanthanum strontium vanadium oxide (LSV), lanthanum strontium tin oxide (LST), etc. as disclosed in International Application No. PCT/US/2006010620, International Publication No. WO 2006/102525 A2, which is incorporated herein by reference. The catalyst used combines a high affinity toward the oxidation of H 2 S along with sustainable behavior using coal syngas as fuel. At high levels of fuel utilization, the preferred product of the reaction utilizing H 2 S is SO 4 Thus, H 2 SO 4 , which has a commercial value, can be produced by the process. The outlet gas stream of the first SOFC stack is free of or containing very low concentrations of H 2 S, such as a few parts per million (ppm). The first stage preferably selectively oxidizes all H 2 S present in the coal syngas fuel stream.
[0042] The outlet gases from the first stage are then conveyed downstream to the second stage. The second stage utilizes more conventional, sulfur-intolerant fuel cell catalyst materials, such as, but not limited to, Ni/YSZ, Ni/gadolinium doped cerium oxide (GDC), and others. Since most if not all H 2 S has been removed (by the first stage) from the gas stream that enters the second stage, the SOFCs used in the second stage show enhanced stability. The combination of these two stages allow the system to utilize fuels containing sulfur species, and this dramatically improves the viability of SOFC technology for distributed generation purposes.
[0043] The two-stage reaction system has been designed to utilize a syngas feed. A simple schematic of the proposed system is shown in FIG. 7 . The SOFCs in the first stage utilize LSV anodes. These SOFCs effectively “scrub” any H 2 S present in the syngas stream via electrochemical oxidation. The outlet gases from this LSV SOFC are fed to another SOFC utilizing conventional Ni anodes. Thus, with no H 2 S remaining in the fuel stream, the Ni anodes more effectively oxidize the remaining fuel species by avoiding SOFC performance degradation and improving system longevity.
[0044] The invention uses two different types of SOFC anodes—one that is active toward H 2 S oxidation, the other that is active toward syngas oxidation—in separate SOFCs placed in series in a gas flow path. In this way, the two SOFC units are able to oxidize a syngas stream containing H 2 S impurities.
[0045] It is necessary that the material used as the SOFC anode in the second stage meet a number of stringent requirements. Catalytic activity towards reactant oxidation as well as high electronic conductivity is required to minimize polarization losses. The porosity of the material must support effective gas transport while possessing good chemical and mechanical compatibility with other parts of the SOFC. Stability over a wide oxygen partial pressure range is necessary due to the differences in oxidizing conditions at the fuel inlet and outlet. For fuel streams containing only H 2 and/or CO, Ni/yttria stabilized zirconia (YSZ) is the standard anode of choice as it satisfies most of these requirements.
[0046] Cathodes used in the second stage of the SOFC system must also have thermal expansion coefficients that closely match electrolytes to avoid mechanical problems during SOFC operation. In addition, chemical stability, low interactions with electrolyte, high electrocatalytic activity and adequate electronic and ionic conductivity are desired in an ideal SOFC cathode. The current orthodox choice for cathode material in SOFCs operating near 1000° C. is strontium-doped LaMnO 3 (LSM), which represents a compromise of the above requirements.
[0047] For the electrolyte layer, three properties are necessary: high conductivity, little electronic conductivity and the ability to conduct oxygen ions. YSZ is the industry standard, as it boasts high conductivity above 700° C., negligible electronic conductivity below 1500° C. and is an oxygen ion conductor. An alternative electrolyte, gadolinium doped ceria (GDC) has greater conductivity than YSZ while also conducting oxygen ions, but has been reported to develop electronic conductivity and is partially reduced in H 2 at temperatures above 600° C.
[0048] Button cells containing sulfur-tolerant LSV anodes are used with a coal syngas feed to oxidize H 2 S present in the fuel stream. These cells, illustrative of the types of cells that can be used in the fuel stream, are shown in FIGS. 5 and 6 . The process and apparatus electrochemically “polish” H 2 S from coal syngas. Lanthanum strontium vanadate (LSV) anodes are used in planar solid oxide fuel cells to effectively “scrub” any H 2 S present in the hot syngas fuel stream via electrochemical oxidation, while leaving behind fuel components such as H 2 and CO. The outlet gases from this LSV SOFC stage are available for combustion or reaction with another SOFC stage utilizing conventional Ni anodes. With no H 2 S remaining in the fuel stream, the Ni anodes are able to effectively oxidize the rest of the syngas while avoiding SOFC performance degradation and improving system longevity.
[0049] The feasibility of the oxidation of H 2 S-containing fuel streams by LSV SOFCs has been demonstrated. FIG. 3 shows a comparison of the performances of Pt and LSV anodes in H 2 S-containing environments. In this study, humidified H 2 was the fuel stream for the first 2 hours of the test. After 2 hours, the fuel stream was changed to a 5% H 2 S/95% H 2 mixture. Although the Pt anode failed quickly after the introduction of H 2 S into the SOFC fuel stream, the SOFC utilizing LSV anodes actually showed an improvement in performance. It is theorized that this phenomenon is attributable to the additional electricity produced from the electrochemical oxidation of H 2 S.
[0050] FIG. 4 shows the impedance spectra for a LSV SOFC in both H 2 and 10% H 2 S/90% H 2 environments. It can be seen that SOFC resistances were reduced by nearly 70% once the H 2 S/H 2 fuel blend was introduced to the system. This rapid transition was also found to be fully reversible. The authors concluded that the reduction in overall polarization resistance was due to easier charge transfer processes at the LSV anode upon introduction of the H 2 S/H 2 fuel blend, and further claim this to be an indication of the preferential oxidation of H 2 S over H 2 at the LSV anode.
[0051] The experimental syngas feed is comprised of 40 mole % CO, 26.3 mole % H 2 , 33.7% N 2 , 300 ppm H 2 S and a relative humidity of 2% in order to approximate the average formulation for syngas derived from Pittsburgh No. 8 coal. Operating temperature (T o ) and electrolyte type (E) of the SOFC as well as porosity (ε) of the SOFC anode play a large role in cell performance. Operating temperature of the LSV SOFC has been tested in the range of 1173 K to 1273 K when utilizing H 2 S/H 2 or H 2 S/N 2 feeds.
[0052] It has been shown experimentally by others that, starting with a fuel gas containing 5% H 2 S and 95% CH 4 , a product gas (the gas downstream of the sulfur-tolerant SOFC) contained the following amounts of H 2 S after flowing through a SOFC having LSV anode material at the current densities (i) indicated:
[0000]
Species
i = 0
i = 160 mA/cm 2
i = 400 mA/cm 2
H 2
32.86%
20.79%
12.09%
CH4
63.74%
71.27%
76.87%
H 2 O
1.52%
5.67%
6.87%
H 2 S
1.37%
1.12%
2.72%
[0053] Experiments performed on a LSV prototype with 30% fuel utilization and i=100 mA/cm 2 , showed that 57% of the H 2 S was converted to materials that would not damage the anode. At i=350 mA/cm 2 , 41% of the H 2 S was converted. Clearly in all cases, LSV (La 0.7 Sr 0.3 VO 3 ) is highly selective to H 2 S. However, as power density increases, the reaction rates tend to move back towards higher utilization of H 2 or other fuel sources, not H 2 S. Thus, the experiments show the viability of the system.
[0054] Although the system described herein describes gaseous fuel, it will become apparent that a liquid fuel can be used. Thus, suitable fuels in any fluidic (gas or liquid) form can be used with the present invention. Of course, other modifications can be made to the embodiments described above. For example, a plurality of SOFC can be mounted in series or in parallel within the first or second stages described above.
[0055] The term “sulfur-tolerant” is defined herein as being substantially unharmed by exposure to significant amounts of sulfur-containing molecules. Likewise, “sulfur-intolerant” is defined herein as being substantially harmed by exposure to significant amounts of sulfur-containing molecules. Something is “harmed” if its power density is diminished by more than about 25%.
[0056] This detailed description in connection with the drawings is intended principally as a description of the presently preferred embodiments of the invention, and is not intended to represent the only form in which the present invention may be constructed or utilized. The description sets forth the designs, functions, means, and methods of implementing the invention in connection with the illustrated embodiments. It is to be understood, however, that the same or equivalent functions and features may be accomplished by different embodiments that are also intended to be encompassed within the spirit and scope of the invention and that various modifications may be adopted without departing from the invention or scope of the following claims. | Conveying gas containing sulfur through a sulfur tolerant planar solid oxide fuel cell (PSOFC) stack for sulfur scrubbing, followed by conveying the gas through a non-sulfur tolerant PSOFC stack. The sulfur tolerant PSOFC stack utilizes anode materials, such as LSV, that selectively convert H 2 S present in the fuel stream to other non-poisoning sulfur compounds. The remaining balance of gases remaining in the completely or near H 2 S-free exhaust fuel stream is then used as the fuel for the conventional PSOFC stack that is downstream of the sulfur-tolerant PSOFC. A broad range of fuels such as gasified coal, natural gas and reformed hydrocarbons are used to produce electricity. | 7 |
TECHNICAL FIELD
The present invention relates to a seat belt tightening system for restricting the pay out of the seat belt and automatically tightening the seat belt by taking up slack therefrom in case of a vehicle crash, and in particular to such seat belt tightening device which has a highly integral and compact structure. The present invention is also related to a novel mechanism for preventing the reverse rotation of a rotary clamping mechanism which can be advantageously used in such vehicle seat belt tightening systems.
BACKGROUND OF THE INVENTION
A vehicle seat is typically equipped with a seat belt to restrain the vehicle occupant from being thrown forward in case of a vehicle crash, and such a seat belt is sometimes provided with a retractor device equipped with an emergency locking retractor (which is referred to as ELR device hereinafter) for locking the winding spool of the seat belt in case of a sudden stop or a crash, however, without restraining the movement of the occupant under normal condition.
An ELR device typically detects a deceleration level indicative of a vehicle crash or a rapid pay-out of the seat belt before it locks up the winding spool in a very short period of time. Therefore, if the amount of the slack of the seat belt in the initial stage is excessive, there is a possibility that the seat belt may be inadequate to restrain the occupant to a necessary extent.
In view of such a problem, various devices for tightening the seat belt in case of a vehicle crash or preloader devices have been proposed:
A. Structures for winding a seat belt by driving the winding spool of the ELR device (refer to Japanese utility model laid out publication No. 54-169316);
B: Structures for pulling in the end of the seat belt opposite to the ELR device end by rotating a winding spool making use of the expansion of a propellant resulting from ignition and explosion thereof (refer to Japanese patent publication No. 53-21574); and
C: Structures for linearly pulling in a part of the seat belt paid out from the ELR device by coupling a clamp for gripping the seat belt to a piston which undergoes a linear displacement by the spring force of a spring or the like (refer to Japanese patent laid open publication No. 60-259553);
However, according to the structures of the categories A and B, if the seat belt is loosely wrapped around the winding spool of the ELR device, most of the power of the drive device is expended on tightly wrapping the seat belt around the winding spool and a sufficient restraint of the vehicle occupant may not be achieved.
According to the structures of the category C, a sufficient tension may be applied to the seat belt without regards to the state of the ELR device, but a relatively large displacement of moveable parts is required for linearly pulling the seat belt, and the size of the device tends to be excessively large in order to ensure a sufficient stroke of pulling the seat belt.
These ELR devices and preloaders are typically provided with a reversion preventing device consisting of a ratchet wheel and a ratchet pawl for permitting free unwinding and winding of the seat belt under normal condition and locking up the winding spool only in case of an emergency (Refer to Japanese patent publication No. 53-21574 and Japanese utility model publication No. 53-25943). However, according to such conventional arrangements, the ratchet pawl is urged into engagement with the ratchet wheel by a spring to prevent the rotation of the ratchet wheel in the reverse direction, and the reliability of such a reversion preventing device is inevitably much dependent on the elasticity of the spring which causes the necessary movement of the ratchet pawl. Therefore, the operation of the reversion preventing device is not entirely free from the chance of a failure if the ratchet pawl should be jammed or mechanically frozen.
BRIEF SUMMARY OF THE INVENTION
In view of such problems of the prior art, a primary objection of the present invention is to provide a vehicle seat belt tightening system which is highly compact requiring a minimum space for installation.
A second object of the present invention is to provide a vehicle seat belt tightening device which requires a minimum amount of power for its operation.
A third object of the present invention is to provide a vehicle seat belt tightening device which is constructed as an integral unit so as to facilitate the work required to mount it on a vehicle and servicing it.
A fourth object of the present invention is to provide a vehicle seat belt tightening device which is reliable of its operation.
These and other objects of the present invention can be accomplished by providing: a vehicle seat belt tightening system for taking up slack from a seat belt in high acceleration or deceleration condition to positively restrain a vehicle occupant but otherwise permitting the seat belt to be paid out to accommodate a movement of the vehicle occupant, comprising: retractor means having a frame and a winding spool pivotally mounted thereon for winding a seat belt thereon; seat belt tightening means integrally attached to the frame at a seat belt outlet end of the retractor means, and provided with clamping means for selectively engaging the seat belt and guide means for guiding a movement of the clamping means in a direction to take up slack from the seat belt; drive means integrally attached to the frame adjacent the seat belt tightening means for selectively activating the seat belt tightening means; and deceleration detecting means integrally attached to the frame adjacent the drive means for activating the drive means when a level of acceleration or deceleration indicative of a vehicle crash is detected.
Thus, since the part of the seat belt paid out from the retractor device is securely gripped by the seat belt tightening means, a desired tension can be applied only to the part of the seat belt which is passed around the body of the vehicle occupant and, thereby, the power from the drive means is efficiently utilized to restrain the vehicle occupant. Further, by arranging the retractor means and the seat belt tightening means adjacent to each other along the seat belt, and integrally providing the drive means and the deceleration detecting means thereto at the same time, the overall size of the system can be significantly reduced.
Furthermore, by converting a linear pulling force of the piston produced by the propellant into a rotary force by means of a pulley and a wire, the expansion of the propellant can be efficiently applied to the piston with a high sealing capability, and an efficient magnification of force is made possible.
A particularly favorable structure may be obtained if the frame comprises a pair of opposing walls for pivotally supporting two lateral ends of the winding spool, the fixed and moveable clamp members being located between the two walls and the pulley being located externally of one of the walls.
To ensure the operation reliability of the system, it is desirable if the clamping means is further provided with ratchet means for preventing rotation of the clamping means in a direction to release the clamping means. A particularly favorable result can be obtained if the ratchet means comprises a fixed engagement member fixedly secured to the frame, a moveable engagement member attached to the base member so as to be moveable in radial direction at least after the clamping means has been brought into its operative condition, the engagement members being provided with teeth which are adapted to be brought into mutual meshing engagement when the moveable engagement member is moved in the radial direction by a tension from the part of the seat belt external to the seat belt tightening system and turned in the direction to pay out the seat belt and which are adapted to be brought out of engagement when the moveable engagement member is turned in the direction to take up slack from the part of the seat belt external to the seat belt tightening system. Preferably, the fixed engagement member consists of a part of the frame having an opening provided with inner teeth defined therein, and the moveable engagement member consists of a gear member having outer teeth and received in the opening so as to be rotatable therein without being interfered by the inner teeth in inoperative condition of the clamping means.
Thus, when the winding torque acting upon the winding spool is removed, the tension from the webbing brings the outer ratchet teeth and the inner ratchet teeth into meshing engagement and positively restrains the reverse rotation of the ratchet wheel. The ratchet wheel may be normally kept in its inoperative state by a breakable member which is adapted to be broken by the activation of the seat belt tightening means.
BRIEF DESCRIPTION OF THE DRAWINGS
Now the present invention is described in the following in terms of a specific embodiment thereof with reference made to the appended drawings, in which:
FIG. 1 is an overall perspective view of a seat belt system to which to which the present invention is applied;
FIG. 2 is a partly broke away from view of the seat belt tightening system according to the present invention;
FIGS. 3 and 4 are right and left side views of the seat belt tightening system shown in FIG. 2;
FIG. 5 is a sectional side view of an embodiment of the deceleration sensor;
FIG. 6 is a sectional front view of the deceleration sensor;
FIGS. 7 and 8 are see through views showing essential parts of the deceleration sensor;
FIGS. 9 through 12 are schematic side views of the deceleration sensor for explaining the operation of the deceleration sensor;
FIG. 13 is a sectional side view taken along line XIII--XIII of FIG. 2;
FIGS. 14 through 16 are views similar to FIG. 13 showing the process of taking up slack from the seat belt with the seat belt tightening unit; and
FIGS. 17 through 19 are schematic side views showing the operation of the device for preventing the reverse rotation of the seat belt tightening unit.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 shows the structure surrounding a seat belt system to which the present invention is applied, and the seat belt 3 extending upwardly from a webbing retractor 2 fixedly attached to a lower part of a center pillar 1 of a passenger compartment is passed through a through ring 4 attached to an upper part of the center pillar 1, and passed downward therefrom. The free end portion 6 of the seat belt 3 is attached to a rear part of a side portion of the seat 5. A tongue plate 7 is provided in the part of the seat belt 3 extending between the through ring 4 and the end portion 6 so as to be slidable along the seat belt 3.
When the vehicle occupant seated in the seat 5 pulls the seat belt 3 out of the webbing retractor 2 and engages the tongue plate 7 with a buckle 8 provided on the side of the seat 5 opposite to the anchor point of the end portion 6 of the seat belt 3, the seat belt 3 will be passed over the shoulder, chest and waist of the vehicle occupant.
As shown in FIGS. 2 through 4, the webbing retractor 2 is provided with an ELR unit 9 for permitting the pay-out and take-up of the seat belt 3 under normal condition, a seat belt tightening unit 10 for removing slack from the seat belt 3 in case of a vehicle crash, a drive unit 11 for supplying rotational power to the seat belt tightening unit 10, and a deceleration sensor 12 for detecting the occurrence of a vehicle crash.
The ELR unit 9 imparts a rotational force to the webbing winding spool for winding the seat belt 3 thereon by means of a spring incorporated therein in the same way as a conventional ELR device, and, in particular in case of a sudden deceleration, prevents the pay-out of the seat belt 3 by means of a conventional inertia locking mechanism not shown in the drawings.
The casing 13 of the seat belt tightening unit 10 is made by bending metallic plate, and one of its mutually opposing side walls 13a rotatably supports a pulley 15 via a journal bearing 14 consisting of a synthetic resin having a self-lubricating property. A wire 16 is passed around this pulley 15, and one of the ends of the wire 16 is connected to the drive unit 11 while the other end thereof is connected to a suitable location of the pulley 15.
The drive unit 11 comprises a cylinder 17 extending in a tangential direction with respect to the pulley 15, a piston 18 slidably received in the cylinder 17, and a propellant 19 accommodated in the base end of the cylinder 17 for applying a propelling force to the piston 18 when ignited, and is securely attached to the upper end of the casing 13 of the seat belt tightening unit 10. And, by the action of the deceleration sensor 12 integrally incorporated in the base end of the cylinder 17, the propellant 19 is ignited for explosion, and the resulting combustion pressure causes the piston 18 to be pushed through the cylinder 17 and the wire 16 to be drivingly pulled, thereby drivingly rotating the pulley 15.
The other side wall 13b of the casing 13 is provided with an opening 20 for receiving a ratchet wheel 21 so as to be rotatable therein without any interference as described hereinafter. A fixed clamp member 22 having an elliptic cross section is interposed between the opposing surfaces of the pulley 15 and the ratchet wheel 21 so as to extend between the two opposing side walls 13a and 13b and so as to be slightly displaced from the center of the pulley 15. Further, a moveable clamp member 23 is rotatably interposed between the pulley 15 and the ratchet wheel 21 by way of a pivot shaft 23a so as to oppose the fixed clamp member 22. Thus, the assembly consisting of the ratchet wheel 21, the clamp members 22 and 23, and the pulley 15 is rotatably supported by the journal bearing 14 in the manner of a cantilever. The external side surface of the ratchet wheel 21 is covered by a resin cover 30 having a pair of projections 29 fitted into corresponding openings 29a provided in the ratchet wheel 21. The moveable clamp member 23 is provided with three ridges 24a, 24b and 24c projecting radially from the center of the pivot shaft 23a thereof and extending laterally between the opposing two walls 13a and 13b. Each of these ridges 24a, 24b and 24c has a length along the axial direction corresponding to the width of the seat belt 3.
In initial condition, a gap 25 (FIG. 3) is defined between the opposing surfaces of the fixed and moveable clamp members 22 and 23 so as to define a vertical slot through which the seat belt not shown in the drawing can pass freely. Further, the opposing surfaces of the clamp members 22 and 23 at the ELR unit end of the gap 25 are provided with a plurality of axial clamp grooves 26a and 26b extending the entire axial length thereof in a substantially complementary fashion relative to each other.
As shown in FIG. 4, three quarters of the outer periphery of the ratchet wheel 21 is provided with sawtooth shaped outer ratchet teeth 27 which are inclined rearwardly as seen along the direction of normal rotation thereof. Five eighths of the inner periphery of the opening 20 is provided with inner ratchet teeth 28 which are complementary to the outer ratchet teeth 27. The inner and outer diameters of the opening 20 and the ratchet wheel 21 are determined in such a manner that the ratchet wheel 21 may rotate relative to the opening 20 with the tips of the outer ratchet teeth 27 and the inner ratchet teeth 28 barely contacting each other or entirely out of contact with each other when the ratchet wheel 21 is placed coaxially with the opening 20.
FIGS. 5 and 6 show the deceleration sensor 12 in greater detail.
A pair of pendulums 33a and 33b serving as sensor masses are suspended at their upper ends from either side of a sensor body 32 of the deceleration sensor 12. These two pendulums 33a and 33b have U-shaped cross sections having open tops. Further, one of them is received by the other, and they are pivotally supported by individual pivot shafts 34a and 34b, which are parallel to each other, so as not to interfere with one another and to swing individually.
An intermediate part of the sensor body 32 interposed between the two pendulums 33a and 33b is provided with a cylindrical guide hole 34 so as to communicate the two end surfaces 32a and 32b of the sensor body along the tangential direction of the swinging motion of the pendulums 33a and 33b. The guide hole 34 is provided with a spring retainer 35 at the opening adjoining one of the end surfaces 32a.
The guide hole 34 receives therein a firing pin 36 for igniting the fuse of the propellant 19. This firing pin 36 comprises a pointed tip 36a, and a plunger 36b which consists of a hollow cylindrical body having an open rear end and slidably received in the guide hole 34. This firing pin 36 is normally biased toward the opening adjoining the other end surface 32b of the sensor body 32 by a pair of coil springs 37 and 38; one of the coil springs 37 having a smaller diameter is interposed between an internal part of the plunger 36b and an annular shoulder surface of a cylindrical part of the spring retainer 35 while the other coil spring 38 is interposed between the end surface of the plunger 36b and an end plate portion of the spring retainer 38.
Further referring to FIG. 7, a trigger arm 39 which is bifurcated from a common rear end 39b into a pair of arm parts is pivotally supported by way of a support shaft 40 which rests upon a shoulder surface 43 of an L-shaped opening 42a provided in each side portion of the outer pendulum 33a. The support shaft 40 is also passed through a vertical slot 41 provided in the sensor body 32 and a relatively large rectangular opening 42b provided in each side portion of the inner pendulum 33b. This trigger arm 39 is crank-shaped as seen from a side (FIG. 5) and U-shaped as seen from the front (FIG. 6) so that the upper open ends 39a of the two arm parts thereof project into the guide hole 34 and engage with an annular shoulder surface 36c provided in the plunger 36b of the firing pin 36.
Thus, since the support shaft 40 can move only in the vertical direction guided by the vertical slot 41 of the sensor body 32 but such a vertical displacement of the support shaft 40 is restricted by the shoulder surface 43 of the L-shaped opening 42a provided in each side portion of the outer pendulum 33a, the trigger arm 39 can only pivot around the support shaft 40. On the other hand, the larger opening 42b provided in each side portion of the inner pendulum 33b does not interfere with the movement of the support shaft 40. However, if the pendulum 33a is moved forward, the support shaft 40 is disengaged from the shoulder surfaces 43 of the openings 42a and can drop downwardly therefrom.
As best shown in FIG. 8, the rear edge of the bottom portion of the inner pendulum 33b is provided with a projection 44 for engaging with the bottom part of a U-shaped rear end 39b of the trigger arm 39. However, if the inner pendulum 33b is moved forward, the rear end 39b of the trigger arm 39 is disengaged from the projection 44, and the trigger arm 39 can rotate around the support shaft 40.
The trigger arm 39 keeps the firing pin 36 stationary in spite of the biasing force of the first and second coil springs 37 and 38 by engaging the free ends 39a of the two arm parts thereof with the annular shoulder surface 36c of the firing pin 36 with the support shaft 40 engaged with the shoulder surfaces 43 of the openings 42a of the outer pendulum 33a and the U-shaped rear end 39b of the trigger arm 39 engaged with the projection 44 of the inner pendulum 33b.
The front edges of the bottom portions of the pendulums 33a and 33b are provided with projections 45a and 45b, respectively. Inside the part of the sensor body 32 opposing these projections 45a and 45b are received biasing springs 46a and 46b which are oriented in parallel with the axial direction of the guide hole 34. These biasing springs 46a and 46b abut the projections 45a and 45b of the pendulums 33a and 33b via guide caps 47a and 47b, whereby the pendulums 33a and 33b are normally urged rearwardly. In this way, the engagement between the rear projections 44 of the inner pendulum 33b and the U-shaped rear end 39b of the trigger arm 39, and the engagement between the shoulder surfaces 43 of the outer pendulum 33a and the pivot shaft 40 of the trigger arm 39 are normally maintained.
Now the operation of the above described embodiment is described in the following with reference to FIGS. 9 through 19.
Under normal running condition of the vehicle, it is so arranged that the biasing forces of the biasing springs 46a and 46b acting upon the pendulums 33a and 33b of the deceleration sensor 12 are more dominant than the inertia forces acting upon the respective pendulums 33a and 33b, and, since the rotation of the trigger arm 39 is prevented by the engagement between the support shaft 40 and the shoulder surfaces 43 of the outer pendulum 33a and the engagement between the rear end 39b of the trigger arm 39 and the projection 44 of the inner pendulum 33b, the firing pin 36 is prevented from moving by the open free ends 39a of the two arm parts of the trigger arm 39 as shown in FIGS. 9 and 11.
Meanwhile, the seat belt tightening unit 10 is normally in the state shown in FIG. 13, and the pay out and the take up of the seat belt 3 can be made freely through the gap 25 defined between the fixed clamp member 22 and the moveable clamp member 23. In order to maintain this state, the projections 29 provided in the resin cover 30 of the ratchet wheel 21 are fitted into the corresponding holes 29a provided in the ratchet wheel 21. These projections 29 are adapted to be easily broken by the torque produced by the drive unit 11 when the latter is activated.
When an acceleration or deceleration in excess of a prescribed level is produced as a result of a vehicle crash, the resulting inertia force causes the pendulums 33a and 33b of the deceleration sensor 12 to be rocked forwardly against the biasing force of the biasing springs 46a and 46b. As a result, the U-shaped rear end 39b of the trigger arm 39 is disengaged from the projection 44 of the inner pendulum 33b. It then follows that the restraint acting upon the firing pin 36 is removed, and the elastic force given from the first and second coil springs 37 and 38 causes the firing pin 36 to be shot forward against the fuse F after displacing the open free ends 39a of the arm parts of the trigger arm 39 out of the way (FIG. 12).
Alternatively, when the support shaft 40 of the trigger arm 39 is disengaged from the shoulder surfaces 43 of the outer pendulum 33a, the open free ends 39a of the arm parts of the trigger arm 39, along with the support shaft 40, drop downward, and the restraint upon the firing pin 36 is removed in the same way as described above with the result that the firing pin 36 is shot forward by the elastic force of the first and second coil springs 37 and 38 against the fuse F after displacing the open ends 39a of the arm parts of the trigger arm 39 out of the way (FIG. 10).
In this way, if either one of the pendulums 33a and 33b rotates due to the inertia forces acting upon them, the firing pin 36 is activated.
When the pointed tip 36a of the firing pin 36 strikes the fuse F, the propellant 19 is ignited, and the resulting explosive increase in pressure pushes up the piston 18. When the piston 18 is thus driven, the wire 16 is pulled in the direction indicated by the arrow P in FIG. 3, and the pulley 15, along with the ratchet wheel 21, is rotated in the direction indicated by the arrow B in FIG. 14.
Thereby, the ridge 24a of the moveable clamp member 23 abuts the seat belt 3. It then follows that the moveable clamp member 23 rotates in the direction indicated by the arrow C by being pressed by the seat belt 3 until the seat belt 3 is firmly wedged between the clamp grooves 26a and 26b as shown in FIG. 15.
Further rotation of the pulley 15 and the moveable clamp member 23 causes the clamp member 23 to act as a lever having a fulcrum at its rotary shaft 23a and its point of application of force at the end portion of the ridge 24a thereby further urging the clamp grooves 26b against the corresponding clamp grooves 26a of the fixed clamp member 22, whereby the seat belt 3 is pulled in the direction indicated by the arrow D as shown in FIG. 16.
During this process, due to the reaction force acting upon the clamp members 22 and 23, the ratchet wheel 21 tends to be pulled downward and the projections 29 are broken. However, because the sawtooth shaped ratchet teeth 27 and 28 of the opening 20 and the ratchet wheel 21 are so selected that the outer ratchet teeth 27 and the inner ratchet teeth 28 can slip relative to each other thereby permitting the seat belt tightening unit 10 to rotate in the direction to take up slack from the seat belt 3. In particular, since the initial contact between the peripheral edges of the opening 20 and the ratchet wheel 21 takes place at the smooth parts of the edges where no teeth are formed, the initial rotational motion of the ratchet wheel 21 immediately after breakage of the projections 26 can be started substantially without obstruction. This is advantageous in ensuring the quick response of the seat belt tightening unit 10.
The further the wire 16 is pulled, the more the seat belt 3 is drawn by the ridges 24a and 24b of the fixed clamp member 22 (FIG. 16).
When the wire 16 is substantially completely pulled in, and the rotational torque acting upon the pulley 15 and the ratchet wheel 21 disappears, the torque arising from the tension of the seat belt 3 starts acting upon the ratchet wheel 21 so as to pull it upwardly and rotate it in the reverse direction (FIG. 17). Thus, the inner ratchet tooth 28T located substantially at the top is engaged by the most adjacent outer ratchet tooth 28T. As a result, a rotational moment M acts upon the ratchet wheel 21 around the point of first engagement 27T and 28T (FIG. 18). Thus, as shown in FIG. 19, the outer ratchet teeth 27 in the region E located ahead of the above mentioned point are brought into meshing engagement with the corresponding inner ratchet teeth 27 so as to positively prevent the reverse rotation of the seat belt tightening unit 10.
Thus, according to the present invention, it is made possible to lock and pull the part of the seat belt paid out from the ELR unit without regards to the internal state of the ELR unit, and any slack in the useful part of the seat belt may be positively removed without being hindered by the action of wrapping the seat belt tightly around a winding spool within the ELR unit. Furthermore, since a thrust is produced by applying the explosive pressure of a propellant upon a piston received in a cylinder, and this liner displacement of the piston is converted into a rotary force of a moveable clamp member by way of a wire and a pulley, the expansion of the propellant can be transmitted to the seat belt tightening unit in a highly efficient manner due to this advantageous structure. Therefore, it is possible to achieve a large stroke take up action of the seat belt using a small power output and a limited space.
Additionally, by mounting the ELR unit and the seat belt tightening unit adjacent to each other on a common casing, and integrally forming the drive unit and the crash detecting unit thereto, the line of signal transmission from the crash detection unit to the drive device and then to the seat belt tightening unit may be simplified, whereby both compact design and high operation reliability of the system can be accomplished. | A vehicle seat belt tightening system for taking up slack from a seat belt in high acceleration or deceleration condition to positively restrain a vehicle occupant but otherwise permitting the seat belt to be paid out to accommodate a movement of the vehicle occupant, comprising: a retractor unit comprising a winding spool, a seat belt tightening unit arranged at a seat belt outlet end of the retractor unit, a drive unit for selectively activating the seat belt tightening unit, and a deceleration detection unit for acting upon the seat belt tightening unit, which are integrally mounted on a common frame. Thus, the reliability of the system is improved and the installing and the servicing of the system is simplified. In particular, the operation reliability may be improved if the reverse rotation of the seat belt tightening unit is prevented by a ratchet mechanism in which a ratchet wheel received in a mutually spaced relationship in an opening provided with inner ratchet teeth and the ratchet wheel is adapted to be displaced into meshing engagement with the inner ratchet teeth of the opening when the ratchet wheel is pulled by tension from the seat belt. | 1 |
BACKGROUND OF THE INVENTION
The present invention is directed to a method and apparatus for providing a locked closed subsurface safety system for protecting petroleum reserves from undesired intervention and/or sabotage.
It is the practice of most safety systems to feature the ability to apply hydraulic pressure or electrical current through a control line to open a downhole safety valve for well production and upon release of this system the valve will close, ceasing all production of any well fluids. However, this very procedure provides the means by which a saboteur could hydraulically or electrically lock open the safety valve from the surface before setting fire to a free flowing well. And in wells where no safety systems exist the well will usually end up burning itself out when the fuel feeding the fire is depleted or until appropriate extinguishing techniques have been applied.
Therefore, the present invention is directed to a surface controlled locked closed subsurface safety system which will close a downhole safety valve and prevent the valve from being reopened through the control line. The valve can only be reopened by conventional wireline procedures which require moving a rig onto location and opening the valve through the interior bore of the production tubing, which requires considerable time and effort. Thus, the present invention protects petroleum reserves from undesired intervention and/or sabotage.
SUMMARY
The present invention is directed to a method of locking closed a subsurface safety system in a well production tubing by actuation from the well surface. The method includes releasably holding the subsurface safety valve in the open position allowing well production through the production tubing. The method also includes closing the subsurface safety valve from the well surface through a control line extending from the safety system to the well surface exteriorly of the bore of the production tubing, and preventing the safety system from being opened through the control line.
In one form of the invention, the control line is a hydraulic control line and the method includes the step of venting the hydraulic control line at a subsurface location.
In still another embodiment of the invention, the method includes the step of preventing the safety system from being opened including mechanically locking the safety system in the closed position inside the production tubing.
Still a further object of the present invention is the provision of a surface controlled locked closed subsurface safety system which includes a subsurface safety system in a well production tubing controlling the flow of well fluids through the tubing. A control line extends from the well surface to the safety system exteriorly of the production tubing for controlling the opening and closing the safety system. Subsurface means are provided connected to the control line and actuated by the control line for preventing the safety system from being opened by the control line. In one embodiment the system includes a hydraulically actuated subsurface safety valve actuated through a hydraulic control line and includes a normally closed vent means connected to the control line. The vent means is actuated to the open position venting the control line upon the actuation by a higher hydraulic pressure in the control line than required for actuation of the safety valve.
In one embodiment the system includes a hydraulically actuated subsurface safety valve positioned in the production tubing, a hydraulic control line connected to the safety valve, a sidepocket mandrel connected in the production tubing above the safety valve, and a normally closed valve positioned in the sidepocket mandrel and connected to the control line and actuated to an open position venting the control line upon the application of a predetermined pressure in the control line.
Still a further object of the present invention is the provision of a subsurface well safety valve including a housing having a bore therethrough, a valve closure member in the bore moving between open and closed positions for controlling the fluid flow through the bore, a flow tube telescopically movable in the housing for controlling the movement of the valve closure member, and biasing means in the housing urging the flow tube in a direction to close the valve. Releasable latch means are provided in the housing releasably holding the flow tube in a position holding the valve in the open position. Actuating means in the housing is adapted to be connected to a control line extending to the well surface and said actuating means is engagable with the releasable latch means for releasing the flow tube and closing the valve. In one form of the invention the actuating means is a hydraulic piston and cylinder assembly.
The releasable latch means may include dog means engaging and preventing movement of the flow tube with shoulder means releasably holding the dogs in engagement with the flow tube. Spring means yieldably acts on the shoulder means.
Other and further objects, features and advantages will be apparent from the following description of presently preferred embodiments of the invention, given for the purpose of disclosure and taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an elevational view, partly in cross section, of one form of the present invention,
FIGS. 2A and 2B are continuations of each other of a fragmentary elevational view, partly in cross section, of one suitable type of hydraulically actuated well safety valve for use in the system of FIG. 1,
FIG. 3 is an enlarged elevational view, partly in cross section, of one suitable valve for use in the sidepocket mandrel of FIG. 1,
FIG. 4 is a fragmentary elevational view, partly in cross section, of another embodiment of the present invention, and
FIG. 5 is an enlarged elevational view of the circled detail A of FIG. 4.
DESCRIPTION OF THE PREFERRED EMBODIMENT
While the present invention in a surface controlled lock closed subsurface safety system will be described, for purposes of illustration only, as using a hydraulically actuated flapper type safety valve, it will be understood that the present invention may be used with other types of safety valves, safety valves having other types of valve closure elements, and electrically actuated solenoid valves as well as hydraulically controlled valves.
Referring now to the drawings, and particularly to FIG. 1, the reference numeral 10, generally indicates a subsurface safety system according to the present invention which is installed in the well production tubing 12 through which well production flows from the well to the well surface and which is enclosed in the normal well casing 14. The present safety system 10 is installed in the tubing and generally includes a sidepocket mandrel 16 with a vent valve 24, and a hydraulically controlled well safety valve 18. The installation may also include other components which form no part of the present invention, such as a packer 20, and landing nipple 22.
The safety valve 18 may be of any suitable hydraulic controlled, or electrically controlled, subsurface well safety valve. For example, the valve 18 may be a Camco TRDP safety valve or other conventional safety valves. A suitable safety valve 18, such as described in U.S. Pat. No. 4,161,219, is shown in FIGS. 2A and 2B and generally includes a housing 30 having a bore 32 therethrough, an annular valve seat 34, a valve closure element 36 adapted to seat on the seat 34. A flow tube 38 is telescopically movable in the body 30 and through the valve seat 34. When the flow tube 38 moves to a downward position, it pushes the valve element 36 away from the valve seat, as best seen in FIG. 2B, and the valve is held in the open position so long as the tube 38 is in the downward position. When the flow tube 38 is moved to the upward position, the valve closure element 36 closes and seats on the seat 34 by action of a spring 40. The valve 18 is closed by the application or removal of hydraulic fluid through a control line 42 leading to the well surface. The hydraulic fluid acts on a piston and cylinder assembly generally, here shown as one assembly, indicated by the reference numeral 44, which includes a piston 46 movable in a cylinder 48. The assembly 44 engages the flow tube 38 for actuating the valve 18. Power spring 50 provides biasing means for biasing the valve to the closed position. A further description of a suitable valve can be found in U.S. Pat. No. 4,161,219, which is incorporated herein by reference.
In conventionally operating safety valves, such as safety valve 18, hydraulic pressure is applied through the control line 42 to open the safety valve 18 for allowing well production therethrough and upon release of the hydraulic pressure in the line 42, the valve 18 will close shutting off all production of any well fluids. However, this very procedure which provides the means by which the safety valve 18 can be controlled from the well surface, makes the safety valve 18 susceptible to being deliberately held open for setting fire to a free flowing well.
The present invention is directed to additionally providing a surface controlled lock closed feature which will provide the necessary equipment to close the downhole safety valve 18 from the control line 42, but prevent the valve 18 from being reopened except through intervention through the interior of the production tubing 12.
However, the present safety system 10 prevents the safety valve 18 from being opened through the control line 42. Referring again to FIG. 1, a conventional sidepocket mandrel 16 is provided. While any suitable sidepocket mandrel can be used, one described more fully in U.S. Pat. No. 3,741,299 may be used having a sidepocket in which a control valve, such as the vent valve 24, may be installed and removed therein. One suitable type of valve is a conventional Camco DCK dump-kill valve and latch, which is conventional, but for purposes of full disclosure is shown in FIG. 3. Referring now to FIG. 3, the vent valve 24 includes a body 52 having upper and lower packing seals 54 for seating in the sidepocket of the mandrel 16 and sealing across openings 17 (FIG. 1) between the sidepocket and the exterior of the mandrel 16. A port 56 in the housing is in communication with the openings 17 in the mandrel 16 which in turn are connected by a T connection 19 to the control line 42. Thus, hydraulic control fluid in the control line 42 is in communication with the port 56. Normally a piston 58 defined by seals 60 and 62 block communication of the port 56 from an interior bore 64 of the valve 24, which in turn is in communication with the bore of the mandrel 16 and bore of the production tubing 12. The piston 58 is held in a locked position by one or more shear screws 66. However, when the hydraulic pressure in the control line 42 is increased to a predetermined value, which is above the operating pressure of the safety valve 18, the shear pins 66 are sheared, the piston 58 moves upwardly allowing hydraulic control fluid in the control line 42 to vent itself through the port 56 and into the interior of the production tubing 12. Venting of the hydraulic control fluid from the line 42 prevents pressurizing the line to keep the safety valve 18 open, and instead the safety valve 18 by having pressure to its piston and cylinder assembly 44 vented, causes the valve 18 to close.
Therefore, in the event that it becomes necessary to lock closed the safety valve 18, a predetermined pressure above the opening pressure of the safety valve 18 is applied to the hydraulic control line 42. The vent valve 24 will then actuate and dump and vent the hydraulic pressure in the line 42 in the control line thus disabling any pressure communication to the valve 18. The valve 18 is now said to be locked closed. Hydraulic pressure cannot reopen the valve. In order to place the safety valve back in operation, the dump-kill valve 24 may be retrieved from the sidepocket mandrel and reset conventionally using conventional wireline methods and tools. Once the valve 24 has been repinned, it may be run back into the mandrel 16, re-establishing the hydraulic circuit in order to operate the subsurface safety valve 18. However, it is to be noted that resetting the safety system 10 requires the use of a rig and wireline tools and operators and thus cannot be quickly accomplished and therefore is a great discouragement to any would-be saboteurs.
Therefore, the safety system 10 is fail-safe, the lockout valve 18 cannot be reopened by pressure through the control line 42 from the well surface and therefore provides enhanced protection of the well reservoir from sabotage or unwanted intervention.
Other and further embodiments of the present invention may be provided as best seen in FIGS. 4 and 5 wherein like parts to those described in connection with FIGS. 1-3 are provided with similar numbers with the addition of suffix "a". In some petroleum wells there are no safety systems such as a hydraulic or solenoid type well safety valve 18 which can be controlled through a control line to the well surface. Therefore, a special safety valve generally indicated by the reference numeral 70 is disclosed for insertion in the production tubing 12 in order to prevent sabotage and to meet the needs of a lock closed system. The valve 70 is a normally open valve but can be activated as disclosed by hydraulic pressure, or an electrically actuated solenoid, to close the valve through a control line 42a and prevent its reopening through the control line 42a. The valve 70 includes a housing 30a having a bore 32a therethrough, a valve closure element 36a adapted to seat on a valve seat 34a and which is held in the open position by a flow tube 38a. Spring biasing means 50a act in a direction to yieldably urge the flow tube 38a to a position allowing the valve 70 to close. However, the flow tube 38a is held in the open position by a releasable latch means in the housing 30a generally indicated by the reference numeral 72. The latch means may include a plurality of dogs 74 engaging a holding notch 76 in the flow tube 38a with shoulder means 78 releasably holding the dogs 74 in the notch 76 and with spring means 80 yieldably acting to retain the shoulder means 78 in its holding position.
Actuating means are provided in the housing 30a such as an electrically actuated solenoid or as here shown a piston and cylinder assembly 44a, which is hydraulically actuated through a control line 42a leading to the well surface. The assembly 44a includes a piston 46a movable in a cylinder 48a. Application of a predetermined hydraulic pressure in the line 42a actuates the piston 46a to engage and move the shoulder 78 downwardly overcoming the spring means 80 until the dogs 74 are aligned with a recess 82 above the shoulder 78. This allows the dogs 74 to move into the recess 82 and out of the holding notch 76 in the flow tube 38a which frees the flow tube 38a for upward movement by the biasing spring 50a. Upward movement of the flow tube 38a out of the way of the valve closure member 36a allows the valve 70 to close. After closure, the valve 70 cannot be reactivated through the control line 42a leading to the well surface.
The flow tube 38a includes a resetting shoulder 90. In order to place the safety valve 70 back into operation after actuation by hydraulic fluid applied through the control line 42a, a conventional wireline tool is used to be inserted into the bore 32a of the valve 70. The tool engages the resetting shoulder 90 and shifts the flow tube 38a downwardly which rotates the flapper valve element 36a to the open position. Once the locking notch 76 moves and becomes aligned with the dogs 74, the power spring 80 moves the locking shoulder 78 upwardly to hold the dogs 74 in the locked position.
The valve 70 may be used in conjunction with the subsurface safety system 10 of FIG. 1 in place of the mandrel 16 and valve 24 provided that the power spring force of spring 80 exceeds the force it takes to open the subsurface safety valve 18. However, it may be more economical to use the sidepocket mandrel 16 and valve 24. However, the sole use of the valve 70 provides the advantages of (1) an economical concept for a disaster solution, (2) it may be solenoid operated if desired, and (3) the lockout valve connot be reopened from the surface through the control line, but can be reopened and reset with wireline tools in the bore of the production tubing.
The present invention, therefore, is well adapted to carry out the objects and attain the ends and advantages mentioned as well as others inherent therein. While presently preferred embodiments of the invention have been given for the purpose of disclosure, numerous changes in the details of construction, arrangement of parts, and steps of the method, will be readily apparent to those skilled in the art and which are encompassed within the spirit of the invention and the scope of the appended claims. | Locking closed a subsurface safety system in a well production tubing from the well surface by releasably holding the subsurface safety valve in the open position. Thereafter closing the subsurface safety system from the well surface through a control line extending exteriorly of the production tubing. Thereafter preventing the safety system from being opened through the control line. | 4 |
TECHNICAL FIELD
This invention relates generally to the formation and use of novel chelate complexes of chlorine dioxide, for use in disinfecting animal tissues and inanimate surfaces, and to treat diseases and wounds. The invention also provides passive and active methods for releasing the chlorine dioxide from such chelates by competitive displacement with selected metal cations.
BACKGROUND OF THE INVENTION
Chlorine dioxide has become increasingly well known as a potent antimicrobial agent, as well as a bleaching material, in many commercial and industrial applications. As a germicide it is finding increasing use in municipal water disinfection, cooling towers and oral malodorants, where it both destroys putrefactive organisms and oxidizes the odorant. It also has been approved recently for reducing poultry pathogens during processing, surpassing the reductions which can be achieved with chlorine. Chlorine dioxide is also used as a bleaching agent in paperboard production and for textiles and flour. However, ClO 2 is a reactive gas which is explosive in air at levels approximating 10%, and it has a low threshold limit value (TLV) classification by OSHA of 0.1 ppm in workers' air. It cannot be compressed and stored, as can chlorine, and water solutions of chlorine dioxide rapidly degrade both through disproportionation to higher- and lower-valent chlorine species and through evaporation. As a result of these limiting properties, it is generally produced "on site," by acidification of chlorite solutions or reduction of chlorates.
Because it has superior destructive properties for bacteria, fungi and viruses, efforts have been made to capture and/or stabilize ClO 2 molecules in aqueous solution for subsequent use as a germicide or for more general oxidative purposes. A series of patents have issued in the last forty years, disclosing the stabilization of ClO 2 solutions by inclusion of various peroxides, such as sodium perborate in U.S. Pat. No. 2,701,781, and sodium carbonate peroxide in U.S. Pat. No. 3,123,521. Chlorine dioxide may form in these solutions after dilution with water, which may reduce the pH sufficiently to produce low levels of the gas at a slow rate, or by direct acidification of the solutions to hasten the process. The stabilized chlorine dioxide in these formulations has been later revealed to predominate in the reduced oxychlorine form of chlorite, with chlorine in the trivalent state, rather than as chlorine in the tetravalent state associated with ClO 2 . The interaction of acidity with chlorites is a well recognized means of converting chlorite to chlorine dioxide. The essence of these stabilized ClO 2 patents is the presence of a peroxide reservoir, which acts to reduce any small levels of free ClO 2 , that may be slowly formed, back to the more stable chlorite form. Analysis of commercially available stabilized chlorine dioxide formulations reveal, at most, only a few parts per million of free, molecular ClO 2 .
A novel polymer composition was disclosed, in U.S. Pat. No. 4,829,129, where aqueous polymeric N-vinyl-α-pyrrolidone (PVP) solutions, ranging from 1% to 60% by weight, are saturated with ClO 2 gas. The gas reacts with the PVP causing the characteristic chlorine dioxide color to disappear. Certain other polymer types are disclosed which possess similar properties. The resulting product is an organically stabilized chlorine dioxide composition which is claimed to be a powerful microbicide, although no examples are provided to confirm this claim. The stabilized ClO 2 is postulated to exist in the reduced, trivalent chlorine, chlorite form, which is stabilized or complexed by the PVP. A related, chemically stabilized chlorite matrix is revealed by Kuhne in U.S. Pat. Nos. 4,507,285 and 4,725,437, which matrices enclose activated oxygen for topical or systemic treatment of diseases and disorders.
In all of these teachings and disclosures there is no indication that free molecular ClO 2 can be held in solution per se, in the tetravalent chlorine form, for subsequent release by means other than acidification of the reduced chlorite form and partial chemical conversion to chlorine dioxide, i.e. from [H + ]+[ClO 2 - ]→→→ClO 2 , [Cl - ], [ClO 3 - ]. In many instances, however, the use of acids is counterindicated for certain applications. Specifically, a continued search has revealed that if significant levels of ClO 2 are required for, say, localized disinfection, wound treatment, or mouth odor oxidation, without the use of acid triggers of chlorite solutions, including so-called stabilized or complexed ClO 2 solutions, no compositions have yet been described which can meet this need. This invention was made as a result of that search.
OBJECTS AND SUMMARY OF THE INVENTION
Accordingly, it is a general object of the present invention to substantially alleviate the above-identified deficiencies of the prior art.
A specific object of the present invention is to provide a composition containing molecular chlorine dioxide, ClO 2 , in a stable chelated form in aqueous solution, without reducing it to the chlorite form.
A further object of the present invention is to provide methods for release of the chlorine dioxide from the chelate avoiding the use of acids.
A further object of the present invention is to provide methods for use of chelated chlorine dioxide compositions for disinfection, wound treatment, oral and body cavity antisepsis and odor reduction, as well as other bleaching and oxidative actions where ClO 2 currently serves.
The present invention provides, in one aspect, a method for preparing stable compositions containing molecular chlorine dioxide in a chelated form, unlike previously-described stabilized chlorine dioxide compositions in which stability is achieved by conversion of the ClO 2 to the chlorite form. The chelates are comprised of the electron-deficient ClO 2 molecule, which can accept an electron, and a chelating agent which can contribute its available electrons to the accepting orbital of the ClO 2 molecule.
In another aspect, the present invention provides for selective release of ClO 2 from the otherwise stable chelated compositions by addition to their aqueous solutions of specific metal cations which displace the chlorine dioxide from the chelate to a degree dependent upon the relative strengths of the chelates of chlorine dioxide and the specific metal cation.
In another aspect of this invention, methods are provided for using the chelated chlorine dioxide compositions, with and without the addition of displacing metal cations, for the same purposes of disinfection, deodorization and bleaching for which unstabilized, molecular chlorine dioxide compositions are currently being employed.
In one embodiment, a chelated ClO 2 composition of this invention is used as a rinse to destroy oral malodorants and reduce the numbers of microorganisms which cause malodor, dental plaque and gum disease. In another embodiment, a ClO 2 chelate is used as a douche. In a further embodiment, a chelated ClO 2 composition is used as a surgical irrigant to provide disinfection and other beneficial effects imparted by the ClO 2 that is released upon contact with the ferric ion of blood hemoglobin in the cavity. In yet another embodiment, a zinc salt is added to a ClO 2 chelate composition which is then used to disinfect the eye or skin surfaces.
These and other aspects of this invention will become evident upon reference to the following detailed description.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides compositions and methods of use of chelated chlorine dioxide complexes, and their subsequent application for disinfection, deodorization, and oxidation as both chelated and thence-liberated free molecular ClO 2 . The invention is based on the fact that the chlorine dioxide molecule exists virtually entirely as a permanent free radical monomer. The theoretical considerations which underlie this state are confirmed, in part, by the dipole moment and paramagnetic nature of the chlorine dioxide molecule. As a free radical, ClO 2 has an unpaired electron diffused in an outer orbital, and can readily accept or presumably share an electronic charge from an electron donor. One class of electron donors is the chelating agents, which have been classically characterized as compounds containing electron-donating atoms that can combine, by coordinate bonding, with single metal ions to form a cyclic structure called a chelation complex, or a chelate. The universal presence of metal ions in these chelates derives from the fact that metal ions, or certain metal ion radicals, are cations which are electron-deficient, and thus positively charged. I have now discovered that chlorine dioxide can function, in the same capacity, as do metal ions, by accepting electronic charges donated by chelating agents.
For descriptive purposes, the ClO 2 chelate formed with the specific chelating agent ethylenediamine tetraacetic acid, as the di-, tri- or tetrasodium salt shall be used to characterize the type of complex compositions that can be formed, and the methods of using such chelates. There are many related chelating agents which may also be used in place, wholly or in part, of this EDTA family. Each of these has somewhat different chemical and physical characteristics, including complex formation constants, qualities which those that are skilled in the art of chelation chemistry would have sufficient familiarity with to modify the ClO 2 chelate appropriate to the desired end need. Specific examples of chelating agents related to EDTA include hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, N-dihydroxyethylglycine and ethylenebis(hydroxyphenylglycine). Other classes of chelating agents, other than those in the aminocarboxylic acid category encompassing EDTA, would include but not be limited to 1,3-diketones, aminoalcohols, aromatic heterocyclic bases, oximes, and tetrapyrroles. Specific examples of 1,3-diketones are acetylacetone and thenoyltrifluoroacetone among others; of aminoalcohols are triethanolamine and N-hydroxyethylethylenediamine among others; of aromatic heterocyclic bases are dipyridyl and o-phenanthroline among others; of oximes are dimethylglyoxime and salicylaldoxime among others; and of tetrapyrroles are tetraphenylporphin and phthalocyanine among others. The characteristic of all of the structures in these classes is the presence of two or more donor atoms spatially situated so that they can coordinate with the same metal ion, or in this case, a chlorine dioxide. The chelate rings which form contain four or more members although five- or six-membered ring chelates are usually the most stable.
The chelate formed by EDTA can be represented by the following steric diagram, where ClO 2 would be contained in a central position that would be occupied by a metal ion in the corresponding metal chelate. ##STR1##
In order for EDTA to function as a chelating agent, at least two of its four carboxylic acid functions should exist in the ionized form, i.e. as C(═O)--O - , so that its electrons are more freely available for donation. Thus chelates may be formed at a range of solution pH's at which EDTA,Na 4 , EDTA,Na 3 , and EDTA,Na 2 forms are stable. The practical lower pH limit of EDTA chelation with ClO 2 is about pH 2.0, which is consistent with the pK a values of the tetra-, tri-, di-, and mono-acid forms of EDTA of 2.00, 2.67, 6.16, and 10.26. Thus, at a pH of 2.67, where half of the EDTA present would be in the form of EDTA,H 3 ,Na and half as EDTA,H 2 ,Na 2 (referred to earlier as EDTA,Na 2 ), only the latter form functions as a chelating agent, and less so as the pH is reduced. In fact, if a ClO 2 .-EDTA complex is prepared from a stoichiometric quantity of EDTA, at a pH where all of the agent was involved in chelation, the subsequent lowering of the solution pH would result in increasing liberation of chelated ClO 2 to the solution.
A more practical means of liberating ClO 2 from a chelate, without the addition of hydrogen ions [H + ] and a resulting pH reduction, is by the introduction of those metal cations which have a greater affinity for the chelating agent than does the ClO 2 . The equilibrium would shift to favor the chelate of the more strongly bound metal cation, resulting in the release of ClO 2 from the chelate. The greater the difference in the formation constants of the two chelates, metal and ClO 2 , the greater the rapidity of displacement. It is also possible to displace ClO 2 from a chelate with a metal cation that forms a weaker complex, by taking advantage of the mass action principle of adding a large excess of the metal salt to a chelate solution. The molar ratio of metal cation added to displace ClO 2 from a chelate.ClO 2 complex to the total amount of chelate in solution is from about 0.1:1 to about 5:1, preferably about 0.5:1 to about 2:1, and most preferably about 1:1 to about 1.5:1.
This can be illustrated by the following study, where the level of ClO 2 displaced from an EDTA.ClO 2 complex [0.04 meq of EDTA,Na 2 +23.5 ppm ClO 2 ] was spectrophotometrically determined at 370 nM five minutes after the addition of 0.2 ml of either a 1% or 2% metal salt solution or 0.5N HCl to 8 ml of the complex. The 1% or 2% concentration was chosen to adjust for the relative level of metal ion in the metal salt selected, in order to have a slight excess of metal ion in solution. The ClO 2 liberated is compared side-by-side with the logarithm of the formation constants of the corresponding EDTA-metal complex. The initial pH of 5 of the complex solution was minimally changed following the additions, except for the HCl addition, where the pH dropped to about
______________________________________ ClO.sub.2 at 5 min.Metal/Cation in ppm log K______________________________________[H.sub.2 O Control] 0.5 --Ba.sup.++ (2%) 0.3 7.8Ca.sup.++ (2%) 0.2 10.7Co.sup.++ (2%) 1.9 16.3Zn.sup.++ (1%) 4.9 16.5Cu.sup.+ (1%) 10.8 18.8H.sup.+ 16.5 --______________________________________
While the measured concentrations below 1 ppm are considered imprecise, there is an apparent trend among these data which indicates that more strongly complexed metals show a greater displacement of ClO 2 from the chelate. This was further established in a subsequent study, using the Fe +++ ion, which forms a stronger EDTA complex than any of the above ions: [log K for Fe +++ /EDTA complex=25.1]. In this study, the same 0.2 ml quantity of a 1% ferric chloride solution was added, several days later, to an aliquot of the same stable chelate solution. The treated solution rapidly developed a yellow-brown color, with an evident ClO 2 odor, and an absorbance at 370 nM corresponding to a ClO 2 level of 41.3 ppm. The reason for the apparently higher level of ClO 2 is unclear, but appears related to the unusual coloration, and increased absorbance at 370 nM, of the solution formed. The solution had a high microbiocidal activity, apparently superior to that of the original, unchelated ClO 2 solution, whereas the untreated EDTA.ClO 2 chelate had minimal activity. The color, and germ killing action may be related to the possible presence of the complex ion [Cl 2 O 4 ] - , the adduct of ClO 2 and ClO 2 - , which has been previously reported and which plays a role in certain ClO 2 oxidation reactions.
It was appropriate to consider one other possible source of ClO 2 production, resulting from the addition of Fe +++ to the chelate solution, in order to properly validate the displacement of ClO 2 from the complex. Ferric ion has been reported to react with chlorite ion, where an electron transfer would result in ferrous ion and ClO 2 formation, i.e.:
Fe.sup.+++ +ClO.sub.2.sup.- →Fe.sup.++ +ClO.sub.2
If excess chlorite existed in the ClO 2 solution to which the EDTA was added, this chlorite might possibly have reacted to form the ClO 2 observed, rather than it originating from displacement from the chelate. However when the same quantity of Fe +++ solution was added to an activated chlorite solution from which the ClO 2 had been allowed to evaporate, leaving behind a residual amount of chlorite, no ClO 2 evolution nor yellow-brown color was noted as with the chelate. Thus the ClO 2 did indeed originate from metallic displacement from the chelate rather than simple oxidation of the chlorite.
This experiment also demonstrated that ClO 2 , as the free molecule, is liberated from the chelate by metallic displacement, as opposed to that which is created by acidification and disproportionation of chlorite in so-called stabilized chlorine dioxide. The rapid evolution of ClO 2 from the complex, at a pH˜5, could not occur with that rapidity by acidification of chlorite. In addition, even if a breakdown of chlorite would slowly occur at pH 5 to form ClO 2 , the relative molar yield of the gas would have been much less, in favor of higher relative yields of chloride ion.
The range of ClO 2 concentrations which form chelate complexes covers the range from about 0 to at least 2500 ppm (0 to 38 meq/liter), and a preferred composition contains from about 1 ppm to about 1000 ppm (0.015 to 15 meq/liter). The level of chelating agent required to maintain stable ClO 2 chelates is generally proportionate to the level of ClO 2 in the solution, from about 0.1 to about 5 times the number of ClO 2 meq, preferably about 0.5 to about 3 times the number of ClO 2 meq, depending upon the nature of the chelate formed (e.g. mono-, di-, or tri-dentate). More preferably, this ratio is from about 0.5 to about 2 times, and most preferably from about 1.0 to about 1.5 times. The ClO 2 may be produced by any of the techniques known to those skilled in the art, whether by in situ oxidation or acidification of chlorite, reduction of chlorate, or external production of the gas by similar means and subsequent bubbling of the gas into water or the chelating solution. When the ClO 2 is produced in situ, the solution is then either adjusted to the desired final pH or the chelating material is introduced followed by pH adjustment. The pH range in which stable chelates may form, depending upon the chelating agent, is about 1.5 to about 13, with a preferred range of about 2 to about 12.
In order to preserve the stability of the ClO 2 in chelated form, a solution containing a chelate should contain cation and proton levels too low to substantially interfere with the formation and duration of a complex between the ClO 2 and the chelating agent. As used throughout the specification and claims, the phrase "absent sufficient metal cations and protons to substantially inhibit binding of the chlorine dioxide to the chelating agent" means that the metal cation and/or proton content of the solution does not substantially shift the equilibrium between the free ClO 2 in solution and the ClO 2 in solution which is in a complex with the chelating agent.
The ClO 2 chelates may be used for disinfection, wound treatment, deodorization, or other oxidative processes either per se or following activation. When used as such, reliance is placed on activation, and release of the ClO 2 by the substrate being contacted, be it surgical wound site, oral, ear canal or vaginal cavity, the skin or inanimate surface. In these situations, release may be effectuated by the presence on, or in the substrate of displacing metal ions, hydrogen ions or other materials which may disrupt the complex. Examples of triggering conditions would be the ferric ion from blood hemoglobin in a wound, calcium and magnesium in the bacterial membranes of gram (-) microorganisms, and the acidity created by lactic-producing bacteria in the vaginal vault. In contacting mucosal surfaces, such as within the vagina, there is a distinct advantage in using a ClO 2 -containing complex, for acid triggered liberation of the germicide, rather than a so-called stabilized chlorine dioxide formulation based on chlorite, because the latter ion is known to be irritating and cytotoxic, whereas ClO 2 is better tolerated by the tissue.
Such chelating agents as EDTA have particular advantage in this invention, since they not only form stable complexes with ClO 2 but also have a well-recognized capacity to enhance the effectiveness of antimicrobials against gram (-) microorganisms. EDTA increases cell wall permeability by chelation of metal ions in their surface, so the chelate may serve a dual role of competitively abstracting metal ions from the microbial surfaces and replacing them, at the site, with liberated, microbiocidal ClO 2 .
The present invention is illustrated by the following examples. Unless otherwise noted, all parts and percentages in the examples as well as the specifications and claims are by weight.
EXAMPLE 1
This example illustrates the preparation of a ClO 2 chelate, by the addition of the chelating agent EDTA,Na 2 to a solution of ClO 2 previously prepared by acidification of a sodium chlorite solution followed by neutralization of the excess acidity.
2 ml of a stock solution containing 15.0 mg/ml of chlorite ion was added to a flask, and the volume taken to 100 ml with deionized water.
8 ml of 0.5N HCl was added to the solution, the flask was covered and mixed, and the contents warmed in a microwave oven to about 50° C. The solution was held for 30 minutes while the yellow ClO 2 gas formed in solution.
About 75 ml of cool deionized water was added to the flask, which was then shaken to dissolve the head space gas into the cool liquid. Then 4 ml of 1.0 N NaOH was added to the mixture, which was stirred, and the volume taken to 200 ml with deionized water.
The absorbance of this solution at 370 nM was 0.499, corresponding to a ClO 2 concentration of 27.1 ppm.
6 ml of an EDTA,Na 2 solution containing 0.05 meq/ml was added to 150 ml of the ClO 2 solution, which decolorized within 1 minute after the mixture was shaken. The absorbance of the solution at 370 nM was now 0.008, corresponding to an unchelated ClO 2 concentration of 0.4 ppm. Based on the dilution factor, the total ClO 2 concentration of this solution would be 26.1 ppm, with 25.7 ppm existing in the chelate form and 0.4 ppm existing free.
EXAMPLE 2
This example illustrates the ability of the EDTA.ClO 2 complex, described in Example 1, to rapidly destroy the pathogenic microorganism Escherichia coli, following displacement of the ClO 2 by Fe +++ in the chelate. The microbiocidal capability of three solutions were evaluated:
1) the unchelated ClO 2 solution, and 1→10 and 1→50 dilutions;
2) the chelated ClO 2 solution, and 1→10 and 1→50 dilutions;
3) the ferric iron-treated chelate of solution 2), where 0.75 ml of a 1% ferric chloride solution was added to 30 ml of solution 2) about 15 minutes before microbiological examination. Undiluted solution and 1→10 and 1→50 dilutions of this were evaluated.
0.1 ml of a challenge inoculum of the E. coli (ATCC No. 8739), suspended in saline, was introduced into 10 ml of the test solution, providing an organism concentration of 5.81 log cfu/ml. After 30 sec. or 2 min., 1 ml aliquots of each solution were transferred to Tryptone Azolectin Tween neutralizing broth, and plated out on Trypticase Soy Agar both directly and in serial 10 1 , 10 2 , and 10 3 dilutions. The following log reductions were obtained for the three solutions at the two contact times:
__________________________________________________________________________ClO.sub.2 Control ClO.sub.2 -Chelate ClO.sub.2 -Chelate + Fe.sup.+++Time undil 1:10 1:50 undil 1:10 1:50 undil 1:10 1:50min log reduction of E. coli__________________________________________________________________________0.5 3.21 3.11 3.51 0.07 -0.01 0 ≧3.81 ≧3.81 ≧3.812.0 3.41 3.33 3.51 0.03 -0.05 -0.02 ≧3.81 ≧3.81 2.86__________________________________________________________________________
These data demonstrate that, while the ClO 2 chelate has no rapid antimicrobial activity against the E. coli organism, once that chelated ClO 2 is displaced by ferric ion the resulting solution has an activity against that organism that is generally superior to that of the original ClO 2 solution. This is true even with the slight dilution of its concentration resulting from introduction of the activating iron solution. These data provide further confirmation that the ClO 2 has not undergone transformation to chlorite ion by introduction of the chelating agent, and then reconversion back to ClO 2 as a result of the iron displacement, since the reconversion is bound to be of less than 100% efficiency; while the data show equal or superior cidal efficacy equivalent to the original ClO 2 concentration.
EXAMPLE 3
This example illustrates the ability of an EDTA.ClO 2 complex, where the ClO 2 was prepared by direct oxidation of chlorite, to rapidly destroy the pathogenic microorganism Staphylococcus aureus, after displacement of the chelated ClO 2 by Fe +++ ion. Specifically, the chlorine dioxide was prepared by fractional oxidation of 200 ml of a 1600 ppm sodium chlorite solution, at pH 6.4, by the addition of 5 ml of a 1260 ppm sodium hypochlorite solution. At the time of preparation, the solution contained 49.3 ppm of ClO 2 , at which time 2 ml of a 0.05 meq/ml solution of EDTA,Na 2 was added to 150 ml of that solution, forming a colorless chelate solution. The unchelated ClO 2 in that solution was determined spectrophotometrically to be 1.5 ppm.
Two days after preparation of the chelate, its inherent cidal capacity was determined relative to that of the original ClO 2 solution, whose concentration had dropped to 41.2 ppm. This was accomplished through the addition of a 0.3 ml quantity of 1% ferric chloride to 12 ml of the chelate solution. The microbiocidal capability of the ClO 2 and the iron-triggered chelate solutions, and dilutions thereof, were evaluated as follows:
1) the unchelated ClO 2 solution, and 1→10 and 1→50 dilutions;
2) the ferric iron-treated chelate of solution 1), and 1→10 and 1→50 dilutions.
0.1 ml of a challenge inoculum of the Staph. aureus (ATCC No. 6538), suspended in saline, was introduced into 10 ml of the test solution, providing an organism concentration of 5.63 log cfu/ml. After 30 sec. or 2 min., 1 ml of each solution, and 10-fold dilutions thereof, were diluted with 100 ml of normal saline, after which the full volumes were passed through 0.45μ Millipore filters. The latter were placed on TSA plates, incubated for 48 hours at 35° C., and the total numbers of organisms per ml were determined. The following log reductions were obtained for the two solutions at the two contact times:
______________________________________ClO.sub.2 Control ClO.sub.2 -ChelateTime undil 1:10 1:50 undil 1:10 1:50min log reduction of S. aureus______________________________________0.5 5.63 5.63 1.57 5.63 5.63 0.682.0 5.63 5.63 5.63 5.63 5.63 5.63______________________________________
This example demonstrates that the ClO 2 released from the chelate is equally capable of destroying this gram (+) pathogen, even though some dilution of the original ClO 2 solution was sustained by dilution with both the EDTA chelating and the ferric chloride solutions. It also indicates that the chelate solution is capable of being stored.
EXAMPLE 4
This example demonstrates the ability of different metal ions to displace ClO 2 from a chelate depending upon the relative affinity of the chelating agent to ClO 2 and the metal ions. To each of three 5 ml portions of the chelated ClO 2 solution of Example 3 were added 1 drop of a 1:100 dilution of a commercial food dye preparation, which contained a mixture of FD&C Reds No. 40 and No. 3. To portion 1), the Control, two drops of water were added; to portion 2), two drops of a Zn ++ solution, providing about 0.15 meq of that ion; to portion 3), two drops of a Fe +++ solution, providing about 0.12 meq of that ion. In solution 3), the pink coloration disappeared immediately; in solution 2), the pink color faded and disappeared over a several hour period; in solution 1), the pink color remained. This illustrates that the Zn ++ ion, which has a weaker formation constant with EDTA (log K=16.5) than with the Fe +++ ion (log K=25.1), takes longer to competitively displace ClO 2 from its EDTA chelate than does ferric ion, so that the more rapidly displaced ClO 2 was able to bleach the pink coloration immediately, whereas the ClO 2 that was more slowly displaced by the zinc ion was only able to destroy the pink coloration at a slower rate.
EXAMPLE 5
This example illustrates the preparation of a highly concentrated solution of a ClO 2 chelate, useful, for example, as an oral rinse, a vaginal douche or an intramammary infusion to treat mastitis. 50 ml of a pH 7.15 solution containing 2255 ppm of chlorine dioxide (1.67 mM per 50 ml), were added to an Erlenmeyer flask containing 5 ml of a solution with 2.5 mM tetrasodium EDTA. Upon combination, the dark yellow color of the ClO 2 solution instantly disappeared, forming a colorless solution at pH 6.66. The UV Absorbance of that solution at 370 nM indicated a residual, unchelated, chlorine dioxide level of 13.8 ppm, which was 0.68% by weight of the total chlorine dioxide present.
When exposed to a strip of chlorine indicator paper, where the color change is based on the starch-iodine reaction, the color that formed corresponded to the highest color comparison strip. This indicated that the solution had an oxidizing power equivalent to a solution containing at least 200 ppm of chlorine, and by calculation at least 500 ppm of ClO 2 . Since the reaction with the color strip took place at a near-neutral pH, the oxidizing power must have been derived from ClO 2 , rather than a chlorite reduction product, since the latter ion, had it formed, will only oxidize the iodide in the indicator paper at acidic pHs, of about 3 and below.
The solution had an acceptable taste, and was found to be an efficient treatment for oral malodor.
It is clear that the present invention is well adapted to carry out the objects, and achieve the ends and advantages mentioned at the outset. While currently preferred embodiments of the invention have been described for purposes of this disclosure, numerous modifications may be made which will readily suggest themselves to those skilled in the art, and which are encompassed within the spirit of the invention disclosed, and as defined in the appended claims. | A novel chelate complex allows the formation of stable solutions of molecular chlorine dioxide. The chelate complexes are composed of the electron-deficient chlorine dioxide molecule, which can accept an electron, and a chelating agent, which can contribute its available electrons to the accepting orbital of the chlorine dioxide molecule. Both active and passive methods of releasing the chlorine dioxide from such chelates by competitive displacement with selected metal cations are presented. In this manner a stabilized solution of molecular chlorine dioxide can be stored until needed and the chlorine dioxide released at time of use for cleaning, disinfection or other uses. | 8 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This is a continuation of U.S. application Ser. No. 13/578,053, filed Aug. 9, 2012. This application relates to and claims priority from Japanese Patent Application No. 2010-041235, filed on Feb. 26, 2010. The entirety of the contents and subject matter of all of the above is incorporated herein by reference.
TECHNICAL FIELD
[0002] The present invention relates to a wireless communication device and a wireless communication method. Particularly, it relates to a wireless communication device and a wireless communication method with real-time performance required.
BACKGROUND ART
[0003] In wireless communication, communication error (communication failure) occurs due to noise, interference, attenuation, etc. When a device is being controlled or monitored using wireless communication, it is necessary to take measures to prevent the device from malfunctioning or prevent monitor information from being missed due to communication error. For this reason, retransmission of communication data is often attempted when communication error occurs.
[0004] In most cases, a communication frame is generally composed of a physical layer header, an MAC header (hereinafter this expression means physical address-including information) and a data field. There has been known a technique in which this data field is further split into cells so that the cells are subjected to packet transmission after an error checking code is added to each of the cells. Since only the finely split cells need to be retransmitted, lowering of transmission efficiency can be suppressed even if communication error occurs due to noise etc. For example, this technique has been disclosed in JP-A-10-93584.
CITATION LIST
Patent Literature
[0005] Patent Literature 1: JP-A-10-93584
SUMMARY OF INVENTION
Technical Problem
[0006] Generally, for example, destination information which is a physical address, and frame type (beacon, response, etc.) are set in an MAC header, and data are set in a data field. Among these, according to the aforementioned background-art technique, measures against communication error can be taken when the communication error occurs in the data field of a communication frame, but no examination has been made on occurrence of communication error in the MAC header.
[0007] In the aforementioned background-art technique, the communication frame has to be inevitably retransmitted when communication error occurs in the MAC header. As a result, since the communication frame has to be retransmitted when communication error occurs in the MAC header, latency in communication occurs to thereby give rise to a problem that real-time performance in communication will be spoiled.
[0008] An object of the invention is to provide a wireless communication device and a wireless communication method in which high real-time performance is achieved by suppressing occurrence of communication latency against error concerned with acquisition of physical address information of a communication frame.
Solution To Problem
[0009] In order to attain the foregoing object, the invention is configured in such a manner that a communication frame for transmission is generated by allocating a plurality of physical address information-including information, data error checking codes for detecting respective errors of the plurality of physical address-including information, and data to a communication frame; data of the generated communication frame are modulated into a signal, the signal is transmitted by wireless, a signal received by wireless is demodulated into a communication frame, presence/absence of respective errors in a plurality of physical address information-including information included in the communication frame is checked based on data error checking codes included in the communication frame, and one is selected from the plurality of physical address information or a predetermined physical address is generated from the plurality of physical address-including information based on the checking; and determination is made as to whether the received communication is addressed to the device itself based on the selected or generated physical address information.
Advantageous Effects of Invention
[0010] According to the invention, it is possible to cope with an error problem concerned with acquisition of physical address information of a communication frame so that it is possible to suppress communication latency and improve real-time performance.
BRIEF DESCRIPTION OF DRAWINGS
[0011] [FIG 1 ] A configuration diagram of a wireless communication device according to a first embodiment of the invention.
[0012] [FIG 2 ] A configuration view showing configuration of a communication frame in the invention.
[0013] [FIG 3 ] A configuration view showing configuration of a communication frame as a reference example.
[0014] [FIG 4 ] A chart showing a processing flow in a redundant header error inspection unit 12 and a majority determination processing unit 13 .
[0015] [FIG 5 ] A view showing an example of majority determination processing of header information.
[0016] [FIG 6 ] A configuration diagram of a wireless communication device according to another embodiment of the invention.
[0017] [ FIG. 7 ] A chart showing a processing flow in a redundant header error inspection unit 12 in FIG. 6 .
DESCRIPTION OF EMBODIMENTS
[0018] The invention will be described below in detail with reference to the drawings.
[0019] FIG. 1 is a block diagram showing an example of a wireless communication device to which the invention is applied. The wireless communication device 1 includes a transmission frame generator unit 2 , an MAC header generator unit 3 , a modulator unit 4 , a wireless transmission processing unit 5 , a transmission control unit 6 , an antenna 7 , a wireless reception processing unit 8 , a carrier sensor unit 9 , a demodulator unit 10 , a reception frame reception processing unit 11 , a redundant header error inspection unit 12 , a majority determination processing unit 13 , and a received data extraction unit 14 .
[0020] The transmission frame generator unit 2 receives transmitted data from an external device (not shown) and one CRC code-including MAC header information from the MAC header generator unit 3 , and generates a transmission frame (corresponding to a communication frame) by allocating the received MAC header information to a plurality of MAC header areas which have been set in advance, and allocating the transmitted data to a data field. For example, destination information and frame type (beacon, response, etc.) are set in the MAC header. The destination information is an MAC address (physical address). The MAC address serves to identify a local address on an LAN (Local Area Network) as against a global address such as a so-called IP address.
[0021] The CRC is called cyclic redundancy check. The CRC code is a code for detecting data error. It is a matter of course that any other error checking code than the CRC code may be used. Besides the error checking code for checking whether data are damaged or not, an error correcting code including a function of checking whether data are damaged or not and restoring the data when the data are damaged, may be used.
[0022] The modulator unit 4 receives communication frame information outputted from the transmission frame generator unit 2 , modulates the communication frame information, and outputs the modulated communication frame information to the wireless transmission processing unit 5 . The transmission control unit 6 determines whether to start a transmission process or not based on a carrier sensing result inputted from the carrier sensor unit 9 , and makes control to start transmission when the carrier sensing result indicates an “idle state”, or makes control to wait for transmission until the carrier sensing result turns into an “idle state” or to switch the wireless channel to another wireless channel when the carrier sensing result indicates a “busy state”. The “carrier sensing” is to check whether the channel is idle or not for emitting radio waves (starting communication) from the wireless communication device, and to emit radio waves only when the channel is idle. The wireless transmission processing unit 5 receives the modulated communication frame information, performs a transmission process including digital-to-analog conversion, frequency conversion, filtering, and power amplification on the modulated communication frame information, and transmits the resulting communication frame information as a radio signal from the antenna 7 .
[0023] The radio signal received through the antenna 7 is inputted to the wireless reception processing unit 8 . The wireless reception processing unit 8 performs a reception process including frequency conversion, filtering, wave detection, analog-to-digital conversion and symbol timing synchronization detection on the radio signal. In addition, the radio signal is always inputted to the wireless reception processing unit 8 at any time except a transmission time and an RSSI signal indicating the received signal strength of the radio signal is outputted to the carrier sensor unit 9 . The carrier sensor unit 9 determines a use condition of the frequency channel based on the RSSI (Received Signal Strength Indication) signal and outputs a determination result to the transmission control unit 6 . When the RSSI (Received Signal
[0024] Strength Indication) signal is not larger than a predetermined threshold, the carrier sensor unit 9 determines that the frequency channel is an “idle state”. When the RSSI signal is larger than the threshold, the carrier sensor unit 9 determines that the frequency channel is a “busy state”.
[0025] When symbol timing synchronization is detected in the radio reception processing unit 8 , a baseband signal obtained by the reception process is outputted to the demodulator unit 10 . The demodulator unit 10 demodulates the baseband signal and outputs the modulated baseband signal as a reception frame to the reception frame reception processing unit 11 . When the destination address of the received data frame is coincident with the address of the wireless communication device 1 , the reception frame reception processing unit 11 outputs the reception frame (corresponding to the communication frame) to the received data extraction unit 14 . When the destination address of the received data frame is not coincident with the address of the wireless communication device 1 , the reception frame reception processing unit 11 discards the reception frame. MAC header information is used for determining whether the destination address of the received data frame is coincident with the address of the wireless communication device 1 or not. Since the MAC header information is allocated to a plurality of MAC headers, the MAC header information allocated to the plurality of MAC headers is used for selecting or generating correct MAC header information and determining whether the destination address is the concerned address (MAC address included in the MAC header information) or not. The redundant header error inspection unit 12 and the majority determination processing unit 13 are used for this purpose. As will be described later, the redundant header error inspection unit 12 serves to select one piece of MAC header information with no occurrence of error from a plurality of pieces of MAC header information. The majority determination processing unit 13 performs majority determination on these pieces of MAC header information (any other logic operation than the majority determination processing may be used) to thereby generate correct MAC header information when all of the plurality of pieces of MAC header information have error. The redundant header error inspection unit 12 and the majority determination processing unit 13 are collectively referred to as a redundancy selection unit. Although an example in which a determination process, a selection process and a generation process are performed on the MAC header information will be shown below, it is matter of course that the MAC address may be extracted directly so that a determination process etc. is performed on the MAC address.
[0026] The received data extraction unit 14 extracts received data by removing the header etc. of the reception frame, and outputs the received data to another device (not shown) connected to the wireless communication device 1 .
[0027] Next, configuration of a communication frame having a plurality of MAC headers will be described with reference to FIG. 2 . The communication frame shown in FIG. 2 is composed of a physical header, MAC header data 1 , a data field, and an FCS. The data field is composed of CRC 1 , an MAC header 2 , an MAC header N, and data. The reason why the data field is composed of the CRC 1 , the MAC header 2 and the MAC header N is in that this system can coexist with an ordinary wireless LAN system. That is, the MAC header data 1 has the same configuration as that of the MAC header of an ordinary wireless LAN device. When the ordinary wireless LAN device receives a communication frame from the wireless communication device, the ordinary wireless LAN device can easily determine whether the communication frame is addressed to the ordinary wireless LAN device or not, because the MAC header data 1 has one and the same data configuration as that of the ordinary wireless LAN device. If the data configuration of the MAC header data 1 is different, the possibility that the ordinary wireless LAN device will make special operation based on specific bit data may be thought of Therefore, measures are taken to prevent such a case from occurring. In FIG. 2 , the MAC header 1 is composed of MAC header data 1 and CRC 1 . The MAC header 2 is composed of MAC header data 2 and CRC 2 . The MAC header N is composed of MAC header data N and CRC N. Each CRC is provided for detecting error of MAC header data at the time of reception. In addition, the FCS may be set to check error for all data ranging from MAC header data 1 to data, or may be set to check error for data because CRC is added to each MAC header. In this manner, a plurality of MAC headers are provided in the configuration of the communication frame of the wireless communication device so that any MAC header is normal even if communication error occurs. Further, an error detecting function is added to each MAC header so that error occurring in any MAC header can be detected easily.
[0028] Although the CRC's are provided here in the separate areas respectively in order to detect error of the MAC header data at the time of reception, the CRC's may be disposed collectively in one area. Further, configuration may be technically made so that error in some of MAC header data can be detected using one CRC.
[0029] FIG. 3 shows configuration of an ordinary wireless LAN communication frame as a reference example. It is found from FIG. 3 that there is no CRC added to an MAC header. In addition, an FCS is set to check error for the MAC header and data. It can be said that the configuration of the communication frame of the wireless communication device is high in reliability and high in resistance to communication error, in comparison with the configuration of the ordinary wireless LAN communication frame.
[0030] FIG. 4 is a processing flow chart for explaining operation of the redundant header error inspection unit 12 and the majority determination processing unit 13 . In FIG. 4 , an error determination process indicates contents of processing performed by the redundant header error inspection unit 12 , and a majority determination process indicates contents of processing performed by the majority determination processing unit 13 . The redundant header error inspection unit 12 fetches header information from the reception frame reception processing unit 11 in step S 1 . That is, MAC header information ranging from the MAC header 1 to the MAC header N in FIG. 2 (referred to as header information for short in FIG. 4 ) is fetched. Then, in step S 2 , the CRC 1 is used for checking whether error has occurred in the header information (MAC header data and CRC) of the MAC header 1 or not. When no error has occurred, the processing flow goes to step S 3 , in which the MAC header information is stored. That is, in this case, the header information of the MAC header 1 with no occurrence of error is stored. The header information of the MAC header 1 is outputted to the reception frame reception processing unit 11 in step S 15 . When error has occurred in the step S 2 , the processing flow goes to step S 4 . The header information of the MAC header 1 with error is stored in the step S 4 . Then, the processing flow goes to step S 5 . As will be described later, the header information of the MAC header 1 with error, stored in the step S 4 is used in the majority determination process of the majority determination processing unit 13 .
[0031] In the step S 5 , the CRC 2 is used for checking whether error has occurred in the MAC header 2 or not. When no error has occurred, the processing flow goes to step S 6 , in which the MAC header information is stored. That is, in this case, the header information of the MAC header 2 with no occurrence of error is stored. The header information of the MAC header 2 is outputted to the reception frame reception processing unit 11 in the step S 15 . When error has occurred in the step S 5 , the processing flow goes to step S 7 . The header information of the MAC header 2 with error is stored in the step S 7 . Then, the processing flow goes to step S 8 .
[0032] In the step S 8 , the CRC N is used for checking whether error has occurred in the MAC header N or not. When no error has occurred, the processing flow goes to step S 9 , in which the MAC header information is stored. That is, the header information of the MAC header N with no occurrence of error is stored in this case. The header information of the MAC header N is outputted to the reception frame reception processing unit 11 in the step S 15 . When error has occurred in the step S 8 , the processing flow goes to step S 10 . The header information of the MAC header N with error is stored in the step S 10 . Then, the processing flow goes to step S 11 .
[0033] The reason why the processing flow goes to the step S 11 is because error has occurred in all the MAC headers. For this reason, the majority determination process is performed by the majority determination processing unit 13 using the header information of the MAC headers stored in the steps S 4 , S 7 and S 10 respectively. The contents of the process are shown in steps S 11 , S 12 , S 13 , S 14 and S 15 . In the step S 11 , majority determination is performed on each bit in all header information as shown in FIG. 5 . For example, since the rightmost bit in each of the MAC headers (referred to as header for short in FIG. 5 ) is logic “1”, the result of the majority determination is logic “1”. In addition, since the leftmost bit in the MAC header 1 is logic “1” and the leftmost bits in the other MAC headers are logic “0”, the result of the majority determination is logic “0”. Consequently, the majority determination result is logic “00010000 . . . 01”. This is a majority determination result about the MAC header data and CRC data.
[0034] In the step S 12 , the CRC of the generated majority determination result is used for determining whether there is error in the majority determination result or not. When no error has occurred, the processing flow goes to the step S 13 , in which majority header information as the generated majority determination result is stored. That is, the majority header information without error is stored in this case. The majority header information is outputted to the reception frame reception processing unit 11 in the step S 15 . When error has occurred in the step S 12 , the processing flow goes to the step S 14 . In the step S 14 , the fact that error has occurred in the MAC header is outputted to the reception frame reception processing unit 11 . In this case, the reception frame reception processing unit 11 discards the reception frame because the destination address of the received data frame is not coincident with the address of the wireless communication device 1 . When the destination address of the received data frame is coincident with the address of the wireless communication device 1 , that is, when the header information is received from the step S 3 , S 6 , S 9 or S 13 , the reception frame reception processing unit 11 outputs the reception frame (corresponding to the communication frame) to the received data extraction unit 14 .
[0035] Next, another embodiment will be described. Incidentally, description about the same parts as those in the previously described embodiment will be omitted. The same reference signs will be given in the drawings.
[0036] FIG. 6 shows configuration of a wireless communication device from which the majority determination processing unit 13 in FIG. 1 has been removed. The case where a very poor communication environment is provided to give rise to occurrence of communication error extremely frequently is rare so that the wireless communication device shown in FIG. 6 can be used sufficiently in an environment in which communication error does not occur frequently. FIG. 7 is a chart showing a processing flow in a redundant header error inspection unit 12 in the wireless communication device shown in FIG. 6 . Since the majority determination process (the steps S 11 , S 12 , and S 13 ) in FIG. 5 can be dispensed with, the steps S 4 , S 7 and S 10 can be also dispensed with accordingly.
[0037] A plurality of MAC headers are provided in one communication frame. Even if communication error occurs in some MAC headers, information of an MAC header with no occurrence of communication error can be selected so that received data can be extracted from a reception frame (corresponding to the communication frame) by MAC processing based on the normal MAC header information. Retransmission of the communication frame which has to be performed in the background art is prevented from being performed and communication latency is prevented from being increased. Thus, effect in the case where the wireless communication device is applied to a monitoring system or a control system with real-time performance required is large. Further, even if communication errors occur in all the plurality of MAC headers, correct MAC header information can be generated based on majority determination of the MAC header information. Accordingly, received data can be extracted from the reception frame (corresponding to the communication frame) based on the generated correct MAC header information. The same effect as that in the above description can be exerted so that the industrial value of the invention is extremely high.
[0038] Describing the characteristic portion of the embodiment collectively, it is characterized by providing: a transmission frame generator unit which receives CRC information-including MAC header information and generates a communication frame by allocating the received CRC information-including MAC header information to a plurality of MAC header areas set in advance in the communication frame and allocating transmission data to a data field in the communication frame; a redundant MAC header error inspection unit which checks presence/absence of error in each MAC header information upon reception and selects MAC header information with no error; and a majority determination processing unit which generates MAC header information with no error based on majority determination processing on all pieces of MAC header information when there are errors in all the pieces of MAC header information; wherein determination is made as to whether a received communication frame is addressed to the device itself or not based on the normal MAC header information obtained by the redundant MAC header error inspection unit or the majority determination processing unit. Further, the embodiment is characterized in that: the communication frame is configured in such a manner that one of MAC headers is allocated to the MAC header of the communication frame while the other MAC headers are allocated to the data field so that one and the same MAC header information is allocated to each of the MAC headers. In addition, in the wireless communication device according to the invention, the number of MAC headers is three or more and CRC information is provided in the MAC header information, presence/absence of error in each MAC header information is checked at the time of reception, MAC header information with no error is selected, and information obtained by majority determination of all the pieces of MAC header information is set as MAC header information when there are errors in all the pieces of MAC header information.
[0039] That is, one communication frame has a plurality of MAC headers so that information of an MAC header with no occurrence of communication error can be used even if communication error (communication failure) occurs in some MAC headers, or correct MAC header information can be generated based on majority determination of the pieces of MAC header information even if errors (failures) occur in all the MAC headers. Accordingly, it is possible to avoid retransmission of the communication frame which has to be performed in the background art, so that it is possible to suppress increase in communication latency to give rise to improvement in real-time performance.
REFERENCE SIGNS LIST
[0000]
1 wireless communication device
2 transmission frame generator unit
3 MAC header generator unit
4 modulator unit
5 wireless transmission processing unit
6 transmission control unit
7 antenna
8 wireless reception processing unit
9 carrier sensor unit
10 demodulator unit
11 reception frame reception processing unit
12 redundant header error inspection unit
13 majority determination processing unit
14 received data extraction unit
15 transmission survey unit | Arrangements with wireless transmitter having: transmission operation processing unit allocating first header information (FHI) including physical address (PA) information to a header, allocates first data error checking code (FDECC) for detecting an error of FHI, second header information (SHI) as redundant header information of FHI, second data error checking code (SDECC) for detecting an error of SHI, divides data field into cell units, and adds third error checking code to each cell, to generate the communication frame; and a wireless transmission unit. A wireless receiver with: wireless receiving unit receiving the frame; reception operation processing unit checking if errors exists in FHI based on FDECC allocated to data field, and if an error, further checks if error in SHI based on SDECC, and if no error, generates a predetermined PA by using SHI, and judges if received communication frame is addressed to own wireless receiver based on generated predetermined PA. | 7 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an outer shuttle of a sewing machine, having a structure such that the outer shuttle accommodates an inner shuttle that grabs an upper thread and accommodates a bobbin around which a lower thread is wound, and a gear shaft having a driven gear connected to a driving gear provided on a lower shaft of a driving source that is rotatably supported in the sewing machine is fixed by press-fitting to a shuttle body.
[0003] 2. Description of the Related Art
[0004] General sewing machines are provided with a shuttle device including an outer shuttle having a cutting edge for grabbing an upper thread and an inner shuttle that accommodates a bobbin around which a lower thread is wound in order to form stitches using the upper thread and the lower thread wound around the bobbin. A gear shaft is attached to a lower end surface of the outer shuttle, and the outer shuttle is rotated by a driving gear that is attached to a lower shaft of the sewing machine to engage with the gear shaft. An outer shuttle in which the shuttle body and the gear shaft are formed of separate members is known. An outer shuttle of this type is disclosed in Japanese Utility Model Registration No. 3054640, for example.
[0005] The shuttle body and the gear shaft are formed of separate members when the two members are formed of different materials and it is difficult to form the same integrally. This is the case where the shuttle body is formed of metal and the gear shaft is formed of a synthetic resin, for example. When constituent elements of a shuttle are formed of separate members and different materials, the manufacturing cost may be decreased. Thus, a shuttle device of a type such that the shuttle body and the gear shaft are formed of separate members may be used depending on the grade of a sewing machine. FIGS. 4A and 4B are schematic views for describing the outer shuttle disclosed in Japanese Utility Model Registration No. 3054640.
SUMMARY OF THE INVENTION
[0006] In the conventional technique disclosed in Japanese Utility Model Registration No. 3054640, a shuttle device of a type such that the shuttle body and the gear shaft of an outer shuttle are formed of separate members has the following problems. That is, a gear shaft a is attached to a bottom portion of a shuttle body b, a driving gear provided in the sewing machine engages with the gear shaft, the driving gear rotates with the driving of a motor, and the rotation is transmitted to the gear shaft a to rotate the shuttle body b.
[0007] The gear shaft a is hollow and a supporting shaft c that horizontally or vertically supports the gear shaft and the shuttle body b is inserted inside the gear shaft a. Then, the outer shuttle having the gear shaft and the shuttle body b rotates about the supporting shaft c. This is the structure of a general shuttle device. The outer shuttle rotates at a very high speed. Thus, if the sewing machine is operated for a long period, a large amount of heat is generated by the driving of the gear shaft b. With this heat, thermal expansion occurs in the gear shaft b.
[0008] However, since the gear shaft a is fixed by press-fitting to the lower surface side of the bottom portion of the shuttle body b, deformation toward the outer side in the radial direction due to thermal expansion is restricted at this press-fitting position. Thus, deformation of the gear shaft a due to thermal expansion develops toward the center in the radial direction of the shaft hole.
[0009] When the deformation of the gear shaft a due to thermal expansion develops toward the center in the radial direction of the shaft hole, the shaft hole of the gear shaft a is deformed to make strong contact with the supporting shaft c accommodated in the gear shaft a (see FIG. 4B ). When such a state is created, the shuttle body as well as the gear shaft may not be able to rotate properly. Thus, the outer shuttle may be unable to perform its role satisfactorily, which may interfere with the stitching operation of the sewing machine.
[0010] Under these circumstances, an object of the present invention is to provide an outer shuttle of a sewing machine, having such a structure that a gear shaft having a shaft support hole formed on an inner circumference thereof is fixed by press-fitting to a shuttle body, the outer shuttle being capable of suppressing thermal expansion of a shaft support hole corresponding to a press-fitting area of the gear shaft to maintain satisfactory rotation.
[0011] As a result of intensive studies to solve the above problems, the inventors have solved the problems by providing, as a first embodiment of the present invention, an outer shuttle of a sewing machine, which accommodates an inner shuttle that grabs an upper thread and accommodates a bobbin around which a lower thread is wound, the outer shuttle including: a gear shaft which has a driven gear connected to a driving gear, provided on a lower shaft, which is a driving source of the outer shuttle that is rotatably supported in the sewing machine, and which also has a shaft support hole formed aligned with an axial center of the driven gear; a shuttle body to which the gear shaft is press-fitted and fixed at the center of rotation of a press-fit receiving hole formed in a bottom portion thereof; and a shuttle support shaft which is inserted into the shaft support hole of the gear shaft of the shuttle body to support the rotation of the shuttle body, wherein a plurality of ridge-shaped portions is formed on an inner circumference of the shaft support hole so as to correspond to a press-fitting depth of the gear shaft.
[0012] A second embodiment of the present invention solves the problems by the outer shuttle of the sewing machine according to the first embodiment, in which the ridge-shaped portions are formed along an axial direction of the shaft support hole at equal intervals in a circumferential direction. A third embodiment of the present invention solves the problems by the outer shuttle of the sewing machine according to the first embodiment, in which the ridge-shaped portions are formed in the shaft support hole in a spiral form.
[0013] A fourth embodiment of the present invention solves the problems by the outer shuttle of the sewing machine according to the first or second embodiment, in which the ridge-shaped portion has a cross-section in the shape of a circular arc that protrudes toward the center in a radial direction of the shaft support hole. A fifth embodiment of the present invention solves the problems by the outer shuttle of the sewing machine according to the first embodiment, in which a diameter at a distal end of the ridge-shaped portion is set to be equal to or larger than an inner diameter of the shaft support hole of the gear shaft.
[0014] In the present invention, the distal end of the gear shaft having the shaft support hole is fixed by press-fitting to the press-fit receiving hole of the shuttle body, and the plurality of ridge-shaped portions is formed on the inner circumference side corresponding to the press-fitting area of the gear shaft. Thus, even when the gear shaft and the shuttle body rotate at a high speed for a long period and thermal expansion occurs, the expanding portion of the gear shaft due to the thermal expansion can expand to the groove-shaped portions between the ridge-shaped portions.
[0015] Moreover, since a plurality of ridge-shaped portions is formed in the inner circumference corresponding to the press-fitting area of the shaft support hole of the gear shaft, the expanding portion can expand to the groove-shaped portions between the ridge-shaped portions and the shape of the shaft support hole is not damaged. Thus, the gear shaft and the shuttle body can maintain satisfactory rotation. The present invention is particularly favourable when the shuttle body is formed of metal and the gear shaft is formed of a synthetic resin which are likely to expand thermally.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1A is a longitudinal sectional view of a first embodiment of the present invention, FIG. 1B is an exploded perspective view of main parts, FIG. 1C is a partially cut-away, enlarged, exploded perspective view of main parts, illustrating a state in which a press-fit receiving hole of a shuttle body is separated from a distal end press-fitting portion of a gear shaft, and FIG. 1D is a partially cut-away, enlarged, exploded perspective view of main parts, illustrating a state in which the press-fit receiving hole of the shuttle body is press-fitted to a distal end press-fitting portion of the gear shaft.
[0017] FIG. 2 is an enlarged cross-sectional plan view of main parts of a press-fitting portion in which thermal expansion has occurred.
[0018] FIG. 3A is a partially cut-away perspective view of main parts, illustrating a modified example of a ridge-shaped portion according to the first embodiment, and FIG. 3B is a partially cut-away perspective view of main parts, illustrating a modified example of a ridge-shaped portion according to a second embodiment.
[0019] FIG. 4A is a partially cut-away perspective view of main parts according to the conventional technique, and FIG. 4B is a cross-sectional plan view of main parts of the conventional technique.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0020] Embodiments of the present invention will be described with reference to the drawings. A shuttle device of the present invention mainly includes a shuttle body A, a gear shaft B, and a shuttle supporting shaft 7 as illustrated in FIGS. 1A, 1B , and the like. The shuttle body A is formed of metal or a synthetic resin such as plastics. A columnar side wall portion 2 is formed on an outer circumference of a substantially disc-shaped bottom portion 1 . A shaft support hole 5 is formed at a central position of the bottom portion 1 . Moreover, reference numeral 9 in the figure is an inner shuttle.
[0021] An accommodation groove 11 to which a magnet plate is attached is formed in an inner bottom surface of the bottom portion 1 (see FIGS. 1A, 1C , and the like). The accommodation groove 11 is a portion of the bottom portion 1 and is included in a portion of the bottom portion 1 .
[0022] A press-fit receiving hole 12 is formed at the center of the bottom portion 1 (see FIGS. 1B to 1D ). A cylindrical portion 12 a that extends downward is formed on a lower surface side of the bottom portion 1 and around the press-fit receiving hole 12 . Engagement portions 13 are formed on the inner circumference of the press-fit receiving hole 12 . The engagement portions 13 are portions that engage with engaged portions formed on a distal end press-fitting portion of the gear shaft.
[0023] The accommodation groove 11 accommodates a magnet bed 81 , a washer 82 , a spring washer 83 , and a permanent magnet 84 . The magnet bed 81 is fixed to the accommodation groove 11 and the permanent magnet 84 is fixed to the bottom portion 1 with the magnet bed 81 interposed. The gear shaft B includes a shaft body 3 , a distal end press-fitting portion 4 , a shaft support hole 5 , and a press-fitting hole 51 (see FIGS. 1A and 1C ). A driven gear 31 is provided in the shaft body 3 .
[0024] The driving gear driven by a motor that is provided on the body side of a sewing machine transmits rotation via the driven gear 31 to rotate the gear shaft B. The distal end press-fitting portion 4 is formed in the distal end of the shaft body 3 and is press-fitted into the press-fit receiving hole 12 of the shuttle body A (see FIG. 1C ). The distal end press-fitting portion 4 has a cylindrical shape and is formed continuously with the distal end of the shaft body 3 .
[0025] The distal end press-fitting portion 4 has a smaller diameter than that of the shaft body 3 so that a step 32 is formed between the distal end press-fitting portion 4 and the shaft body 3 (see FIG. 1C ). The step 32 has a role of restricting a press-fitting depth when the distal end press-fitting portion 4 of the gear shaft B is press-fitted into the press-fit receiving hole 12 and makes the press-fitting depth of the gear shaft B into the press-fit receiving hole 12 uniform.
[0026] Engaging portions 41 are formed on the outer circumference of the distal end press-fitting portion 4 . The engaging portions 41 engage with the engagement portions 13 formed on the press-fit receiving hole 12 to reinforce a press-fitting structure of the distal end press-fitting portion 4 and the press-fit receiving hole 12 and prevent idle rotation. Further, although plural engagement portions 13 and plural engaging portions 41 are formed, only one engagement portion and only one engaging portion may be formed.
[0027] A shaft support hole 5 is formed along an axial direction of the shaft body 3 . Moreover, a press-fitting hole 51 is formed on the inner circumference side of the distal end press-fitting portion 4 (see FIGS. 1A and 1C ). The press-fitting hole 51 is formed as a portion of the shaft support hole 5 and is positioned near the upper end of the shaft support hole 5 (see FIGS. 1A and 1C ). The press-fitting hole 51 is formed so as to correspond to the press-fitting depth when the distal end press-fitting portion 4 of the gear shaft B is press-fitted into the press-fit receiving hole 12 of the shuttle body A.
[0028] A plurality of ridge-shaped portions 61 is formed on the inner circumferential surface of the press-fitting hole 51 (see FIGS. 1C, 1D , and the like). The ridge-shaped portions 61 have a plurality of embodiments. As described above, the ridge-shaped portions 61 formed in the press-fitting hole 51 are also formed so as to correspond to the press-fitting depth when the distal end press-fitting portion 4 of the gear shaft B is press-fitted into the press-fit receiving hole 12 of the shuttle body A. A shuttle supporting shaft 7 (described later) is inserted in and supported by the shaft support hole of the gear shaft B. The inner diameter of the shaft support hole 5 is set such that the shuttle body A can smoothly rotate around the shuttle supporting shaft 7 without any rattling.
[0029] In the press-fitting hole 51 , the diameter at the distal end of the ridge-shaped portions 61 is set to be equal to or larger than the inner diameter of the shaft support hole 5 . Thus, the ridge-shaped portions 61 are not in contact with the shuttle supporting shaft 7 (see FIG. 2 ). Thus, even when the ridge-shaped portions 61 are deformed in a radial direction due to thermal expansion, the ridge-shaped portions 61 will not make direct contact with the shuttle supporting shaft 7 and will not affect the rotation of the shuttle body A.
[0030] According to a first embodiment of the ridge-shaped portions 61 , the ridge-shaped portions are formed along the axial direction at equal intervals in the circumferential direction. In this embodiment, the number of ridge-shaped portions 61 is eight. However, the number of ridge-shaped portions 61 is not limited to eight but may be smaller than or larger than eight. That is, it is sufficient that the plurality of ridge-shaped portions 61 makes uniform contact with the shuttle supporting shaft 7 in the circumferential direction and create a stable supporting state.
[0031] According to a second embodiment of the ridge-shaped portions 61 , a plurality of ridge-shaped portions 61 is formed in a spiral form on the inner circumferential surface of the press-fitting hole 51 (see FIG. 3B ). The plurality of ridge-shaped portions 61 formed in the spiral form is formed in a substantially internal thread form. Moreover, groove-shaped portions 62 are also formed in a spiral form.
[0032] A distal end of each ridge-shaped portion 61 in the radial direction of the press-fitting hole 51 has a cross-section in the shape of a circular arc that protrudes toward the center in the radial direction of the press-fitting hole 51 . Due to this, the shuttle supporting shaft 7 is supported in the press-fitting hole 51 in a substantially linearly contacting state. Moreover, the distal ends of the ridge-shaped portions 61 may have the same surface shape as an inner circumferential surface other than the press-fitting area (that is, the inner circumferential surface of the shaft support hole 5 ). In this case, the plurality of ridge-shaped portions 61 almost make surface contact with the outer circumference of the shuttle supporting shaft 7 .
[0033] The shuttle supporting shaft 7 includes a supporting shaft portion 71 and a flange portion 72 . The attachment direction of the shuttle supporting shaft 7 is determined among vertical and horizontal depending on whether the outer shuttle rotates on a horizontal surface or on a vertical surface. The supporting shaft portion 71 is inserted into the press-fit receiving hole 12 of the shuttle body A and the press-fitting hole 51 and the shaft support hole 5 of the gear shaft B, and the flange portion 72 is disposed in the accommodation groove 11 of the shuttle body A.
[0034] In the present invention, in a structure in which the distal end press-fitting portion 4 of the gear shaft B is press-fitted and fixed to the press-fit receiving hole 12 of the shuttle body A, a plurality of ridge-shaped portions 61 is formed on the inner circumference side of the press-fitting hole 51 corresponding to the press-fitting area of the distal end press-fitting portion 4 and the press-fit receiving hole 12 . Even when the gear shaft B and the shuttle body A rotate at a high speed for a long period and thermal expansion occurs, the expanding portion due to the thermal expansion in the press-fitting portion can expand to the plurality of groove-shaped portions 62 formed between the plurality of ridge-shaped portions 61 (see FIG. 2 ).
[0035] That is, the outer circumferential portion of the distal end press-fitting portion 4 of the gear shaft B is surrounded by the press-fit receiving hole 12 . Thus, the distal end press-fitting portion 4 of the gear shaft B cannot expand toward the outer side in the radial direction. Therefore, the distal end press-fitting portion 4 thermally expands toward the center in the radial direction from the inner circumference side.
[0036] In this state, on the inner circumference side of the distal end press-fitting portion 4 , the protruding portion due to thermal expansion presses the outer circumference of the shuttle supporting shaft 7 so that the shuttle body A and the gear shaft B cannot rotate properly. However, since the press-fitting hole 51 has the plurality of ridge-shaped portions 61 , the portions that protrude due to thermal expansion can expand to the plurality of groove-shaped portions 62 formed between the plurality of ridge-shaped portions 61 (see FIG. 2 ).
[0037] Due to this, even when thermal expansion occurs in the gear shaft B, the shape of the press-fitting hole 51 is rarely damaged, and the press-fitting hole 51 of the gear shaft B can maintain satisfactory rotation of the shuttle body A and the gear shaft B without pressing the outer circumference of the shuttle supporting shaft 7 . The present invention is particularly favourable when the gear shaft B is formed of synthetic resins and the shuttle body A is formed of metal.
[0038] According to the second embodiment, since the ridge-shaped portions are formed along the axial center of the shaft support hole at equal intervals in the circumferential direction, it is possible to simplify the structure. According to the third embodiment, since the ridge-shaped portions are formed in the shaft support hole in a spiral form, it is possible to increase the effective length of each ridge-shaped portion and to increase the expanding portion due to thermal expansion.
[0039] According to the fourth embodiment, since the ridge-shaped portion has a cross-section in the shape of a circular arc that protrudes toward the center in the radial direction of the distal end shaft supporting portion, it is possible to decrease the contacting area of the ridge-shaped portion and the supporting shaft and to decrease the rotation resistance between the gear shaft and the supporting shaft. According to the fifth embodiment, since the adjacent ridge-shaped portions are at the same surface as an inner circumferential surface other than a press-fitting area, it is possible to allow the supporting shaft to make uniform contact with the shaft support hole of the gear shaft. | An outer shuttle of a sewing machine, which accommodates an inner shuttle that grabs an upper thread and accommodates a bobbin around which a lower thread is wound, includes: a gear shaft which has a driven gear connected to a driving gear, provided on a lower shaft, which is a driving source of the outer shuttle that is rotatably supported in the sewing machine, and which also has a shaft support hole formed aligned with an axial center of the driven gear; a shuttle body to which the gear shaft is press-fitted and fixed at the center of rotation of a press-fit receiving hole formed in a bottom portion thereof; and a shuttle supporting shaft which is inserted into the shaft support hole of the gear shaft of the shuttle body to support the rotation of the shuttle body. | 3 |
RELATED APPLICATIONS
The present application is related to U.S. Provisional Patent Application, Ser. No. 61/287,590, filed on Dec. 17, 2010, which is incorporated herein by reference and to which priority is claimed pursuant to 35 USC 119.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to methodologies to analyze breast density based on magnetic resonance imaging (MRI).
2. Description of the Prior Art
Mammary gland architecture may play an important role in determining the susceptibility of developing breast cancer. The most well-studied parameter is mammographic density, evaluated as the percentage of dense tissue area over the total breast area on mammograms. There are numerous studies reporting mammographic density as a strong risk factor; the higher the percentage, the higher the breast cancer risk. Increased density over time has also been shown to be associated with higher cancer incidence. There is also evidence suggesting that the relative distribution of adipose and fibroglandular tissue (referred as the breast parenchymal pattern in this specification) is involved in cancer development. The adipose tissue that is abundantly present around the ductal epithelium of the mammary gland may function as a slow release depot for lipid-soluble carcinogenic agents, and thus may affect cancer risk. However, the relationship between parenchymal pattern and cancer risk has never been reported, possibly due to the lack of both the imaging modality necessary to reveal the distribution pattern and the appropriate analysis methods.
Several studies have applied texture analysis to analyze the distribution pattern of the projected dense tissue on mammograms, and shown differences between women with invasive cancer and women without cancer. There are also differences between high-risk women carrying the BRCA1 and BRCA2 gene and low-risk women, which is possibly due to lobular branching promoted by these genes. Since the mammogram is a two-dimensional (two dimensional) projection image, texture analysis can be used to characterize the amount and/or the heterogeneity/homogeneity of dense tissue. However, as these features arise in part from the way that tissues overlap on the projected image, the analyzed parameters may be affected by different positioning of the breast and the degrees of compression.
What is needed is a three-dimensional imaging technique to reveal the respective distribution of the fatty and fibroglandular tissues. The investigation of the relationship between cancer risk and breast parenchymal pattern will only be meaningful when the parameters can be reliably measured. MRI provides three dimensional images of the breast, and that allows for the slice-by-slice segmentation of the fibroglandular and the fatty tissues for the evaluation of breast parenchymal pattern. To date, only a few studies have investigated the percent breast density using MRI, and the relative distribution pattern of the fatty and fibroglandular tissues has not yet been reported. The wealth of the three dimensional information that can be provided by MRI has yet to be fully explored. With the establishment of the American Cancer Society guidelines for annual MRI screening for high-risk women, many more clinical breast MRI examinations will be performed. Development of reliable methods to measure the extent of density and to characterize the parenchymal pattern may provide additional information contributing to a better management plan for these women.
BRIEF SUMMARY OF THE INVENTION
In the illustrated embodiment we disclose a method to study the morphology of fibroglandular tissue distribution using three-dimensional breast MRI, which is not subject to the tissue overlapping problem.
The illustrated embodiment of the invention is directed to a method to analyze breast density based on magnetic resonance imaging (MRI). Systems for analyzing breast density based on two-dimensional mammogram are commercially available. The disclosed method of the illustrated embodiments is based on MRI, which acquires three-dimensional images and can be used to analyze not only the amount of dense tissue, but also the morphological distribution of the dense tissue using automated computerized analysis of the MRI data. Breast density has been shown to predict the individual woman's risk of developing breast cancer.
While analysis systems for breast MRI have been previously devised, the main function is to display abnormal lesions, so what is needed is a system for analyzing the density of normal breast. This information may be used to provide a better management plan for patients receiving breast MRI.
In order to analyze the morphology of dense tissue in the breast, first a segmentation method to separate breast from the body is employed. Then computer algorithms are applied to separate the dense and fatty tissues in the breast in the MR image data. There is evidence in the literature that not only the amount of dense tissue but the relative distribution between the dense and fatty tissues may contribute to the development of breast cancer. The quantitative computerized method developed by us can be applied to analyze the morphological distribution of dense tissue in the breast, which has never been shown before.
In addition to four individual parameters (circularity, convexity, irregularity, and compactness), we further developed a composite score by combining these four parameters with different weightings. The morphology analysis algorithms, and the entire breast density segmentation and analysis system are novel. The advantage of the illustrated embodiments are that they can perform the entire procedure in an computer or data processor, starting from raw MR images. The system performs breast segmentation, dense tissue segmentation, and complete the analysis of dense tissue volume, percent density, as well as the morphological analysis. The analysis software reads the MR images from one study of the patient. The operator identifies a body landmark from the images, and the software automatically performs all segmentation procedures and gives a report to show all analyzed values as will be described below in greater detail.
In the illustrated embodiment four parameters, namely circularity, convexity, irregularity, and compactness, which are sensitive to the shape and margin of segmented fibroglandular tissue, were analyzed for 230 patients. Cases were assigned to one of two distinct parenchymal breast patterns: Intermingled pattern with intermixed fatty and fibroglandular tissue (Type I, N=141), and central pattern with confined fibroglandular tissue inside surrounded by fatty tissue outside (Type C, N=89). For each analyzed parameter, the differentiation between these two patterns was analyzed using a two-tailed t-test based on transformed parameters to no al distribution, as well as distribution histograms and receiver operator characteristic (ROC) analysis.
These two groups of patients were well matched both in age (50±11 vs 50±11) and in fibroglandular tissue volume (Type I: 104±62 cm 3 vs Type C: 112±73 cm 3 ). Between Type I and Type C breasts, all four morphological parameters showed significant differences that could be used to differentiate between the two breast types. In the ROC analysis, among all four parameters, the “compactness” could achieve the highest area under the curve of 0.84, and when all four parameters were combined, the AUC could be further increased to 0.94.
The results suggest that these morphological parameters analyzed from three dimensional MRI can be used to distinguish between intermingled and central dense tissue distribution patterns, and hence may be used to characterize breast parenchymal pattern quantitatively. The availability of these quantitative morphological parameters may facilitate the investigation of the relationship between parenchymal pattern and breast cancer risk.
More specifically the illustrated embodiments of the invention include a method to analyze breast density based on magnetic resonance imaging (MRI) of a breast of a patient comprising the steps of segmenting an MR image of the breast from one set of three-dimensional breast MRI images, and analyzing the amount of dense tissue and the morphological distribution of the dense tissue.
The step of analyzing the amount of dense tissue and the morphological distribution of the dense tissue further includes the step of analyzing the density of normal breast tissue to provide a management plan for patients receiving breast MRI or to predict the risk of developing breast cancer.
The step of analyzing the amount of dense tissue and the morphological distribution of the dense tissue includes segmenting tissue data to separate breast tissue from other body tissue, separating tissue data of the dense and fatty tissues in the breast, and analyzing the morphological distribution of dense tissue in the breast to derive one or more three dimensional morphological parameters of the dense tissue distribution.
The method further includes the step of generating a composite score by combining one or more three dimensional morphological parameters of the dense tissue distribution with different weightings.
The step of segmenting an MR image of the breast includes the step of starting from raw MR images.
The method further includes the step of performing breast segmentation, dense tissue segmentation, and complete the analysis of dense tissue volume, percent density, as well as the morphological analysis from one MRI study on a patient.
The method further includes the step of identifying a body landmark from the MR images, automatically performing all segmentation procedures, and generating a report to show all analyzed values.
The illustrated embodiment also includes a method for breast cancer treatment of a patient comprising the step of determining three dimensional morphological parameters of circularity; convexity, irregularity, and compactness of the breast tissue of the patient to characterize dense tissue distribution patterns based on three dimensional MRI data.
The method further includes the step of assessing cancer risk, predicting efficacy of chemoprevention drugs, or planning optimal breast treatment management.
The method further includes the step of quantitatively characterizing and distinguishing distribution patterns of the dense tissues in breast tissue having an intermingled pattern (Type I), and a central pattern (Type C).
The step of determining the three dimensional morphological parameter of circularity comprises determining
circularity= V within /V fibro
where V within is the volume of fibroglandular tissue within the sphere of effective diameter D eff =2×(3·V fibro /4π) 1/3 and V fibro is the total volume of fibroglandular tissue.
The step of determining circularity comprises identifying a centroid of fibroglandular tissue in the MRI of a breast, defining a sphere with diameter of D eff with respect to the centroid, measuring a volume of the fibroglandular tissues within the sphere, and determining a ratio of the volume of the fibroglandular tissues within the sphere to the total fibroglandular tissue within the breast to quantitatively define the circularity.
The step of determining the three dimensional morphological parameter of convexity comprises determining
convexity= V fibro /V convex ,
where V convex is the volume of the minimum convex hull containing border voxels of the fibroglandular tissue identified using a gift wrapping algorithm and V fibro is the total volume of fibroglandular tissue.
The step of determining the three dimensional morphological parameter of irregularity comprises determining
irregularity=1 −πD eff 2 /S fibro ,
where S fibro is the surface area of fibroglandular tissue, identifying a centroid of fibroglandular tissue in the MRI of a breast, defining a sphere with diameter of D eff with respect to the centroid, D eff =2×(3·V fibro /4π) 1/3 , and where V fibro is the total volume of fibroglandular tissue.
The step of determining the three dimensional morphological parameter of compactness comprises determining
compactness= S fibro 3/2 /V fibro
where S fibro is the surface area of fibroglandular tissue, and where V fibro is the total volume of fibroglandular tissue.
The method further includes the step of combining the three dimensional morphological parameters of circularity, convexity, irregularity, and compactness of the breast tissue of the patient to characterize dense tissue distribution patterns based on three dimensional MRI data to generate a single three dimensional morphological parameter to characterize dense tissue distribution patterns based on three dimensional MRI data.
The single three dimensional morphological parameter is generated by the computation of 0.3+0.8×Circularity+0.7×Convexity 1/2 −0.2×Irregularity 1/2 −0.1×Compactness 1/2 .
The illustrated embodiments further include an apparatus to analyze breast density based on magnetic resonance imaging (MRI) of a breast of a patient comprising means or a data processor configured for segmenting an MR image of the breast from one set of three-dimensional breast MRI images; and means or configuration of the data processor for analyzing the amount of dense tissue and the morphological distribution of the dense tissue.
The means or data processor for analyzing the amount of dense tissue and the morphological distribution of the dense tissue comprises means for determining three dimensional morphological parameters of circularity, convexity, irregularity, and compactness of the breast tissue of the patient to characterize dense tissue distribution patterns based on three dimensional MRI data.
The means or data processor for determining three dimensional morphological parameters of circularity, convexity, irregularity, and compactness of the breast tissue of the patient further comprises means for combining the three dimensional morphological parameters of circularity, convexity, irregularity, and compactness of the breast tissue of the patient into a single three dimensional morphological parameter to characterize dense tissue distribution patterns based on three dimensional MRI data.
While the apparatus and method has or will be described for the sake of grammatical fluidity with functional explanations, it is to be expressly understood that the claims, unless expressly formulated under 35 USC 112, are not to be construed as necessarily limited in any way by the construction of “means” or “steps” limitations, but are to be accorded the full scope of the meaning and equivalents of the definition provided by the claims under the judicial doctrine of equivalents, and in the case where the claims are expressly formulated under 35 USC 112 are to be accorded full statutory equivalents under 35 USC 112. The invention can be better visualized by turning now to the following drawings wherein like elements are referenced by like numerals.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 a - 1 c a MRI images of three case examples, including one fatty breast ( FIG. 1 a ), one Type I case (intermingled pattern, FIG. 1 b ), and one Type C case (central pattern, FIG. 1 c ). For each case, five axial view MR images from five imaging slices selected from superior to inferior directions are shown. There are no breast lesions on these images. The percent density is 5.4% for the fatty breast, 14.1% for the Type I case, and 13.9% for the Type C case.
FIGS. 2 a - 2 c are bar plots for comparing the age, fibroglandular tissue volume, and the percent density among three subject groups respectively. The fatty breast group (indicated as Type F) is significantly older, and has the smallest fibroglandular tissue volume and the lowest percent density compared to the intermingled type (Type I) and the central type (Type C). The Type I and Type C groups have comparable age, fibroglandular tissue volume, and the percent density, thus they cannot be separated based on these parameters.
FIG. 3 is an illustration of the calculation of the circularity and the convexity index. Only one slice is shown as an example, but the analysis was performed in three dimensions. For circularity, a sphere with effective diameter D eff is drawn, and the ratio between the fibroglandular tissue volume within the sphere and the total fibroglandular tissue volume is calculated as the circularity index. The intermingled pattern (top) has a circularity index of 0.42 and the central pattern (bottom) has a higher index of 0.86. For convexity, the minimum convex hull is drawn, and the ratio between the total fibroglandular tissue volume and the convex hall volume is calculated as the convexity index. The Intermingled pattern (top) has a convexity index of 0.36 and the central pattern (bottom) has a higher index of 0.73.
FIGS. 4 a - 4 d are histograms of four morphological parameters differentiating the intermingled pattern (Type I, dashed curve) and the central pattern (Type C, solid curve), FIG. 4 a —circularity index, FIG. 4 b —convexity index, FIG. 4 c —irregularity index, and FIG. 4 d —compactness index. The intermingled pattern group has lower circularity and convexity, and higher irregularity and compactness compared to the central pattern group. The cases with high and low indices are illustrated in FIGS. 5-8 .
FIGS. 5 a and 5 b are MRI images illustrating that the circularity index is sensitive to the spherical vs nonspherical shapes. The FIG. 5 a case is an intermingled pattern with percent density=9.6% and circularity index=0.29, ranking 33 in all 230 cases. The FIG. 5 b case is a central pattern with a similar percent density=9.8%, and a higher circularity index=0.58, ranking 187 in all 230 cases.
FIGS. 6 a and 6 b are MRI images which illustrate that the convexity index is sensitive to the convex vs concave shapes. The FIG. 6 a case is an intermingled pattern with percent density=10.9% and convexity index=0.20, ranking #30 in all 230 cases. The FIG. 6 b case is a central pattern with percent density=11.6%, and a higher convexity index=0.46, ranking #180 in all 230 cases.
FIGS. 7 a and 7 b illustrate that the irregularity index is sensitive to the irregular vs smooth margins. FIG. 7 a is an intermingled pattern with percent density=15.1% and irregularity index=0.74, ranking #190 in all 230 cases. FIG. 7 b is a central pattern with percent density=15.6%, and a lower irregularity index=0.54, ranking #26 in all 230 cases.
FIGS. 8 a and 8 b illustrate that the compactness index is sensitive to both shape and margin. Round shape with smooth margin has a relatively low compactness index. FIG. 8 a is an intermingled pattern with percent density=12.9% and compactness index=17.5, ranking #180 in all 230 cases. FIG. 8 b is a central pattern with the percent density=11.8%, and a lower compactness index=6.7, ranking #32 in all 230 cases.
FIG. 9 is a graph of the ROC curves, showing sensitivity as a function of 1-specificity. When only using the compactness index the AUC is 0.84, and when using all four morphology parameters combined, the AUC is improved to 0.94.
The invention and its various embodiments can now be better understood by turning to the following detailed description of the preferred embodiments which are presented as illustrated examples of the invention defined in the claims. It is expressly understood that the invention as defined by the claims may be broader than the illustrated embodiments described below.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
We have previously published an analysis method utilizing computer algorithms to segment the fibroglandular tissue for quantitative measurement of the percent density in the whole breast using MRI. In the illustrated embodiment we address a new question: In addition to the percent density, we use quantitative parameters to characterize the distribution pattern of the dense tissues. As an initial approach, we analyzed two distinct breast parenchymal patterns that can be classified visually: The intermingled pattern with intermixed fatty and fibroglandular tissues, and the central pattern with confined fibroglandular tissue inside surrounded by fatty tissue outside. Breasts from these two groups may have comparable percent densities, but differ in the distribution pattern of their dense tissue. Four different morphological parameters were calculated based on the three dimensional distribution pattern of segmented fibroglandular tissues, and their capacity to differentiate between the intermingled and the central patterns were evaluated using respective histograms and the receiver operating characteristic (ROC) analysis.
In medical imaging, the ROC analysis is commonly used for differentiating between malignant and benign tumors, with “sensitivity” as the ability to correctly diagnose malignant lesions and “specificity” as the ability to correctly diagnose benign lesions. In this specification, the ROC analysis is used to differentiate between two different breast parenchymal patterns shown on MRI, the central pattern (Type C) and the intermingled pattern (Type I), using the radiologist's reading as the ground truth; sensitivity referred to the ability to correctly diagnose Type I, and specificity referred to the ability to correctly diagnose Type C. In order to better understand the physical representation of the analyzed morphological parameters, cases with high and low index parameters were graphically depicted for visual comparison. The parameter that can differentiate between these two distinct patterns may then be used to provide a quantitative measure of parenchymal patterns, to facilitate the investigation of the relationship between parenchymal pattern and cancer risk.
Patient Database
In a review of our independent review board (IRB)-approved research breast MRI database from 2004 to 2006, 509 consecutive patients with either suspicious lesions or confirmed breast cancer were studied. Of these, 301 patients who had unilateral breast disease and for whom age and race information was available were included in this study. The radiology and pathology reports for each patient were reviewed to confirm that the disease was present in only one breast, and the breast density was only analyzed for the normal contralateral breast. Patients who had fatty breasts with the percent density <7% (N=71) as measured by MRI were classified as the fatty breast group. An example is shown in FIG. 1 a . Since this group could easily be classified based on percent density alone, they were not included in morphology analysis. The remaining 230 patients were used for the analysis of breast parenchymal pattern.
The MRI studies were acquired using a Philips Eclipse 1.5T scanner. The images were acquired using a nonfat sat T1-weighted three dimensional SPGR (RF-FAST) pulse sequence, with TR=8.1 ms, TE=4.0 ms, flip angle=20°, matrix size=256×256, and field of view varying between 32 and 38 cm. A fixed number of 32 slices, each 4 nm thick, were used to cover the whole breasts. All 32 imaging slices were analyzed.
Classification of Breast Parenchymal Pattern to Type I Vs Type C
The parenchymal pattern of each case was classified into one of two types that are commonly seen on breast MRI: Type I, the intermingled pattern with mixed fatty and fibroglandular tissues, and Type C, the central pattern with confined fibroglandular tissue inside surrounded by fat outside. The criteria used to differentiate between the two patterns were as follows: The central pattern was assigned when (1) most of the fibroglandular tissue was centrally located and peripherally surrounded by fatty tissue, (2) the interface between fatty and dense tissues could either be smooth or irregular, and (3) a small amount of scattered fatty tissues could be present within the fibroglandular tissue. If the criteria for the central pattern were not met, the case was assigned to the intermingled pattern group. For extreme cases of the intermingled pattern, the fibroglandular and fatty tissues could be intermixed throughout the entire breast.
The parenchymal patterns of all cases were visually inspected twice by an experienced radiologist and once by an experienced physicist using the same criteria. They were blind to each other's assignments. Between the first and second reading of the radiologist, there were eight discrepant cases among 230 cases (3.5%). There were six discrepant cases (2.6%) between the physicist's reading and radiologist's first reading, and 14 discrepant cases (6%) between physicist's reading and radiologist's second reading. All discrepant cases were reviewed by both observers together to reach a consensus agreement, and this consensus assignment was used as the ground truth. Finally, of the 230 cases, N=141 was classified as Type I, and N=89 was classified as Type C. FIG. 1 b shows a typical intermingled pattern (Type I), with mixed fibroglandular tissues and fatty tissues throughout the whole breast. FIG. 1 c illustrates a typical example of Type C, showing confined fibroglandular tissue inside surrounded by fatty tissue outside.
Quantitative Assessment of Breast Parenchymal Patterns
The whole breast and the fibroglandular tissues were segmented on each slice using a computerized method. An initial cut of the breast region based on each individual woman's body landmarks was performed, and then the boundary of the breast was determined using clustering-based segmentation with the b-spline curve fitting to exclude chest wall muscle, followed by dynamic searching to exclude skin. Then, within the segmented breast, the adaptive fuzzy c-means clustering algorithm was applied to segment the fibroglandular tissues.
Based on the segmentation results from all 32 slices, the total fibroglandular tissue volume and the percent density normalized to total breast volume were calculated. FIG. 2 a shows the bar plot of the age, fibroglandular tissue volume, and the percent density of the three subject groups for comparison, which consist of fatty (N=71), Type I (N=141), and Type C (N=89) breasts. It can be seen that the fatty breast group is significantly older, and this group can be well separated from the other two groups based on the lower dense tissue volume or the lower percent density. However, breasts from the Type I and Type C groups have comparable age, dense tissue volume, and percent density, and thus cannot be separated.
In order to characterize the different morphological distribution patterns between Type I and Type C, we analyzed four morphological parameters that are sensitive to shape, namely circularity and convexity, and margin which is related to the ratio between the surface area and the total volume, irregularity and compactness for the segmented fibroglandular tissues. Circularity is defined as
Circularity= V within /V fibro ,
where V within is the volume of fibroglandular tissue within the sphere of effective diameter D eff =2×(3·V fibro /4π) 1/3 , and V fibro is the total volume of fibroglandular tissue, as illustrated in FIG. 3 . The centroid of the fibroglandular tissues was first identified, and a sphere with diameter of D eff was drawn. The volume of the fibroglandular tissues within the sphere was measured, and the ratio to the total fibroglandular tissue was defined as the circularity. As shown in FIG. 3 , the case with the central pattern has the V within close to the V fibro and hence has a higher circularity compared to the case with the intermingled pattern. A perfect sphere will have the highest circularity index of one.
Convexity is defined as
Convexity= V fibro /V convex ,
where V convex is the volume of the minimum convex hull containing the border voxels of the fibroglandular tissue identified using the gift wrapping algorithm, as illustrated in FIG. 3 . The gift wrapping algorithm is performed as follows: Starting from the leftmost vertex, at each step the polygon formed by three consecutive vertices is inspected. If the resulting angle is concave, then the middle point is discarded and the next vertex (along the polygon) is added for testing. If the angle is convex, then the process is repeated by moving to the next vertex. As shown in FIG. 3 , the case with the central pattern has the convex volume closer to the fibroglandular tissue volume, and hence has a higher convexity index compared to the case with the intermingled pattern. A perfect sphere will have the highest convexity index of 1.
Irregularity is defined as
Irregularity=1 −πD eff 2 /S fibro ,
where S fibro is the surface area of fibroglandular tissue. The irregularity index compares the total surface area to the surface area of a sphere with effective diameter D eff . A perfect sphere will have the lowest irregularity index of zero.
Compactness is defined as
Compactness= S fibro 3/2 /V fibro .
The compactness is related to the ratio between the total surface area and the total volume. A sphere with smooth boundaries will have the lowest compactness index. A highly nonconvex pattern with rough boundaries will have a high compactness index.
Statistical Analysis
The distributions of each analyzed parameter in all patients were examined using the Kolmogorov-Smirnov test, and were transformed to normal distribution for statistical analysis. The parameters of age and circularity were already normally distributed, and did not need further transformation. The natural logarithm (ln) transformation was applied to fibroglandular tissue volume, while the square root (sqrt) transformation was applied to the parameters: percent density, convexity, irregularity, and compactness. Two-way analysis of variance was used to examine mean differences among the three parenchymal patterns of fatty, intermingled (Type I), and central (Type C) for age, (ln) fibroglandular tissue volume, and (sqrt) percent density. The ability of the four morphological parameters (circularity, convexity, irregularity, and compactness) to differentiate between the intermingled (Type I) and the central pattern (Type C) groups was first evaluated using a two-tailed t-test for the transformed parameters. For each morphological parameter, the values from all analyzed cases were ranked in order, and the distribution between the Type I and Type C patterns was plotted as histograms for comparison. Two cases with comparable densities, one with high index and one with low index (selected from the neighborhood of #35 and #195 ranking among all 230 cases), were graphically depicted as examples for visual inspection of their different parenchymal distribution patterns.
In addition to the individual analysis of each parameter, the linear regression model (enter method) using all four parameters together was applied to evaluate differences between the Type I and Type C patterns. The performance was evaluated using the ROC analysis with fourfold cross validation. All cases were first randomly assigned into four subcohorts, with each subcohort containing approximately the same proportion of Type C and Type cases. Three subcohorts were combined as the training set and the remaining subcohort was used as the validating set. For each training set, logistic model selection was applied to all four morphological features. The generated models were then applied to its corresponding validating set. Then, the determined diagnostic classifier could be used to predict a parenchymal pattern being Type I or Type C, based on the threshold level. The sensitivity was defined as the ability to correctly classify the intermingled pattern (Type I), while specificity was defined as the ability to correctly classify the central type (Type C). The sensitivity and specificity in the entire data set were calculated from a full range of thresholds (from 0.0-1.0 with an interval of 0.05), and then the ROC curve was constructed using all data points at different thresholds by plotting sensitivity verses one specificity. The area under the ROC curve (AUC) of all models were then listed in ascending order, and the one with the highest AUC was chosen. Finally, this model was applied to the entire cohort to obtain the final classification results. An analyses were performed using the SPSS 15.0 package (SPSS Inc., Chicago, Ill.).
Results—Age, Fibroglandular Tissue Volume, and Percent Density
As shown in FIGS. 2 a - 2 c , the fatty breast group could be easily separated from the Type I and Type C groups. They were significantly older in age (59±10 yr old), and had significantly lower fibroglandular tissue volume (48±31 cm 3 ) and lower percent density (5.2±4.4%). The mean age of patients was 50±11 yr old in the intermingled pattern (Type I) group and 50±11 yr old in the central pattern (Type C) group, so these two groups were well matched in age. The mean fibroglandular tissue volumes in these two groups were (Type I: 104±62 cm 3 vs Type C: 112±73 cm 3 ), and the percent densities were (Type I: 15.3±8.1% vs Type C: 16.7±10.1%). The density was slightly higher in the central pattern group, but the difference was not statistically significant.
Results—Morphological Parameters
The results of all density parameters calculated from the segmented fibroglandular tissues for Type I (intermingled) and Type C (central) cases are summarized in Table I. The four morphological parameters circularity, convexity, irregularity, and compactness all showed significant differences between the two patterns when comparing the transformed parameters (to the normal distribution) using the two-tailed t-test, suggesting that these features may be used to quantitatively characterize the parenchymal patterns. FIGS. 4 a - 4 d show the relative distribution histograms of these four morphological features between Type I (intermingled) and Type C (central) groups. Different distribution curves in these two patterns were clearly noted. In order to better understand the link between these quantitative parameters and the physical representation of fibroglandular tissue distributions, the indices from all 230 cases were sorted in ascending order, and the cases with comparable percent density but with high ranking (#180-210/230) vs low ranking (#20-50/230) indices were selected for visual comparison.
Morphological Feature—Circularity
Two examples are demonstrated in FIGS. 5 a and 5 b to illustrate the circularity index, which is defined to analyze the shape of the distribution relative to a sphere of effective diameter. The two cases have similar percent densities (9.6% vs 9.8%) but different parenchymal distribution patterns. FIG. 5( a ) shows a linearly structured fibroglandular pattern with a low circularity index=0.29 (ranking #33/230, Type I), and the FIG. 5( b ) case shows a round fibroglandular region with a high circularity index=0.58 (ranking #187/230, Type C). In all 230 cases, the circularity index was significantly lower for the intermingled pattern than for the central pattern (0.36±0.13 vs 0.50±0.12, p<0.001).
Morphological Feature—Convexity
The convexity index is defined to analyze the shape with respect to the minimum convex hull containing the border voxels. Two examples are demonstrated in FIGS. 6 a and 6 b . In FIG. 6 a the specimen with a low convexity index=0.20 (ranking #30/230, Type I), has a lower occupancy within the corresponding convex hulled area, while in FIG. 6 b the specimen with a high convexity index=0.46 (ranking #180/230, Type C), has a higher occupancy. These two specimens have comparable percent densities (10.9% vs 11.6%). In all 230 cases, the convexity index was significantly lower for the intermingled pattern than for the central pattern (0.27(0.08 vs 0.38(0.10, p) 0.001).
Morphological Feature—Irregularity
The irregularity index is defined to compare the total surface area to the surface area of a sphere with effective diameter D eff . Two examples with high and low irregularity indices are shown in FIGS. 7 a and 7 b . They have similar percent densities (15.1% vs 15.6%) but different parenchymal distribution patterns. The case with a high irregularity index=0.74 (ranking #190/230) has an intermingled pattern showing an irregular border, and the case with a low irregularity index=0.54 (ranking #26/230) has a central pattern with a smooth border. In all 230 cases, the irregularity index was significantly higher for the intermingled pattern compared to the central pattern (0.69±0.07 vs 0.61±0.09, p<0.001).
Morphological Feature—Compactness
The compactness index is defined to compare the ratio between the total surface area and the total volume. Two cases with comparable percent densities (Type I: 12.9% vs Type C: 11.8%) are shown in FIGS. 8 a - 8 b . The case with a high compactness index=17.5 (ranking #180/230) has an intermingled pattern, and the case with a low index=6.7 (ranking #32/230) has a central pattern. In all 230 cases, the compactness index was higher for the intermingled pattern than for the central pattern (14.2±5.2 vs 8.6±4.5, p<0.001). Among all four analyzed morphological parameters, the compactness index was the best parameter to differentiate between these two parenchymal patterns, and showed the widest separation between the histogram curves of these two groups, as shown in FIG. 4( d ).
Group Differentiation Using Roc Analysis
The power of these four morphological parameters in differentiating between the Type I and Type C patterns was analyzed individually using ROC analysis. As suggested by the histogram analysis shown in FIGS. 4 a - 4 d , the compactness index was the best single predictor among all four parameters, which attained the highest AUC of 0.84. These four parameters have distinctly different definitions, and in theory, they are sensitive to different aspects of the distribution. However, in reality, they are all related to shape and margin, and are highly correlated. When all four morphological parameters were combined together using the equation shown below, the AUC could be further increased to 0.94
0.3+0.8×Circularity+0.7×Convexity 1/2 −0.2×Irregularity 1/2 −0.1×Compactness 1/2 .
A threshold value can be set to classify cases as either Type I or Type C, for example, a value less than 0.5 could represent Type I, while a value greater than 0.5 could represent Type C. The ROC curves can be generated using different threshold values, shown in FIG. 9 . The results demonstrate that adding the other three parameters to the compactness index can further improve the AUC; therefore, they have a complementary role.
In this specification we disclosed an method of using quantitative morphological features to characterize the three dimensional distribution patterns of fibroglandular tissue. As an initial approach for validating the value of these quantitative morphological parameters, showed whether these parameters could differentiate between two distinct patterns (intermingled and central pattern) that could be easily separated visually. After excluding the 71 fatty breast cases with percent density <7%, there were a total of 230 remaining cases. The ground truth to separate them into Type I and Type C was carefully established. The densities (percentage and volume) in these two groups were similar, and the ages of the patients in these two groups were also well matched. All four analyzed morphological features showed significant differences between these two patterns, and when combined they could achieve an AUC of 0.94 in the ROC analysis. The intermingled pattern had significantly higher compactness and irregularity and lower circularity and convexity indices compared to those of the central pattern. The results strongly suggest that it is feasible to characterize different distribution patterns of fibroglandular tissues using quantitative morphological measures.
We further disclosed the association of the extracted quantitative features with the visual MRI representation of fibroglandular tissue distribution. Examples from cases with high vs low index are demonstrated graphically in FIGS. 5-8 . The circularity and convexity indices were related to shape, while irregularity index was more sensitive to margin. The compactness index reflected the ratio between the surface area and the volume, and was associated with both shape and margin. Possibly due to its sensitivity to both shape and margin, the compactness had the greatest ability to differentiate between the intermingled and the central patterns. These results demonstrated that it is feasible to use quantitative parameters to describe the three dimensional density distribution on breast MRI.
Texture parameters are coma commonly used to analyze the density distribution on mammography. The analyzed texture information represents the amount and/or the heterogeneity/homogeneity of dense tissue distribution on mammograms. Because the texture parameters are analyzed on the projection image, one main contributing factor comes from the overlapping pattern of the dense and fatty tissues. For example, skewness can distinguish fatty tissues (positive value) from dense tissues (negative value). The prior art has introduced another two texture features, coarseness and contrast, to describe the spatial relationship between fatty and dense tissues. There was evidence suggesting that the distribution of fibroglandular tissue is associated with cancer risk. Prior art practitioners have used texture features to compare between the high-risk BRCA1/BRCA2 mutation carriers and low-risk women, and found that the BRCA1/BRCA2 mutation carriers tend to have more heterogeneously dense tissues (high coarseness and low contrast). Very recently, a systematic study has been published to assess breast tissue texture using Markovian cooccurrence matrices, run-length analysis, Laws features, wavelet decomposition, and Fourier analysis. Following a comprehensive evaluation of a large community-based screening population of approximately 750 women, they have reported that the analyzed texture features predicted breast cancer risk at the same magnitude as did the percent breast density. The texture features at low spatial frequencies (i.e., coarser mammographic textures) were found to be the strongest predictors of breast cancer risk. However, we also note that numerical values of texture features tend to vary with differences in acquisition variables such as compression force, angle, kVp, etc.
We would like to point out that the density analyzed based on mammogram cannot be generalized to predict the results analyzed from MRI. The density measurements by MRI and mammography have been shown highly correlated. However, all these studies also consistently showed that the mammographic density was higher than the density measured on MRI, which was attributed to two-dimensional vs three-dimensional image acquisitions. Mammography only acquires one projection image, and is not sufficient for analyzing the relative spatial distribution of dense and fatty tissues. On the other hand, MRI provides detailed three dimensional distribution patterns of fibroglandular tissue, hence not subject to the issue of tissue overlapping. Therefore, although both modalities show contrast between dense and fatty tissues, the texture results analyzed from mammography cannot be directly compared to the parenchymal patterns analyzed from dense tissue morphology on MRI. In fact, we have also performed texture analysis using gray level co-occurrence matrix and Laws texture features on MR images, but found them inferior to the morphology analysis reported here to differentiate between Type I and Type C. In texture analysis, the entire image is analyzed, and a major part of the measured texture parameters is derived from the amount of fatty issue contained within the image, which is not of our interest. The morphology analysis approach used in the illustrated embodiment is based on segmented fibroglandular tissue, and this provides much more specific information when compared to blind texture analysis.
It has been reported that the distribution of the mammary gland is associated with the development breast cancer. For example, the BRCA1 and BRCA2 genes promote lobular branching, and the resulting denser and more heterogeneous breast parenchyma leads to increased cancer risk. The risk for breast cancer associated with mammographic density may be explained by the combined effects of mitogens (which influence cell proliferation and the size of the cell population in the breast) and mutagens (which influence the likelihood of genetic damage to those cells). Fatty tissue has been demonstrated to have the ability to generate products to augment the growth of mammary carcinoma cells. Having more surface interaction between the fibroglandular and fatty tissue may be related to increased breast cancer risk by releasing lipid-soluble carcinogens into the intimate fibroglandular tissue. It is reasonable to expect that the intermingled pattern shown on MRI is more likely to show a heterogeneous pattern on two dimensional mammograms. Similar as the concept of using texture analysis on mammogram to correlate with risk, the MRI-based analysis technique that we reported in this specification has the potential to facilitate the investigation of the relationship between breast parenchymal pattern and cancer risk. We have provided strong evidence to demonstrate that the four analyzed parameters can differentiate between the central pattern and the intermingled pattern. No other group has ever reported on the analysis of breast density morphology based on MRI.
There are several cautions to be noted in this study. First, the data sets were from a research MRI database, therefore, at is not representing a general population. However, our purpose is to develop quantitative measures to distinguish between these two patterns (Type I and Type C), and as long as we have a good case number for each group, the data set can be used to test how well the quantitative parameters analyzed in this study can differentiate between these two groups.
Second, we did not analyze the fatty breast cases. As shown in FIGS. 1 a - 1 c , since the contrast between fibroglandular and fatty tissues is not strong, the segmentation of the fibroglandular tissue may not be reliable for performing further morphology analysis. On the other hand, the fatty breasts can be easily classified based on the percent density alone, so further morphology analysis may not be needed.
Third, the ground truth was established using visual inspection, which is subject to variations of observers. To minimize this observer bias, we had a total of three reading sessions by two observers (a radiologist and a physicist), and any case that had discrepant assignments among three readings was discussed to reach a consensus.
Fourth, the best classifier combining all four morphological parameters was obtained using fourfold cross validation within the same data set, not from independent training and validation data sets. To reduce variability, multiple rounds of cross-validation were performed using different partitions, and the validation results were averaged over the rounds. If an independent data set is available, we can further test the ability of each individual parameter and the combined classifier shown in Eq. (1) to differentiate between Type I and Type C patterns.
In summary, the illustrated embodiment demonstrates that the four morphological parameters (circularity, convexity, irregularity, and compactness) can be used to characterize dense tissue distribution patterns based on MRI, and they can be used to investigate the relationship between parenchymal pattern and the cancer risk. For example, between two women who have similar percent density, but have differing parenchymal patterns (e.g., central type vs mixed type), who will have a higher risk of developing cancer? Our method to characterize the morphology of the fibroglandular tissues provides an essential foundation for such research in the future. Breast density is a well-established risk factor, and a consensus has been reached by the Breast Cancer Prevention Collaborative Group to incorporate quantitative breast density into risk models. The change in breast density has also been shown to be a good surrogate marker for predicting the efficacy of chemoprevention drugs. In the future when the role of the morphological breast density features is established, they may also be incorporated into the risk models to further improve the accuracy in predicting each individual woman's cancer risk, for making a decision about the optimal management plan.
Many alterations and modifications may be made by those having ordinary skill in the art without departing from the spirit and scope of the invention. Therefore, it must be understood that the illustrated embodiment has been set forth only for the purposes of example and that it should not be taken as limiting the invention as defined by the following invention and its various embodiments.
Therefore, it must be understood that the illustrated embodiment has been set forth only for the purposes of example and that it should not be taken as limiting the invention as defined by the following claims. For example, notwithstanding the fact that the elements of a claim are set forth below in a certain combination, it must be expressly understood that the invention includes other combinations of fewer, more or different elements, which are disclosed in above even when not initially claimed in such combinations. A teaching that two elements are combined in a claimed combination is further to be understood as also allowing for a claimed combination in which the two elements are not combined with each other, but may be used alone or combined in other combinations. The excision of any disclosed element of the invention is explicitly contemplated as within the scope of the invention.
The words used in this specification to describe the invention and its various embodiments are to be understood not only in the sense of their commonly defined meanings, but to include by special definition in this specification structure, material or acts beyond the scope of the commonly defined meanings. Thus if an element can be understood in the context of this specification as including more than one meaning, then its use in a claim must be understood as being generic to all possible meanings supported by the specification and by the word itself.
The definitions of the words or elements of the following claims are, therefore, defined in this specification to include not only the combination of elements which are literally set forth, but all equivalent structure, material or acts for performing substantially the same function in substantially the same way to obtain substantially the same result. In this sense it is therefore contemplated that an equivalent substitution of two or more elements may be made for any one of the elements in the claims below or that a single element may be substituted for two or more elements in a claim. Although elements may be described above as acting in certain combinations and even initially claimed as such, it is to be expressly understood that one or more elements from a claimed combination can in some cases be excised from the combination and that the claimed combination may be directed to a subcombination or variation of a subcombination.
Insubstantial changes from the claimed subject matter as viewed by a person with ordinary skill in the art, now known or later devised, are expressly contemplated as being equivalently within the scope of the claims. Therefore, obvious substitutions now or later known to one with ordinary skill in the art are defined to be within the scope of the defined elements.
The claims are thus to be understood to include what is specifically illustrated and described above, what is conceptionally equivalent, what can be obviously substituted and also what essentially incorporates the essential idea of the invention. | A method and apparatus configured to analyze breast density based on magnetic resonance imaging (MRI) of a breast of a patient includes the steps of segmenting an MR image of the breast from one set of three-dimensional breast MRI images, and analyzing the amount of dense tissue and the morphological distribution of the dense tissue and a data processor configured by software to perform these steps. Analyzing the amount of dense tissue and the morphological distribution of the dense tissue includes the steps of segmenting tissue data to separate breast tissue from other body tissue, separating tissue data of the dense and fatty tissues in the breast, and analyzing the morphological distribution of dense tissue in the breast to derive one or more three dimensional morphological parameters of the dense tissue distribution. | 6 |
FIELD OF THE INVENTION
The present invention relates to digital filters and, in particular, to a FIR (finite impulse response) digital filter for achieving a transfer function equivalent to one obtained by cascade-connecting one or more moving average filters.
BACKGROUND OF THE INVENTION
In general, a FIR digital filter, as shown in FIG. 1, has a non-recursive configuration comprising k one-clock delay elements D1-Dk, k+1 multipliers M1-M(k+1) for multiplication of the respective tap coefficients b 0 -b k+1 , and an adder A1 for adding these products. The transfer function H(z) of this FIR filter is given by the following equation. ##EQU1##
In order to realize the configuration by means of hardware, a product-sum operation circuit as shown in FIG. 2 has been generally employed. In FIG. 2, the respective tap coefficients stored in a ROM (Read Only Memory) 1 and the input X are sequentially multiplied together by a multiplier 2 in accordance with the clock timing. The respective results are sequentially entered to an accumulative adder 5 comprising an adder 3 and an accumulator 4, which plays parts of the delay elements D1 to Dk and the adder A1 of FIG. 1. Thus, the transfer function as shown in equation (1) can be realized.
The filter output Y is output at each time when the accumulative adder 5 has operated (k+1) times. In other words, the output Y of the FIR filter is caused by 1/(k+1) decimation of the output of the accumulator 4. However, since this decimation frequency is two or more times as great as a frequency of the passband of this filter, there is no problem occurring in the resulting filter output.
The moving average filter is obtained by setting all the tap coefficients b 0 -b k+1 of the FIR filter shown in FIG. 1 to 1. In consequence, from the equation (1), the transfer function of the moving average filter can be given by the following equation. ##EQU2## As seen from this equation (2), the moving average filter is a nonpolar or all-zero lowpass filter in which k zero points are assigned at equal intervals on a unit circle of the z-plane with a zero point and a pole canceling out at z=1. Such a moving average filter can be realized in the circuit of FIG. 2 by setting all the tap coefficients of the ROM 1 to 1 or by only the accumulative adder 5.
The FIR filter in which two or more moving average filters are cascade-connected has the tap coefficients each being a positive integer. In consequence, the function of the multiplier in the product-sum operation circuit can be realized by the adder so that the amount of hardware is reduced.
In particular, in the FIR filter where two moving average filters are cascade-connected, its tap coefficients can be represented by a monotone increasing or decreasing function. Assuming that the two moving average filters cascade-connected have (k+1) and (l+1) tap coefficients, respectively, its transfer function can be given by the following equation. ##EQU3## As shown by this equation, the tap coefficients sequentially increase one by one up to the (l+1)th tap, become a constant value (l+1) from the (l+1)th tap up to the (k+1)th tap, and sequentially decrement one by one from the (k+1)th tap to the last tap. Therefore, in the FIR filter which realizes such a transfer function by means of hardware, it becomes possible to produce the tap coefficients by using an up/down counter in place of the ROM 1 to thereby further reduce the hardware amount.
However, in the conventional arrangement as shown in FIG. 2, if three or more moving average filters are cascade-connected to form a FIR filter, the monotoneity of the tap coefficients described above disappears. As a result, a ROM for storing the tap coefficients becomes necessary, therefore it is difficult to drastically reduce the hardware amount.
SUMMARY OF THE INVENTION
A digital filter is comprised of one or more pairs of an integrator and a differentiator which are cascade-connected, thus realizing a transfer function equivalent to one resulting from cascade-connecting at least one moving average filter.
The integrator is comprised of a first delay element and a first adder. The first adder has 2's complement operating function to change its polarity on overflow.
The differentiator is comprised of a second delay element and a second adder, the second adder having bits of the same number as the first adder and having 2's complement operating function to change its polarity on overflow, that is, the same function as that of the first adder.
A pair of the integrator and the differentiator described above permits the multiple cascade connection with the drastically reduced amount of hardware. A plurality of pairs of them which are merely cascade-connected can realize the transfer function obtained by cascade-connecting the plurality of moving average filters.
If the transfer function to be realized is equivalent to a power of the transfer function of a single moving average filter, then it becomes possible to further reduce the amount of hardware.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
FIG. 1 is a basic block diagram for explaining a FIR digital filter;
FIG. 2 is a block diagram illustrating a specific embodiment of a conventional digital filter;
FIG. 3 is a block diagram illustrating a first embodiment of the digital filter according to the present invention;
FIG. 4 is an explanatory graph of the operation of an adder in the present invention;
FIG. 5 is a timing chart illustrating the operation of the present invention;
FIG. 6 is a block diagram of a second embodiment of the digital filter according to the present invention; and
FIG. 7 is a graphic view of the frequency characteristic of the second embodiment.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 3, a first embodiment of the digital filter according to the present invention has an arrangement in which a digital integrator INT1 and a digital differentiator DIF1 are cascade-connected providing the transfer function equivalent to that of a moving average filter.
The integrator INT1 is comprised of an adder 101 and a 1-clock pulse delay element 102. The adder 101 receives the filter input signal X and the output signal from a delay element 102, and outputs the signal Y 1 which is the input of the delay element 102 as well as the output signal of the integrator INT1. The adder 101, as will be described later, has a 2's complement operating function to invert its polarity on overflow. The binary representation existing in the adder 101 is seen to be comprised of a sign digit and the 2's complement.
The differentiator DIF1 is comprised of an adder 103 and a (k+1)-clock pulse delay element 104. The adder 103 has the same number of bits and the same function as those of the adder 101. The output signal Y 1 from the integrator INT1 is input to the adder 103 and the delay element 104. The output signal Y 2 from the delay element 104 is input to the adder 103 as -Y 2 , which outputs the filter output signal Y.
Since the transfer function of the integrator INT1 is defined by 1/(1-Z -1 ) and the transfer function of the differentiator DIF1 1-Z - (k+1), it is apparent by referring to the equation (2) that this cascade connection of the integrator INT1 and the differentiator DIF1 realizes a moving average filter.
In the arrangement in which the integrator INT1 and the differentiator DIF1 are cascade-connected, it is important that the adders 101 and 103 have the 2's complement operating function to change the polarity on overflow. Since the output of an integrator diverges in response to its DC input, it is indispensable to eliminate this effect. As that solution, in this embodiment, the adder 101 of the integrator INT1 and the adder 103 of the differentiator DIF1 have the 2's complement operating function to invert the polarity on overflow to achieve the normal filter output Y.
The inverting operation of the polarity of the adders 101 and 103 is carried out as shown in FIG. 4. In FIG. 4, the horizontal axis represents the values resulting from adding two values X 1 and X 2 entered to the adder while the vertical axis represents the output values of that adder. For example, when N=3, if the value X 1 +X 2 is the binary representation `0111`, then the output of the adder represents the numerical value +6, while if the value X 1 +X 2 overflows with the binary representation `1000`, the numerical value represented by the output of the adder is turned into -7 because the polarity of the adder is inverted.
Referring to the timing chart of FIG. 5, the operation of the FIR filter according to this embodiment is hereinafter described. By way of example, the filter input X is set to a step signal like a step function. When the input X rises, the output signal Y 1 of the integrator INT1 also starts to rise:, and is input to the adder 103 and the delay element 104 of the differentiator DIF1. The signal Y 2 starts to rise, as in the signal Y 1 , delay time (k+1)T by the delay element 104 after the signal Y 1 starts to rise, where T denotes the clock period. Since the adder 101 or 103 is inverted in its polarity on overflow, as described above, the signals Y 1 and Y 2 generate the trajectories as indicated in FIG. 5. In consequence, the adder 103 which receives the signals Y 1 and -Y 2 emits the filter output signal Y as shown in FIG. 5. Even if the output Y 1 of the integrator INT1 diverges in response to the step input X, the filter output Y from the differentiator DIF remains in a normal state.
Referring to FIG. 6, another embodiment of the present invention has an arrangement in which integrators INT1 and INT2 and differentiators DIF1 and DIF2 are cascade-connected. The integrator INT1 and the differentiator DIF1 have the same arrangements as those of FIG. 3, respectively. The integrator INT2 is comprised of an adder 201 and a 1-clock pulse delay element 202, the adder 201 having a 2's complement operating function to change its polarity on overflow, as in the integrator INT1. The differentiator DIF2 is comprised of an adder 203 and a (l+1)-clock pulse delay element 204, the adder 203 having a 2's complement operating function to invert its polarity on overflow.
Such a digital filter is equivalent to the filter in which two moving average filters are cascade-connected: one with (k+1) taps and the other with (l+1) taps, and its transfer function is given by the following equation. ##EQU4##
In the digital filter illustrated in FIG. 6, its frequency characteristic with k=15, l=62, and the DC gain 0 dB is shown in FIG. 7.
As described above, only by additionally connecting a pair of the integrator and the differentiator to the filter as shown in FIG. 3, a digital filter equivalent to the filter in which two moving average filters are cascade-connected can readily be realized. Similarly, a digital filter where three or more moving average filters are cascade-connected can be readily realized by only cascade-connecting three or more pairs of integrators and differentiators. This can eliminate the ROM which has been necessary to store the tap coefficients.
Further, if the transfer function H(z) to be realized, as the following equation (5), is given by a power of the transfer function of a moving average filter, it becomes possible to drastically reduce the hardware amount because the delay element of the integrator can be operated in accordance with the frequency-divided clock of 1/(k+1) the master clock frequency. ##EQU5##
As described above, the digital filter according to the present invention is comprised of at least one pair of the integrator and the differentiator each having the same adder with a two's complement operating function to invert its polarity on overflow. As a result, it becomes possible to readily realize the transfer function equivalent to one resulting from cascade-connecting one or more moving average filters with a small scale hardware amount. | A cascade digital filer has a plurality of cascade-connecting pairs of integrators and differentiators to realize a transfer function obtained by cascade-connecting a plurality of moving average filters. Each of the integrators includes an adder which has a two's complement operating function which inverts its polarity on overflow. Each of the differentiators also includes an adder which has the same number of bits and the same function as does the adder of integrator. The adder in each of the integrators and differentiators prevents the output of the digital filter from diverging, thus resulting in normal filtered output. | 7 |
CROSS-REFERENCE TO RELATED APPLICATION
This application is a Divisional of U.S. patent application Ser. No. 10/967,613 filed Oct. 18, 2004 now U.S. Pat. No. 7,017,519 and entitled “Self-Cleaning Pet Litter Apparatus and Related Method.”
TECHNICAL FIELD
The present invention pertains to litter boxes for use by animals, typically cats. More particularly, this invention is directed toward apparatus which operates in a self-cleaning fashion, either automatically or manually, to remove waste materials deposited in the litter, thereby obviating the need for frequent and periodic service by the animal's owner.
BACKGROUND OF THE INVENTION
Domestic pets, particularly cats, typically utilize a litter box for their waste needs. Such litter boxes fall into two categories, the totally manual pan or container which carries a quantity of litter and the automatic or self-cleaning variety, which also carries a quantity of litter. The present invention pertains to the latter category and the patent literature does include a variety of such devices. U.S. Pat. No. 6,568,348, for instance, is directed to a circular litter device that extracts waste from litter material by rotating a rake or the chamber. Due to rotation of the rake or chamber, solid waste is extracted from the litter material using tines, and such waste is pushed to the outer perimeter of the chamber. The curvature of the rake allows the rake to cooperate with a scoop, which simultaneously removes solid waste from the rake and retracts into a tunnel, as the rake passes thereby.
U.S. Pat. Nos. 6,401,661 and 6,234,112 are both directed to a self cleaning pet litter box. The pet litter container is rotatably mounted on a base member, and rotates to move the pet litter over a sieve. The sieve is ramped shaped and therefore, clumped portions of the pet litter that are not sifted through its openings are forced upwardly toward a conveyer. The conveyer serves to carry the clumped portions of pet litter away from the pet litter container.
U.S. Pat. No. 6,286,459 is directed to a litter container with a rotary movement sieve. The sieve is attached to a rotatable ring around the upper portion of a container. As the sieve rotates, clumped portions of solid waste are captured thereon. Since the sieve is removable, the sieve, and the clumped portions of solid waste can be removed from the container.
U.S. Pat. Nos. 6,082,302 and 5,447,812, are both directed to a rectangular litter device that extracts waste from litter material using a comb that traverses the pan lengthwise, eventually conveying waste clumps into a receptacle at the front of the device.
U.S. Pat. No. 4,574,735 is directed to a circular litter device that extracts waste from litter material using a rake which sweeps through a circular chamber. In this device, the waste material is deposited into a container which is rotated to sanitize and deodorize the contents.
The foregoing automatic litter devices have provided a variety of styles and mechanisms to facilitate periodic cleaning of the litter. Nonetheless, the apparatus of the present invention provides a novel approach to the design and operation of such devices by providing a single drive mechanism for the operation of all moving elements as well as other features not present in combination in a single device heretofore.
SUMMARY OF THE INVENTION
In accordance with the present invention, a self-cleaning litter apparatus that separates and extracts clumped litter waste material from litter material contained therein during use is provided. The litter apparatus includes a chamber adapted to contain a quantity of litter material. The chamber is rotatable about a centrally disposed axis. A rake is disposed within the chamber. The rake includes a plurality of tines for receiving clumped litter waste material from the litter material and for extracting the clumped litter waste material from the chamber. The rake is rotatable about an axis which is spaced apart from the chamber axis. A drive assembly is provided for simultaneously rotating the chamber about the chamber axis and for rotating the rake about the rake axis. The rake sweeps through the litter material while clumped litter waste material is directed toward the rake by rotation of the chamber to thereby separate clumped litter waste material from the litter material in the chamber, collect the separated clumped litter material in the rake and extract the separated clumped litter material from the chamber.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an isometric view depicting the self-cleaning litter apparatus of the present invention;
FIG. 2 is an exploded isometric view of the self-cleaning litter apparatus of the present invention;
FIG. 3 is an isometric view depicting the underside of the self-cleaning litter apparatus of the present invention;
FIG. 4 is an isometric view depicting the underside of the litter pan;
FIG. 5 is a partial isometric view depicting the turntable of the self-cleaning litter apparatus;
FIG. 6 is an isometric view depicting the underside of the turntable;
FIG. 7 is a partial isometric view depicting the base of the self-cleaning litter apparatus and related components for driving the turntable;
FIG. 8 is a side elevation of a weight sensor, depicted over the contact rails carried in the base;
FIG. 9 is an isometric view of a weight sensor, depicted over the contact rails carried in the base;
FIG. 10 is another isometric view depicting the underside of the turntable and the drive mechanism, with portions of the apparatus removed for clarity;
FIG. 11 is a cross-sectional view of the apparatus, depicting the base, turntable, litter pan and rake assembly;
FIG. 11A is an enlarged cross-section of the area 11 A, depicted in FIG. 11 ;
FIG. 11B is an enlarged cross-section of the area 11 B, depicted in FIG. 11 ;
FIG. 11C is an enlarged cross-section of the area 11 C, depicted in FIG. 11 ;
FIGS. 12–16 are isometric views of the litter apparatus of the present invention, depicting the rake sequentially moving from rest, through the litter pan, out of the litter pan and depositing waste litter material into the receptacle;
FIG. 17 is a partial isometric view, depicting the rake assembly;
FIG. 18 is a partial isometric view, looking from the front of the apparatus, depicting the rake assembly in relation to the cam member for rotation of the rake;
FIG. 19 is a partial isometric view, looking down and from the rear side of the apparatus, depicting the rake assembly in relation to the cam members for rotation of the rake and lifting the cover on the receptacle;
FIG. 20 is a partial isometric view, similar to FIG. 18 , with components removed to reveal the drive mechanism and the rake assembly;
FIG. 21 is a side elevation of the rake assembly, separately from the apparatus and the drive mechanism positioned beneath the base;
FIG. 22 is a partial isometric view, looking down and from the rear side of the apparatus, depicting the rake assembly and the rake at rest;
FIG. 23 is a partial isometric view, looking down and from the rear side of the apparatus, depicting the rake assembly and the rake at rest;
FIG. 24 is a partial isometric view, looking from the rear side of the apparatus, depicting the rake assembly and rake at rest with the receptacle cover closed;
FIG. 25 is a partial isometric view, similar to FIG. 24 , with the receptacle cover opening for receipt of litter waste;
FIG. 26 is a block diagram of the control and sensors for the litter apparatus; and
FIG. 27 is a block diagram of the weight sensing mechanism.
DETAILED DESCRIPTION OF THE INVENTION
With reference to FIGS. 1 and 2 , a self-cleaning litter apparatus according to the present invention, is depicted generally by the numeral 30 . It includes a main base, generally 31 , which carries a turntable, generally 32 , a litter pan, generally 33 , received onto the turntable, a shield 34 , a hood 35 , a rake assembly, indicated generally by the numeral 36 , a waste receptacle 37 , a housing 38 for the drive mechanism, which will be described subsequently and a ramp 39 , which may optionally provide a mat 40 , for the purpose of cleaning litter from the pet upon exiting the apparatus. Of these components, the hood 35 and the ramp 39 are both optional, as the self-cleaning features of the apparatus do not require the presence of either component. In order to aid in manufacturing, while providing strength and reasonable cost, the various components are manufactured from a conventional thermoplastic, such as ABS or a polyolefin, such as polyethylene or polypropylene. Other components, such as the internal gears can be manufactured from nylon.
The hood 35 provides a domed top 41 which terminates in an outwardly extending annular flange 42 . A recess 43 is provided in the top 41 for receipt of an air filter element 44 , which is removable from the underside of the hood. A handle 45 , is molded into the top over the recess. The front of the hood 35 provides an opening 46 , through which the cat, or other domestic pet, enters and leaves the litter apparatus.
The shield 34 is removable, lifting off of the litter pan 33 , when the latter is to be cleaned. It comprises a truncated annular flange, the outer wall 47 of which frictionally engages the inner wall 48 of the hood 35 . The outer wall 47 is recessed, to provide an opening 49 , extending across less than one-half of the front of shield 35 , to allow for movement of the rake assembly 36 , as will be described later.
The litter pan 33 includes a body 50 having a circular base 51 , a continuous upwardly extending sidewall 52 , terminating in an outwardly extending annular flange 53 . In FIG. 7 , the bottom of pan of 33 is depicted, showing the underside 54 of base 51 . Underside 54 provides a several projections at various positions. A coupling, generally 55 , is centrally located and includes a ring 56 encompassing a recess 58 , for receipt of a hub-spindle assembly, generally 59 , carried centrally of the turntable 32 . Radiating outwardly from the ring 56 are a plurality of fins 60 , which mate with the spindle, as will be described in greater detail below, so that as the turntable 32 is rotated, the litter pan 33 is likewise rotated.
Radially outwardly of the coupling 55 are a plurality of feet 61 , which are received in foot wells 62 , provided in the floor 63 of the turntable 32 ( FIG. 5 ). Radially outwardly of the feet 61 are a plurality of buttons 65 , which engage weight sensors, generally 66 , which are carried by the turntable 32 .
The turntable 32 is depicted in FIGS. 5 , 6 , and 10 to which reference should be made next. Beginning with FIGS. 5 and 6 , the turntable is generally dish shaped and has a raised central floor 63 which extends over a major portion of the diameter. It terminates with downward sidewall, which forms the inner wall 70 of an annular trough 71 , beneath the floor. The trough continues to an outer wall 72 , which extends upwardly to join an outer rim 73 , slightly lower than the floor 63 . An outer ring wall 74 extends upwardly from the rim 73 , terminating in an upper face 75 and upstanding peripheral rim 76 . On the outside of outer ring wall 74 , a ring gear 78 is formed, which allows the turntable to be rotated.
In FIG. 6 , the turntable is viewed from its underside, where it can be seen that the trough 71 has a plurality of discontinuities, each extending partially upwardly within the trough providing platforms 80 , each carrying a weight sensor 66 . As depicted in the drawing, six such platforms 80 are shown, although the turntable could be modified to provide more or less than six so long as a sufficient number are present to sense the weight of an animal in the litter pan, which will be explained hereinbelow. Returning to FIG. 5 and the upper side of turntable 32 , the foot wells 62 in central floor 63 are coplanar with the trough 71 and are bounded by leading and trailing ramps, 81 , 82 , which help orient the placement of the litter pan 33 and engagement of the feet 61 in the wells 62 .
At the center of the turntable, is the hub-spindle assembly 59 , comprising a hub 85 and a spindle 86 . The hub 85 is a small diameter cup which extends from and below the turntable floor 63 and terminates in a raised shelf 88 , also beneath the plane of the floor 63 . The spindle 86 , depicted in FIG. 11B , provides two intersecting semi-elliptical members 89 which terminate in a rounded end upon which the recess 58 in the coupling member 55 of litter pan 33 rests, so as to be tiltably rotatable thereon. The members 89 are carried by a platform 90 and extending downwardly therefrom are four fingers 91 disposed at 90° angles from each other. The spindle fingers 91 are snapped into an open base hub 92 , formed in the floor 93 of main base 31 (see FIG. 3 ).
The fingers 91 have outwardly extending flanges 94 , which lock against the bottom edge 95 of base hub 92 . As also shown in FIG. 11B , a screw 96 , carrying a spacer 98 is driven into the central body 99 of spindle 86 , which urges the fingers 91 into engagement with the base hub 92 . In this manner the turntable 32 is fastened to the base and can likewise be disassembled by first removing the screw 96 . To aid rotation of the turntable 32 over the base hub 92 of the base 31 , a washer 100 is interposed.
The floor 93 of main base 31 is partially depicted in FIG. 7 and in cross-section in FIG. 11 , to which reference should be made next. Generally, the floor 93 is molded to allow for the turntable 32 to rotate freely therein, the latter having been mounted therein as previously described. In addition, the base also provides two other mechanisms—one to assist rotation of the turntable and one that works as part of the weight sensing mechanism, which will be described subsequently. The base has an exterior wall 103 , for appearance and enclosing the drive mechanism.
As clearly depicted in FIGS. 7 and 11A , the floor 93 of main base 31 carries an annular trough 104 , near its periphery. Radially outwardly from the trough 104 is a raised shelf 105 , which extends to the inner wall 106 of base 31 . A plurality of wheels 108 are fit into recesses 109 in shelf 105 , each said wheel being rotatably mounted about an axle 110 , pressed into a mating well 111 carried in the underside of shelf 105 . The wheels 108 protrude outwardly from the shelf 105 , as depicted in FIG. 7 , where they will periodically engage the outer edge 112 of annular trough 71 (see the underside of turntable 32 ) to keep it centered and supported about the spindle 86 . The number of wheels is not crucial to the operation of the apparatus, so long as they are equally spaced about the circumference. Typically, four wheels are adequate.
A like plurality of rollers 113 are carried in semi-cylindrical recesses 114 , in the shelf 105 . The rollers reduce friction between the turntable 32 and main base 31 as the turntable is rotated therein. The combined support and centering can be seen schematically in FIG. 10 , where the main base has been removed from view, leaving the rollers 113 and wheels 108 in place against the underside of turntable 32 . Again, the number of rollers 113 is not crucial to the operation of the apparatus, so long as they are equally spaced about the circumference. Typically, eight rollers are adequate. Together, the rollers and wheels provide a supporting and centering mechanism, indicated generally by the numeral 115 , for the turntable 32 .
The weight sensing mechanism is indicated generally by the numeral 120 and it includes the weight sensors 66 and a track assembly, generally 121 . Referring to FIG. 7 , the track assembly comprises a pair of electrically conductive outer and inner rails 122 , 123 , respectively. The rails are mounted in the annular trough 104 , which is formed into a raised shelf 125 , and extends upwardly from the floor 93 of the base 31 . Spacers 126 , made from plastic or other non-conductive material, are located periodically around the shelf 125 in a number sufficient to maintain the rails parallel to each other. The spacers are suitably fastened within the trough 104 by screws, not shown, passing though apertures 128 and their width forces the opposed rails against the walls of the trough so as to remain immovable therein. An end of the outer rail 122 is bent and passes through an aperture 130 in the base to the underside and is connected electrically to a power source (not shown). The opposite end of rail 122 is brought around the trough 104 and into contact with the beginning end. In similar fashion, an end of the inner rail 123 is bent and passes to a shield 131 , where a wire (not shown) is connected, fed around tab 132 and through aperture 133 in the base to the underside for connection to the power source. The opposite end of rail 123 is brought around the trough 104 and into contact with the beginning end.
The weight sensors 66 are depicted in FIGS. 8 and 9 . Each sensor comprises a body 135 , an opposed set of conductive spring feet 136 , 138 and a compression spring 139 . The body, in turn, is formed of two pieces, a head 140 , having a square shaft 141 , extending downwardly therefrom, and a T-shaped base 142 , also square and which terminates in a cross-wise foot 143 (see FIG. 11A ). The T-shaped base 142 is assembled from beneath the turntable 32 , though a square aperture 144 ( FIG. 6 ) and the head 140 is positioned from above the turntable after first installing the compression spring 139 about the shaft 141 . The shaft 141 is fit within an accommodating passage formed in the base 142 . Finally, the spring feet 136 , 138 are connected by way of a flat shoe 145 , of plastic or similar material, with a screw 146 which joins the shoe 145 to the base 142 and finally to the shaft 141 . The shoe 145 is wider than the aperture 144 and prevents the sensor 66 from being removed from the turntable 32 .
Two installed sensors 66 are depicted in FIG. 5 , each being positioned on a platform 148 raised up within the trough 71 . With reference to FIGS. 11C and 11A , the turntable 32 is presented, in cross-section, resting upon the rollers 113 and centered among the wheels 108 . The buttons 65 , carried on the underside of the litter pan 33 are depicted in contact with the head 140 from a sensor 66 . In the positions shown the two make contact, however, the head has not been forced down, which would result in the spring feet 136 , 138 contacting the rails 122 , 123 . When the apparatus 30 is not occupied by an animal, this is the normal or operational condition. The pan is balanced on the spindle 86 , as previously described and is either stationary, or rotating during self-cleaning. Typically, a cleaning cycle is activated automatically after the expiration of a pre-set time, for instance, 30 minutes following the last activity in the apparatus. This ensures first that the pet has not decided to return and second, that the self-clumping litter has adequate time to solidify liquid waste, so that it can be readily removed from the litter as a solid mass.
At such time, the drive mechanism will be activated to clean the litter, as will be described hereinbelow. In operation, the weight of the animal in the pan is sufficient to cause it to tilt slightly about the spindle 86 , e.g., approximately 2°, which causes one of the buttons 65 to engage an opposed head from sensor 66 . If the buttons 65 are not employed on the pan 33 , the pan may be required to tilt a little more until the underside of the pan is brought into contact with the head of a sensor 66 . Contact with the head 140 causes the feet to make contact with the rails which sends a signal to a controller.
With reference to FIG. 7 , the inner wall 106 of base 31 is shown, as is a port 150 , through which a drive gear 151 partially extends, sufficient to engage ring gear 78 from the turntable 32 and thereby cause rotation of the turntable and litter pan 33 , carried thereon. The drive mechanism will be described subsequently but at this point it is sufficient to note that when gear 151 is rotated counter clockwise, when viewed from above, the turntable will rotate in a clockwise direction, which begins and continues during a self-cleaning cycle. Concurrent with such rotation of the litter pan 33 , the rake assembly 36 is driven in a clockwise direction through the litter in the rotating pan and eventually to deposit waste material into the waste receptacle of the apparatus, indicated generally by the numeral 37 . The receptacle provides a separate container 153 , having a floor 154 and a hinged door 155 , which is automatically opened during a self-cleaning cycle.
With reference next to FIGS. 1 and 12 – 16 , the operation of the apparatus during a self-cleaning cycle will be discussed. For the sake of clarity no litter has been depicted in the litter pan 33 . As is common in self-cleaning litter apparatus, a self-clumping litter is recommended and it operates by clumping liquid waste, e.g., urine, into a single mass, which can then be scooped away, much the same as solid waste. In FIGS. 1 and 12 , the apparatus 30 is at rest. In this position, the tines from the rake 160 are almost contacting the bottom 51 of litter pan 33 , where they are submerged in the litter to scoop beneath any clumps of waste material.
As the apparatus is cycled, which can either be controlled to operate automatically within a pre-set time of non-activity by the pet or, upon activation manually by the pet owner, the pan 33 is moving in its clockwise rotation and the rake assembly 36 is also moving in a clockwise fashion, arcuately across and through the pan. The assembly 36 moves from a rest or parked position, against the inner wall 161 of the shield 34 , near the opening 48 , proceeding in a countercurrent fashion through the litter, as depicted in FIG. 13 . In FIGS. 12–16 , the door 155 has been removed for clarity and a door pusher 162 is shown. Its movement will be described subsequently. In FIGS. 12 and 13 , the door pusher has not begun to move and thus, the door 155 remains closed. In FIG. 14 , as the rake assembly 36 continues its sweep through the litter, the door pusher 162 has begun upward movement, that is, it rotates from the entrance side 163 of the container, adjacent the shield 34 , toward the opposite, hinged side 164 of the container. As this occurs, the door 155 (not shown) which rests on the pusher is likewise beginning to lift, opening the receptacle.
In FIG. 15 , the rake 160 has lifted out of the litter pan 33 and has rotated upon its axis to hold waste clumps within the rake 160 and door pusher 162 has moved further upwardly. Finally, in FIG. 16 , the rake has first moved directly over the receptacle 37 and then rotated all the way upon its axis, allowing gravity to free the waste and waste clumps from the tines and fall into the open container 153 . The door pusher 162 is in its highest position and the door 155 will be completely open. At the end of this forward or first part of the cycle, the motor driving the mechanism is reversed, causing the retraction of the rake back into the litter pan, beneath the litter to its original resting position. While this reversal of the rake proceeds, the turntable is also reversed, to rotate counter-clockwise as the rake 160 moves downwardly through the litter and the door 155 is allowed to close.
While the foregoing explanation has referred to rotations in clockwise and counter-clockwise directions, such orientations are only applicable to the apparatus as shown in the drawings. Accordingly, it is to be understood that the specific directions of rotation do not constitute limitations on the practice of the present invention, as it will be appreciated that an apparatus manufactured as a mirror image of the apparatus 30 , would operate in the opposite directions, as the pan and rake moved first from the parked position and later returned to the parked position.
In order to ensure that waste and waste clumps are driven toward the tines, several stationary tines 165 are provided from an extension 166 provided radially inwardly from the opening 148 in the shield. As the pan 33 rotates, any clumps that were deposited or formed near the inner wall 168 of the pan will, upon rotation in clockwise fashion, be driven radially inwardly upon contacting the stationary tines 165 , where they will be in a path to be scooped away by the rake assembly 36 . As will become apparent subsequently, the turntable and pan rotate at a significantly higher rpm than the counter rotation of the rake assembly. In this manner, essentially all of the waste material is driven into the path of the oncoming rake assembly before it actually makes its complete pass through the litter. Generally, it is preferred to have the pan rotate at approximately three and one-half times the arcuate rotation of the rake assembly 36 , although ratios greater than or less than 3.5:1 are not necessarily precluded. What is important is that the ratio be high enough so that all or most of the waste material meets with the rake for removal from the pan.
Next, the rake assembly shall be described with specific reference to FIG. 21 , which depicts a skeletonized structure of the rake assembly 36 , which resides on the upper side of the apparatus 30 and the drive mechanism, indicated generally by the numeral 170 , which is housed in the main base, more particularly, in the drive housing, indicated by the numeral 38 . To protect the pet as well as the owner, the moving parts of the drive mechanism are located in the lower, inside portion of the main base, as depicted in FIG. 20 , where the various components of the apparatus have been removed to reveal the relationship between the assembly 36 and mechanism 170 .
The rake assembly 36 provides a central steel shaft 172 , hexagonal in cross-section for the various components it carries. Beginning at the left end, as viewed in FIG. 21 , the rake holder 173 is attached, which carries the rake 160 , discussed hereinabove. The rake holder is semi-arcuate, of a lesser diameter than the shield 34 , in order to fit closely to the inside wall 161 when the rake holder is in its parked or rest position. The tines of rake 160 are affixed to the underside of the holder and project straight down to almost the face 51 of litter pan 33 where they are then bent forward, parallel to the pan to form a flat scoop 174 (see FIG. 25 ). Several lateral tines 175 are affixed to the outermost end tine, to prevent waste materials from falling off the end of the scoop. The rake holder 173 is firmly joined to the shaft 172 , with the rake lock 176 . The rake holder can provide a bayonette-type of fitting to the shaft so that twisting the rake lock one-half turn will release the rake holder from the shaft for cleaning purposes as well as disassembly of the basic components of the apparatus.
The next component on the shaft is a small wheel 178 , which is held in place with an e-ring 179 . Adjacent the wheel is a small cam 180 , followed next by the upper main driving shaft 181 . A torsion spring 182 encircles the shaft 172 next and its two legs (not shown) are connected, one into the back of upper main driving shaft 181 and the other into a hole in shaft 172 , biasing the shaft to rotate in clockwise fashion, as viewed in FIG. 21 . Immediately adjacent the spring 182 is another e-ring 183 , which holds a large wheel 184 in place on the shaft and at the far end of the shaft, is a key cam wheel 185 .
The upper main driving shaft 181 has a circular plate 190 at its midsection and a cylindrical base 191 , into which a vertical, hexagonally-shaped steel shaft 192 is located. The base member 191 passes through an aperture in rake assembly base 193 , as depicted in FIG. 19 , the circular plate 190 providing a bearing surface for the rotation of upper main drive shaft 181 and related components upon the rake assembly base. The rake assembly base, in turn, is fastened to the upper floor 194 in drive housing 38 (see FIG. 22 ) and is accessible when the cover 195 ( FIG. 1 ) is unfastened from housing 38 . Beneath the rake assembly base and the floor 194 , the lower main driving shaft 196 is attached to the steel shaft 192 , which is visible in FIG. 23 , where the floor 194 has been removed.
Returning to FIG. 21 , the drive mechanism 170 provides a series of intermeshing gears as follows. Gear 151 , at the far left of the drawing is the gear that drives ring gear 78 beneath the turntable 32 . Meshing with it are gears 200 and 201 , journalled to the same shaft 202 . Gear 201 meshes with upper drive gear 203 , which is driven by a motor 204 , which is affixed to a mount 205 , provided on upper gear housing 206 , depicted in FIG. 25 . A suitable motor is of the type usually found in cordless screw drivers, which are 12 volt, and run at approximately 10,000 to 12,000 rpm. A current source of such motors is Mabuchi or Gold Effort. Of course, other motors can be employed and may require a different ratio of gears. The motor is powered by a conventional 12 volt transformer and a power output jack can be plugged into a suitable receptacle, provided on the exterior of the main base 31 , as at 199 (see FIGS. 22 and 25 ). As such means are well understood in the art, the transformer and related wiring necessary to operate the apparatus 30 have neither been depicted nor, described herein. Of course, the apparatus 30 could be provided with a battery compartment and battery, as an alternative source of power. Such devices are well known in the art and have not been depicted herein.
Beneath upper drive gear 203 is lower drive gear 207 and beneath gear 207 is a bushing 208 . Lower drive gear 207 meshes with gear 209 , journalled on shaft 210 and carrying gear 211 . Gear 211 meshes with gear 212 . Immediately above gear 212 is a small gear 213 , then a large gear 214 , and another small gear 215 all four being journalled on shaft 216 . Large gear 214 meshes with gear 218 , which drives the shaft 192 to rotate the rake assembly 36 . Gear 213 , in turn, meshes with gear 219 , behind it and another small gear 220 is located above 219 , both being journalled on a shaft 221 , visible in FIG. 20 . As will become apparent, the apparatus 30 operates from a single motor, as part of the drive mechanism 170 , which concurrently rotates the pan 33 , rotates the rake assembly and opens the cover 155 of waste receptacle 37 . As viewed in FIG. 20 , the various gears are mounted on a lower gear housing 222 , itself mounted to the floor 223 of a lower compartment 224 , which is housed within the main base 31 , next to the waste receptacle 37 .
In FIG. 17 , the inboard and outboard side walls 228 , 229 , extending up from the drive housing 38 and surrounding around the floor 193 , define an upper compartment, generally 230 . Two removable gate guilders, 231 and 232 are provided at the front of the compartment 230 . The guilder 232 is shown in FIG. 17 and provides a slot 234 , to accommodate the small wheel 178 of assembly 36 . A curvilinear front wall 235 of compartment 230 , slightly lower than side walls 228 , 229 , provides an upper edge 236 along which the wheel 178 rolls. Inside of the front wall 235 are a series of vertical tabs 238 which follow the curvilinear contour of the wall, leaving a narrow channel 239 , as depicted in FIG. 18 , into which a flexible shield member 240 is positioned (see FIG. 22 ).
The shield 240 can be a length of clear plastic material and is provided with a hole 241 of sufficient diameter to receive the wheel 178 of rake assembly 36 . Although not shown in the drawings, the cover 195 also provides a continuous sidewall which mates with the sidewalls 228 , 229 . The front portion of the sidewall of cover 195 is also curvilinear and the cover provides another series of tabs, similar to the tabs 238 , and another channel is formed. When fully assembled, the shield member 240 is positioned between the two channels and slides therein as the rake assembly traverses from the parked position in the litter pan to the dumping position over the waste receptacle. Its purpose is to minimize the entrance of dust or litter grains from the litter pan into the compartment 230 .
Referring now to FIGS. 17 and 22 , adjacent the rake assembly base 193 , a arcuate platform 245 is provided on the floor 194 of compartment 230 . The arc traversed is approximately 90° and the platform is raised sufficiently to contact the large wheel 184 of rake assembly 36 in order to provide support for the rake holder 173 as it traverses the litter, carrying waste material. Behind platform 245 a second platform 246 is provided, higher than platform 245 . Unlike the former, which has only a flat upper surface, the platform 246 has a generally flat upper surface, transitioning to a downward ramp 248 which curves toward and joins the floor 194 . A third platform 249 is provided on the rake assembly base 193 , in front of the first platform 245 . Platform 249 has a ramped upper surface which begins at the rake assembly base and rises to approximately the height of the first platform 245 . It is, however, considerably shorter in length than the first two platforms.
The key cam wheel 185 at the opposite end of rake holder 173 has a rounded top and flat underside 250 which rides along the surface of the second platform 246 . Extending downwardly from the underside 250 is a cam 251 , which is engageable with a step 252 , along side of and integral with the second platform 246 . As the rake holder 173 begins its sweep across the litter pan, an edge of the underside 250 from cam wheel 185 is passed along the horizontal surface of platform 246 , moving from the rest position, depicted in FIG. 12 . Just prior to the position depicted in FIG. 13 , the cam 251 begins to contact the step 252 , which starts an upward rotation of the rake holder 173 , into a waste holding position. At this point, a minor rotation of the main driving shaft 181 occurs so that the opposite edge of the underside 250 from cam wheel 185 contacts the horizontal surface of platform 246 . With the rotation of the rake holder 173 , it is elevated out of the pan 33 , to clear the shield 34 and eventually empty its contents into the waste receptacle 37 , as depicted in FIGS. 14–16 . Along the way, the cam wheel 185 is freed from the platform 246 . Toward the end of the forward cycle, the small cam 180 makes contact with the third platform 249 . As the cam 180 follows the ramp on platform 249 , it is rotated which, in turn, rotates the rake holder 173 in a counter-clockwise direction, as viewed from the distal end, so that the contents carried by the scoop 175 are emptied into the waste receptacle 37 , as depicted schematically in FIG. 16 .
For the return cycle, the drive mechanism 170 is reversed, causing the rake holder 173 to move out of the waste receptacle toward a position of rest in the litter pan. Initial movement rotates the rake holder 173 sufficiently to clear the receptacle as the cam 180 retraces its movement over the third platform 249 . Continued rotation of the upper main driving shaft 181 causes the cam 251 to engage the second platform 246 , whereby the rake holder 173 is again returned to its leveled, or scooping position in the litter contained in the pan 33 . The torsion spring 182 assists here, biasing the rake holder 173 counter-clockwise so that the flat scoop 174 is driven into the litter. Thereafter, the driving shaft 181 concludes its rotation until the rake holder 173 is parked in its initial rest position.
The floor 194 and sidewall 229 of drive housing 38 are removable as a unit and together house a lower compartment, generally 256 , of the base 31 . Behind the second platform 246 is a small compartment 258 , which receives a controller 259 for operation of the apparatus 30 . The compartment 258 extends into the lower compartment and provides a slot holder 260 , housed within the base 31 . A control button 261 is provided for manual operation of the apparatus. One embodiment of apparatus is fully self-cleaning, by which is meant that the cleaning cycle being described occurs without intervention by the pet owner. Nonetheless, should the pet owner wish to initiate a cycle, the power button 261 can be activated. The apparatus 30 can also be manufactured as a manual duty device, in which instance, the circuit board is not programmed to initiate a self-cleaning cycle automatically but rather the pet owner can do so upon demand. It is to be understood that while a button is depicted, the apparatus could also be provided with a foot control switch or a remote switch. Other means of automatic activation could be initiated from a micro-chip, embedded in the collar worn by the pet. None of the foregoing devices are depicted or described, as they are well known in the art.
With reference to FIG. 19 , the lower compartment 256 is exposed and reference should be made to the lower main driving shaft 196 . It is to be appreciated that several upper components have been removed to reveal elements in the lower compartment 256 and in so doing, several of the remaining elements depicted appear to be floating. At the lower end of base 196 , an inwardly directed link arm 264 extends radially out and an outwardly directed cam 265 extends radially out, approximately 165° from the link arm. The cam 265 is engage able with opposed inboard and outboard limit switches, 266 and 268 , respectively. Both switches are mounted to struts, not shown, that are provided in the underside of the floor 194 , which has been removed. The inboard switch 266 functions to reverse the cleaning of the pan ( FIG. 16 ) so that the rake assembly 36 returns to its parked position ( FIG. 12 ). The outboard switch 268 signals the apparatus to stop movement, until the next cleaning cycle is to be activated.
With reference next to FIGS. 10 and 24 , the mechanism for opening the waste receptacle, which is indicated generally by the numeral 270 , will be described. It includes a link arm 271 , a lever 272 , and the door pusher 162 , described previously. These work in conjunction with the inwardly directed link arm 264 . One end of the link arm 271 is pivotally connected to the inwardly directed link arm 264 , at 273 . The other end is connected to the lever 272 at 274 , and the lever 272 is itself pivotally connected at 275 to the underside of the floor 194 .
As the inwardly directed link arm 264 is rotated during the forward movement (cleaning) of an operation cycle, the link arm 271 urges the lever 272 to move rearwardly, as viewed in FIG. 25 . A cam 276 , provided by the lever 272 engages the underside of door pusher 162 , which begins to rise. The pusher 162 is pivotally mounted to a wall 278 of the waste receptacle 37 at 279 . In FIG. 25 , the engagement of the door pusher 162 with the waste receptacle cover 155 , as it is being lifted, is depicted. The various stages of upward movement of the door pusher 162 are also apparent in the sequential views, FIGS. 12–16 , described hereinabove, where the cover had been removed for clarity.
General Operation
Having described the components of the apparatus 30 , a general discussion of the self-cleaning cycle follows. Normally, the apparatus is at rest, which occurs whenever the apparatus has been filled with litter, turned on and is awaiting use by the pet. When the pet enters the apparatus, beginning at the ramp 39 and entering into the litter pan 33 , the weight of the animal depresses the turntable 32 , so that one of the weight sensors 66 makes contact with the rails 122 , 123 . In other words, the weight sensing mechanism 120 ; which comprises the weight sensors and the track assembly 121 , is provided for the actuation of a petinitiated cleaning cycle. The controller is preferably programmed to signal the timer after the weight of the animal has engaged a weight sensor with the rails for a minimum of 3 to 5 seconds. In other words, a brief contact between the sensor and rails will not cause a cycle to be initiated, because the pet would not have used the litter box. After the animal concludes its business and exits the apparatus, the turntable is again fully righted upon the spindle 86 and a signal is generated to the controller 259 to begin activation of a cleaning cycle, within a pre-determined time. Recognizing that the pet may return, a sufficient period is usually 30 minutes. Additionally, the apparatus employs self-clumping litter, which requires several minutes to absorb liquid waste and form a solid having sufficient integrity to be moved. Once begun, a cycle is completed in approximately two minutes and during this period, the sensors are no longer active.
The controller 259 is a micro-processor based device that includes the necessary hardware, timer, software and memory for executing and performing the various functions of the apparatus 30 . As will be described, the controller receives a number of electrical inputs from certain components and, depending upon the sequence of their receipt, generates electrical output signals to those components from which input signals were received and other components. The controller 259 receives electrical power from the power source 199 which may be either from an AC residential power supply, DC batteries or the like. The controller 259 may receive a cycle input from a switch 261 . Once energized, the controller is able to receive input from the weight sensing mechanism 120 , as well as an inboard limit switch 266 and an outboard limit switch 268 . And the controller 259 is then able to control operation of a motor 204 which in turn operates the turntable as previously described. The motor 204 also receives power from the power source 199 . It will be appreciated that the motor 199 may receive power from a separate power source that is of a different value or different format, than received by the controller. Or the controller 259 may directly supply power to the motor that is stepped-up or stepped-down an appropriate amount.
Returning now to the operation of the apparatus, the controller 259 includes an internal timer that is actuated upon exiting of the animal. Once this time has passed, the motor is energized and as a result three movements are commenced by the controller 259 —the litter pan 33 is rotated clockwise and counter-clockwise, the rake assembly 36 begins a slower rotation through the litter and litter pan 33 , and the cover of the waste receptacle 37 is raised.
Following one-half completion of the cycle, where the scoop 174 has deposited litter clumps and solid waste matter into the receptacle 37 , the inboard limit switch 266 is activated by the inwardly directed link arm 264 , from lower main driving shaft 196 , which sends another signal to the controller to reverse rotation of the motor. As this occurs, the rake assembly withdraws from the receptacle 37 , the cover is closed and the assembly moves down into the litter as it simultaneously rotates back (counter-clockwise, as shown) to its parked position, with the scoop 174 submerged in the litter. Concurrently, the litter pan and turntable are also rotating in a clockwise direction, as shown. When the outwardly directed cam 265 from the upper main driving shaft 181 contacts outboard limit switch 266 , a signal is sent to the controller. While the rake has almost returned to its parked position, the forward motion of a new cycle is commenced and run for approximately 2 seconds. The effect of this action is that the backlash is taken up from the gears of the drive mechanism and as a result, the rake is actually moved rearwardly the last remaining increment to its fully parked position against or very near to the wall inner wall 161 of dust shield 42 . Once the cycle is complete, all further movement ceases until either another cycle is initiated by the pet or, the owner elects to cycle the apparatus manually by activating the switch 261 or similar control switch.
Another feature of the apparatus, which is programmed into the controller, is a motor overload circuit. During a cycle, should the rake encounter an obstruction that the motor cannot overcome, the amperage to the motor will increase until an overload switch signals the controller to reverse the drive mechanism. Such switches, or overload protectors, are known in the art and do not constitute a limitation of the apparatus. Typically, a clump of solidified waste may have adhered to the surface of the pan, perhaps due to low litter volume and the clump may have a mass that cannot be immediately moved by the rake. By design and programming, the rake will return to its parked position and in several seconds a new cycle will commence. Generally, a second pass at the large clump or other obstruction is sufficient to remove or move it and the cycle continues. If not, a third park and re-initiation is programmed and if that attempt is still unsuccessful, the rake returns to rest or park and the apparatus is shut-down. A red LED or similar indicator is activated by the controller to provide a visual signal to the pet owner that the apparatus is unable to operate a cleaning cycle. The owner can then determine the nature of the problem and correct it so that the cycle can then be performed. In this instance, it is likely the owner would then initiate a cycle manually, to view operation and confirm that the previous problem no longer exists.
As noted hereinabove, an embodiment of the apparatus 30 is also within the scope of the invention which does not self-clean automatically, that is, when the pet leaves the apparatus. To initiate self-cleaning, the pet owner decides when by pushing the button 261 or similar switch and the apparatus proceeds to follow the cycle just described. Such apparatus would not employ the sensing mechanism 120 and, because a tiltable litter pan would not be required, the turntable could also be eliminated, in which instance the pan would be driven directly.
Thus, it should be evident that the apparatus and method of the present invention are effective for self-cleaning of litter devices, employing rotatable litter pans. Although the foregoing explanation has been directed to the apparatus depicted in the drawings, it will be appreciated by those skilled in the art, that certain components could be varied or modified to obtain the same operation. One such modification envisioned is the combination of the turntable and litter pan into a single component, rather than two separate components. Another modification is in the sensing mechanism 120 . As described in the drawings, sensors are provided in the turntable and rails in the base, so that contact can be made. However, the location could be reversed, by placing the rails or similar elements in the turntable which would be engageable with sensors from beneath. So long as the tilting of the pan provides a signal to the controller to activate the drive mechanism, the relative position of the necessary components can be varied to suit manufacturing as well as consumer preferences.
Based upon the foregoing disclosure, it should now be apparent that the use of the litter apparatus described herein will carry out the objects set forth hereinabove. It is, therefore, to be understood that any variations evident fall within the scope of the claimed invention and thus, the selection of specific component elements can be determined without departing from the spirit of the invention herein disclosed and described. Thus, the scope of the invention shall include all modifications and variations that may fall within the scope of the attached claims. | A self-cleaning litter apparatus that separates and extracts clumped litter waste material from litter material contained therein during use includes a chamber adapted to contain a quantity of litter material. The chamber is rotatable about a centrally disposed axis. A rake is disposed within the chamber. The rake is rotatable about an axis which is spaced apart from the chamber axis. A drive assembly is provided for simultaneously rotating the chamber about the chamber axis and for rotating the rake about the rake axis. The rake sweeps through the litter material while clumped litter waste material is directed toward the rake by rotation of the chamber to thereby separate clumped litter waste material from the litter material in the chamber, collect the separated clumped litter material in the rake and extract the separated clumped litter material from the chamber. | 0 |
CROSS-REFERENCE
This application claims priority from Provisional Patent Application Ser. No. 61/661,480 filed on Jun. 19, 2012.
FIELD OF THE INVENTION
This invention relates to a caution tape holder that can be inserted into an opening in a prior art safety cone or other object for retaining the tape above the cone and establishing a safety zone. The unique design and profile of the caution tape holder does not damage the caution tape or the safety cone, and permits the safety cones to be stacked on top of one another in a nested fashion for storage with the caution tape holder installed thereon.
BACKGROUND
Oftentimes it is necessary for workers and/or first responders to establish a safety or work zone to complete the task at hand. The creation of such a temporary safety and/or work zone is typically accomplished through a combination of safety cones and caution tape. More specifically, the safety cones are placed along the perimeter of the safety/work zone and strung together using caution tape. For example, when it is desirable to divert traffic or otherwise block off a designated construction zone, construction workers will typically place safety cones along the perimeter of the area being cordoned off and string said cones together with caution tape. Typically, the caution tape is tied or stapled to the cones, which is not only time consuming to install/de-install but also tends to damage the tape and/or cones so that they cannot be reused.
Consequently, there exists in the art a long-felt need for a device for removably attaching caution tape or other items, such as warning flags, to a safety cone, traffic barrel, etc. There also exists in the art a long felt need for a caution tape holder that does not cause damage to the caution tape or to the object to which it is attached, thereby enabling the reuse of said items. Moreover, there is a long felt need for a caution tape holder for removable attachment to a safety cone, wherein a plurality of safety cones may be stacked for easy storage without first having to remove the caution tape holders attached thereto. Finally, there is a long-felt need for a caution tape holder that accomplishes all of the forgoing objectives and that is relatively inexpensive to manufacture, and safe and easy to use.
SUMMARY
The following presents a simplified summary in order to provide a basic understanding of some aspects of the disclosed innovation. This summary is not an extensive overview, and it is not intended to identify key/critical elements or to delineate the scope thereof. Its sole purpose is to present some concepts in a simplified form as a prelude to the more detailed description that is presented later.
The subject matter disclosed and claimed herein, in one aspect thereof, is a caution tape holder for removable attachment to a safety cone wherein neither the safety cone, the device nor the caution tape is damaged during installation or removal. In a preferred embodiment of the present invention, the caution tape holder is comprised of an integrally formed top and body portions, wherein said top portion further comprises an opening and a slot for receipt of a length of prior art caution tape, and wherein said body portion is further comprised of a plurality of ridges and valleys for removably insertion into an opening in a safety cone or other object.
The caution tape holder of the present invention permits a user to removably attach the holder and other items, such as caution tape, warning flags and the like, to a prior art safety cone. Proper use of the caution tape holder will not result in damage to the caution tape, the caution tape holder, or to the safety cone to which they are attached, thereby enabling the reuse of said items. The unique design and profile of the caution tape holder also permits the safety cones to be stacked on top of one another for relatively easy storage with the caution tape holder installed thereon. Finally, the caution tape holder of the present invention is relatively inexpensive to manufacture, and safe and easy to use.
To the accomplishment of the foregoing and related ends, certain illustrative aspects of the disclosed innovation are described herein in connection with the following description and the annexed drawings. These aspects are indicative, however, of but a few of the various ways in which the principles disclosed herein can be employed and is intended to include all such aspects and their equivalents. Other advantages and novel features will become apparent from the following detailed description when considered in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a perspective view of a preferred embodiment of the caution tape holder of the present invention.
FIG. 2 illustrates a front elevational view of the preferred embodiment of the caution tape holder of the present invention.
FIG. 3 illustrates a perspective view of an alternative embodiment of the caution tape holder of the present invention.
FIG. 4 illustrates a perspective view of the preferred embodiment of the caution tape holder of the present invention being inserted into a safety cone.
FIG. 5 illustrates a perspective view of the preferred embodiment of the caution tape holder of the present invention installed on a safety cone and supporting a length of caution tape.
FIG. 6 illustrates a perspective view of a plurality of caution tape holders of the present invention installed on safety cones and cordoning off a safety zone.
DETAILED DESCRIPTION
The innovation is now described with reference to the drawings, wherein like reference numerals are used to refer to like elements throughout. In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding thereof. It may be evident, however, that the innovation can be practiced without these specific details.
Referring initially to the drawings, FIG. 1 illustrates a perspective view of a preferred embodiment of caution tape holder 100 of the present invention. Holder 100 is comprised of a top portion 110 and a body portion 130 , wherein said top and body portions 110 , 130 are preferably integrally formed. Nonetheless, it is also contemplated that top portion 110 and body portion 130 may be two separate components, fixedly or removably attached to each other by any common means known in the art. Inasmuch as the holder is typically deployed outdoors and exposed to the elements such as rain, snow, sleet, etc., holder 100 is preferably comprised of ABS (acrylonitrile-butadiene-strene) plastic or some other generally weather-resistant material such as plastic, aluminum, wood, rubber, or the like.
In a preferred embodiment of the present invention, top portion 110 is generally cylindrical in shape and further comprised of a top surface 112 , a side surface 114 , and a bottom surface 116 . The thickness of top portion 110 , as measured between top surface 112 and bottom surface 114 is preferably between 7/16ths and ¾ inches, and the overall diameter of top portion 110 is preferably between 1⅝ths and 2 inches. Nonetheless, it is also contemplated that other shapes and dimensions could also be utilized without affecting the overall concept of the present invention, provided that the shape and/or size of top portion 110 is such that top portion 110 is not permitted to pass through an opening 230 in a prior art safety cone 200 .
As best illustrated in FIG. 1 , top surface 112 of top portion 110 is preferably comprised of an opening 1120 therein that leads to a slot 1140 formed in side surface 114 of top portion 110 . More specifically, and as described more fully below, a length of prior art caution tape 250 can be passed through opening 1120 and removably retained in slot 1140 without damaging tape 250 . While the overall shape and dimensions of opening 1120 and slot 1140 may vary to suit user need and/or preference, in a preferred embodiment of the present invention the width of opening 1120 will be less than the width of slot 1140 to reduce the likelihood that caution tape 250 will prematurely detach from holder 100 . For example, the width of opening 1120 is preferably between 3/16ths and 5/16ths of an inch, and the width of slot 1140 is preferably between ⅞ths and one inch. Opening 1120 may also have a generally curved appearance, as shown in FIG. 1 , to further reduce the likelihood that caution tape 250 will become prematurely or unintentionally detached from holder 100 .
As illustrated in FIGS. 1 and 2 , body portion 130 is a generally conically-shaped mass comprised of an outer surface 132 and a bottom 136 located opposite of top portion 110 . Body portion 130 may be a solid mass or hollowed out. For example, bottom 136 may have an opening (not shown) therein to reduce the overall weight of holder 100 .
In a preferred embodiment of the present invention, outer surface 132 is further comprised of more than one ridge 1322 and more than one valley 1326 , wherein the diameter of each ridge 1322 and valley 1326 is less than the diameter of top portion 110 and decreases in size along outer surface 132 in the direction of bottom 136 . For example, the outside diameter of the valley 1326 nearest top portion 110 is preferably between 1¼ and 1⅝ths inches, whereas the outside diameter of the adjacent valley 1326 closer to bottom 136 is preferably between 1 1/16th and 1¼ inches and less than the diameter of the previous valley 1326 near top portion 110 . Likewise, and by way of example, the outside diameter of the ridge 1322 nearest top portion 110 is preferably between 1⅜ths and 1⅝ths inches, whereas the outside diameter of the adjacent ridge 1322 closer to bottom 136 is preferably between 1 5/16ths and 1 9/16ths inches and less than the diameter of the previous ridge 1322 near top portion 110 .
As described more fully below, most prior art safety cones 200 have an opening 230 that is either 1 1/16th or 1 5/16th inches in diameter. Accordingly, in a more preferred embodiment of the present invention, body portion 130 has two ridges 1322 of differing and decreasing diameters to accommodates the two different standard sizes of openings 230 in prior art safety cones 200 . Nonetheless, it is contemplated that body portion 130 could also have more or less ridges 1322 and valleys 1326 to suit user preference and/or a particular application without affecting the overall concept of the present invention. Indeed, FIG. 3 depicts an alternative embodiment of holder 300 comprised of a top portion 310 and a bottom portion 330 . Similar to the holder depicted in FIGS. 1 and 2 , top portion 310 is further comprised of a top surface 312 , a side surface 314 , and a bottom surface 316 . The thickness of top portion 310 , as measured between top surface 312 and bottom surface 314 is preferably between 7/16ths and ¾ of an inch, and the overall diameter of top portion 310 is preferably between 1 5/16ths and 1⅝ths inches. Nonetheless, it is also contemplated that other shapes and dimensions could also be utilized without affecting the overall concept of the present invention, provided that the shape and/or size of top portion 310 is such that top portion 310 is not permitted to pass through opening 230 in a prior art safety cone 200 .
Top surface 312 of top portion 310 is preferably comprised of an opening 3120 therein that leads to a slot 3140 formed in side surface 314 of top portion 310 . More specifically, and as described above, a length of prior art caution tape 250 can be passed through opening 3120 and removably retained in slot 3140 without damaging tape 250 . While the overall shape and dimensions of opening 3120 and slot 3140 may vary to suit user need and/or preference, in a preferred embodiment of the present invention the width of opening 3120 will be less than the width of slot 3140 to reduce the likelihood that caution tape 250 will prematurely detach from holder 300 . For example, the width of opening 3120 is preferably between ¼ and ⅜ths of an inch, and the width of slot 3140 is preferably between ⅝ths and ⅞ths of an inch. Opening 3120 may also have a generally curved appearance (not shown) similar to that of holder 100 in FIG. 1 to further reduce the likelihood that caution tape 250 will become prematurely or unintentionally detached from holder 300 .
As illustrated in FIG. 3 , body portion 330 is a generally conically-shaped mass comprised of an outer surface 332 and a bottom 336 located opposite of top portion 310 . Body portion 330 may be a solid mass or hollowed out. For example, bottom 336 may have an opening (not shown) therein to reduce the overall weight of holder 300 .
Outer surface 332 is further comprised of a single ridge 3322 and at least one valley 3326 , wherein the diameter of ridge 3322 and at least one valley 3326 are both less than the diameter of top portion 310 . For example, the outside diameter of the at least one valley 3326 nearest top portion 310 is preferably between one and 1¼ inches, and the outside diameter of the ridge 3322 nearest top portion 310 is preferably between 1⅛th and 1⅜ths inches. Nonetheless, it is contemplated that other shapes and sizes could also be employed to suit user preference or a particular application, provided that head portion 310 is not permitted to pass through opening 230 in prior art cone 200 .
Having now described the overall structure of multiple embodiments of caution tape holder 100 , 300 , the general structure of prior art safety cone 200 and the use and usefulness of holder 100 , 300 will now be summarized. FIG. 4 illustrates a perspective view of the preferred embodiment of the caution tape holder 100 of the present invention being inserted into safety cone 200 . Safety cones 200 are well known in the art and are typically comprised of a base 210 for contacting the ground or other generally horizontal surface, a generally conically shaped body portion 220 that rests atop of base 210 and a generally circular opening 230 at the top of body portion 220 . The two most common sizes of opening 230 in cone portion 220 are 1 1/16ths and 1 5/16th inches in diameter. Accordingly, as described above, the overall shape and size of holder 100 should be such that body portion 130 may be inserted into opening 230 to create a friction fit between the outer surface 132 of body portion 130 and cone body portion 220 . More specifically, if safety cone 200 is of the type having an opening 230 with a diameter of approximately 1 1/16th inches (i.e., the smaller of the two most frequently used sized openings), only the smaller of the two ridges 1322 would fit within opening 230 and the larger of the two ridges 1322 (i.e., the one nearest top portion 110 ) would rest atop of cone body portion 220 above opening 230 . By comparison, if safety cone 200 is of the type having an opening 230 with a diameter of approximately 1 5/16ths inches (i.e., the larger of the two most frequently used sized openings), both of ridges 1322 would fit within opening 230 and only the top portion 110 would rest atop of cone body portion 220 above opening 230 . Consequently, it can be appreciated that the preferred embodiment of holder 100 can be used with either of the two most common types of prior art cones 200 .
Once holder 100 has been properly installed atop of prior art cone 200 , a user (not shown) may removably attach a length of caution tape 250 to holder 100 by inserting tape 250 through opening 1120 in top surface 112 and into slot 1140 , as best shown in FIG. 5 . In this manner, caution tape 250 may be removably attached to a prior art safety cone 200 relatively quickly and easily, and without damaging tape 250 or cone 200 . Further, in the preferred embodiment of the present invention depicted in FIG. 1 , the width of opening 1120 is less than the width of slot 1140 to reduce the likelihood that caution tape 250 will prematurely detach from holder 100 . In the same embodiment, opening 1120 also has a generally curved appearance across top surface 112 to further reduce the likelihood that caution tape 250 will become prematurely or unintentionally detached from holder 100 .
FIG. 6 illustrates a perspective view of a plurality of caution tape holders 100 of the present invention installed on prior art safety cones 200 to cordon off a safety zone. As an important feature of the present invention, once the safety zone is no longer needed, a user (not shown) can quickly and easily remove tape 250 from slot 1140 via opening 1120 without damaging the tape 250 or the prior art cone 200 , ensuring that both can be reused in the future.
Consequently, the various embodiments of caution tape holder 100 of the present invention permit a user to removably attach the holder 100 , 300 and other items, such as caution tape 250 , warning flags and the like, to a prior art safety cone 200 or other object with an opening therein. Proper use of the caution tape holder 100 , 300 will not result in damage to the caution tape 250 , holder 100 , 300 , or to the safety cone 200 to which they are attached, thereby enabling the reuse of said items. The unique design and profile of the caution tape holders 100 , 300 described herein also permits the safety cones 200 to be stacked on top of one another for relatively easy storage with the caution tape holder 100 installed thereon. Finally, the caution tape holder 100 , 300 of the present invention is relatively inexpensive to manufacture, and safe and easy to use.
Other variations are within the spirit of the present invention. Thus, while the invention is susceptible to various modifications and alternative constructions, a certain illustrated embodiment thereof is shown in the drawings and has been described above in detail. It should be understood, however, that there is no intention to limit the invention to the specific form or forms disclosed, but on the contrary, the intention is to cover all modifications, alternative constructions, and equivalents falling within the spirit and scope of the invention, as defined in the appended claims.
The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to,”) unless otherwise noted. The term “connected” is to be construed as partly or wholly contained within, attached to, or joined together, even if there is something intervening. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate embodiments of the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
Preferred embodiments of this invention are described herein. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventor expects skilled artisans to employ such variations as appropriate, and the inventor intends for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context. | A caution tape holder for removable attaching a length of caution tape to a prior art safety cone. The caution tape holder is comprised of a top portion and a body portion, wherein said top portion extends at least partially out of an opening in a safety cone and has an opening therein for receipt of a length of caution tape. The caution tape holder of the present invention can be used in conjunction with a variety of different sized safety cones and will not damage the safety cone or the length of caution tape used therewith, nor does it necessitate the threading of the tape through a narrow opening. Additionally, the caution tape holder will not unduly interfere with the stacking and storage of prior art safety cones in a nesting fashion. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a vehicle of the so called "off-road" type. More particularly, this invention relates to construction equipment including an adaptable off-road type vehicle that both oscillates and articulates facilitating its use in a wide variety of operations.
2. Description of the Prior Art
A wide variety of off-road type vehicles have been known in the prior art. Each type of vehicle has been expensive and not used fully, since it was ordinarily connected with a particular type of attachment. As described in my co-pending application entitled "Adaptable Combination of Vehicle and Attachments", Ser. No. 919,179, filed June 26, 1978, there is provided an adaptable expensive vehicle that can be used with a wide variety of attachments such as augers, dump beds, ditch digging equipment, back hoes, revolving jib cranes, fork lifts and the like to more fully utilize the vehicle. This type of flexibility in the wide variety of uses necessitates a vehicle that is highly flexible, highly maneuverable and the like. This demands a vehicle that will articulate to afford the high degree maneuverability and ease of steering; and also a vehicle that oscillates, or can attain a more nearly level, or horizontal, platform for operation of the attachments. This type of vehicle that both articulates and oscillates has not been available in the prior art, particularly having the features delineated hereinafter.
SUMMARY OF THE INVENTION
Accordingly, it is an object of this invention to provide an adaptable off-road vehicle that both oscillates and articulates, allevating the deficiencies of the prior art.
It is a specific object of this invention to provide a vehicle having front and rear sections that are connected about a vertical articulation axis to enable highly maneuverable steering; and that can be tilted with respect to the terrain, or wheels of the vehicle, to attain a more nearly level platform for most effective operation of one or more attachments connected to the vehicle.
These and other objects will become apparent from the descriptive matter hereinafter, particularly when taken in conjunction with the appended drawings.
In accordance with this invention there is provided an adaptable off-road vehicle that includes: (a) a frame carrying a prime mover and drive means, an operators console and control for controlling movement of the vehicle and power means for operating attachments; (b) a plurality of at least four wheels carrying the frame; (c) steering means for steering the vehicle; the improvement comprising means for affecting both articulation and oscillation of the vehicle and including: (d) having the frame formed into two sections, including a first section and a second section, with an articulation joint including a vertical interconnection and steering rams disposed a distance from the pivotal interconnection enabling operator control of the articulation; (e) attachmeans on the first section for mounting the attachments; and (f) a leveling means on the first section operable to effect a predetermined angular position with respect to a straight line between the wheels carrying the first section; and control disposed in the operators console and connected with the leveling means and the power means for enabling operator control of the oscillation whereby the first section can be positioned more nearly level than otherwise. In specific embodiments, the level means includes hydraulically operable rams and the power source includes a hydraulic pump for supplying high pressure hydraulic fluid, and the control includes a hydraulic fluid flow control valve for effecting and holding the predetermined position with a liquid lock.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an isometric view of an adaptable off-road vehicle in accordance with this invention.
FIG. 2 is a schematic view of the front section of the vehicle of FIG. 1, showing schematically the hydraulically operable leveling means.
DESCRIPTION OF PREFERRED EMBODIMENTS
This invention can be understood more clearly by referring to the figures in conjunction with the following descriptive matter. Referring to FIG. 1, the adaptable off-road vehicle 11 has its frame 13 mounted on wheels 15. The frame 13 carries a prime mover 17 for powering the vehicle 11 and driving a power means, or power source, 19 for power in operating respective attachments. A steering means 21 is provided for steering the vehicle.
The vehicle 11 comprises a plurality of sections, including a first, or front, section 23 and a second, or rear, section 25. The vehicle 11 in the illustrated embodiment is an articulated vehicle, articulating about a central vertical axis interconnection 27. The axis interconnection 27 comprises a plurality of pins 29 inserted through respective apertures 31 in the respective clevices 33 emplaced over the steering lug 35 with the apertures in alignment for receiving the pins 29.
The frame 13 is formed of suitably strong structural materials, such as steel or the like, that has been welded into place to support the respective elements in accordance with conventional engineering technology in this art. The rear section 25 encloses the operators console 37 having usual controls, seat and the like.
The respective wheels 15 may comprise any of the usual types of wheels. As illustrated, they include hydraulic motor driven wheels with tires around the periphery. The hydraulics are connected with suitable controls, pump and reservoir in a hydrostatic system having at least conventional forward and rearward operating capability. The four wheels 15 are employed for supporting in a very stable manner each of the four corners of the frame 13.
The prime mover 17 is an internal combustion engine; specifically, a diesel in the illustrated embodiment. It drives the power means which comprises a pair of hydraulic pumps supplying high pressure hydraulic fluid for the hydrostatic drive system, as well as a hydraulic system for powering the respective attachments.
Steering means 21 comprises the usual steering wheel and hydraulic ram, such as ram 38 that is fluidly connected with the steering means 21 and operable to effect articulation of the frame 13 about the central vertical axis 27.
Expressed otherwise, the basic vehicle 11 is a tractor that has a four-wheel drive and articulated power unit and is adapted to use remotely operated, hydraulically powered tools, or attachments, whether they are fastenable to the machine or used remotely therefrom. The hydraulic power unit can accommodate high pressure circuits of from 2 gallons a minute up to 8 gallons a minute on one auxiliary system and 6 gallons a minute to 26 gallons a minute in the main hydraulic circuits for driving the attachments. The vehicle 11 has plug-in quick-connect hydraulic circuit fittings 39 that enable the hydraulic lines on the respective attachments to be plugged in, in the same way that an electric cord may be plugged into a wall socket. The respective receptacles and plugs have respective valves immediately adjacent the ends for preventing unwanted flow when the fittings are unplugged. This facilitates hydraulic interconnection of the respective attachments such that both they and the hydraulic circuits on the vehicle remain filled with hydraulic fluid.
The illustrated embodiment of the vehicle is available in either standard or heavy duty versions. The vehicle will handle up to about 5,000 pounds on the fork lift attachment. As illustrated, the wheels on the heavy duty version employs tires that are 19 inches wide. The vehicle steers 90° total articulation, 45° on either side of the longitudinal axis of the aligned sections.
As described in the aforementioned patent application Ser. No. 919,179, the descriptive matter of which is incorporated herein by reference for details that are omitted herefrom, respective first and second portions of attachment means may be employed to facilitate mounting of the respective attachments. A typical first portion 41 is illustrated. As illustrated the respective first portion 41 comprises respective tracks 43 that are spaced a predetermined distance d apart so as to mount clevices on the attachments. Suitable apertures 45 are spaced a predetermined distace l apart along the respective tracks 43 so as to form mounting lugs, or mounting stations, for mounting the attachments. Vertical track means 47 are provided similarly for mounting attachments on the front of the vehicle 11. One particular advantage and feature of this vehicle 11 is the combination of the articulation feature for high maneuverability and the oscillation means, or leveling means, 51, FIGS. 1 and 2. The front wheels 15 are connected laterally by an axle 53.
Pivotally carried by the axle 53 is a main structural frame member 55, called the front frame member, FIG. 2. The front frame member 55 supports the platform of the front section 23. The front frame member 55 and the axle member 53 are pivotally connected together at a pivot joint 57 near their respective midpoints. The pivot joint 57 may be formed by a pin 59 inserted through apertures through mounting lugs 61 and the front frame member 55. The mounting lugs 61 are affixed to the axle 53, as by welding.
The leveling means 51 includes two hydraulic rams 63, 65 that are connected with the front frame member 55 and the axle 53 on the right and left sides at predetermined lateral distances from the pivot joint 57. As illustrated, the respective hydraulic rams 63, 65 are connected with the axle at respective pivot joints, such as pivot joint 67. Pivot joint 67 may comprise a pin shaft having disposed thereabout and connected therewith a connecting rod end, or head, such as a bolted connecting rod end. The connecting rod end is shown connected with the cylinder portion of the hydraulic ram. The respective hydraulic rams are connected via their extensible rod, with pivot joints 69. The pivot joints 69, similarily, may be comprised of a pin shaft, such as formed by a bolt or the like in combination with a surrounding rod end, or head. If desired, of course, the pivot joints may employ bushings or the like between the shaft and rod end to facilitate the respective pivotal motion without excessive wear and to facilitate repair. Of course, the hydraulic rams can be physically connected upside down from the illustrated connections, if desired. As implied hereinbefore, each ram comprises a cylinder 71 and an extensible rod 73 with suitable interior piston connected with the rod so as to extend or retract the rod responsive to hydraulic pressure on the respective side of the piston (the piston being inside the cylinder 71 and not shown). The respective hydraulic rams 63 and 65 are fluidly connected with the source of high pressure hydraulic fluid and a control for positioning the front frame member 65 at a predetermined angle with respect to the axle 53.
Referring to FIG. 2, the power source includes a hydraulic pump 75 that is connected by a suction line 77 with a hydraulic fluid reservoir 79. The suction line 77 may be low pressure hydraulic fluid hose. The pump 75 is connected via high pressure hydraulic hose, or hydraulic line 81 with a control, such as the control valve 83. The control valve 83 is an open center valve with locked ports such that the desired degree of tilting may be effected by moving the control handle 85. One a desired position is attained, the control handle 85 is moved to the neutral position to hold the predetermined and attained position.
The control valve 83 is connected via high pressure hydraulic lines 87, 89 with a lock valve 91. The lock valve 91 prevents any hydraulic bleed-off and insures a solid liquid lock for holding an attained position. The lock valve 91 is connected via high pressure hydraulic line, such as the high pressure hydraulic hoses 93, 95 with the respective connections for tilting right or tilting left with respect to the front axle 53. Specifically, the hydraulic line 93 is connected with the cylinder port 97 of the hydraulic ram 65 and with the rod port 99 of the hydraulic ram 63 for forcing a tilt to the right. In converse manner, the hydraulic line 95 is connected with the rod port 101 of the ram 65 and with the cylinder port 103 of the ram 63 for forcing a tilt to the left. Of course, when the high pressure fluid is directed into the line 93 and in the respective connected ports, low pressure fluid is vented to be returned via lines 95 and 89 to the hydraulic reservoir 79. The hydraulic reservior 79 is connected with the control valve 83 through the low pressure hydraulic line 105. The respective connections of the respective lines with the elements are designed to hold the pressure that will be exerted thereon. Ordinarily, high pressure hydraulic line connectors may be connected with threaded nipples on the end of suitable fittings on the respective valves and rams.
In operation, a given attachment will be mounted on the tracks 41 and driven to the site using appropriate controls, steering and the like. At the operating site, the front section 23 will be leveled by the operator. Specifically, the handle 85 will be pushed or pulled in the appropriate direction to tilt the front frame member 55 to the right with respect to the axle 53 (or to the left, as the case may be). Specifically, if tilting to the right is to be done, the control handle 85 is moved to send high pressure fluid through the line 87, lock valve 91 and line 93 to force the piston upwardly in the ram 65, extending the rod 73. Simultaneously, high pressure hydraulic fluid is sent to the rod port 99 to move the piston downwardly in the ram 63 and pivot the front frame member clockwise in FIG. 2 about the pivot joint 57, effecting a tilt to the right with respect to the axle 53. This allows attaining a substantially horizontal platform, within the limits of operation, for most effective operation of the attachment mounted on the front section 23. When the handle 85 is returned to the neutral position, as by spring loading or manual return, the lock valve 91 locks the hydraulic fluids to afford a positive fluid lock and hold the attained angle.
Conversly, when the tilt is to be to the left, high pressure hydraulic fluid is fed through the line 89 and lock valve 91 and line 95 to effect a tilt to the left. When the control handle 85 is moved to the neutral position, a positive lock is afforded by the lock valve 91 and the attained tilt to the left is retained.
When it is desired to return to the same or another location, the control handle is moved to place the front frame member 55 substantially parallel to the axis 53 when driving on level roads or the like.
Many of the hydraulic hoses and interconnections are not shown on the vehicle 11 in the interest of simplicity and since this involves state of the art technology.
The usual materials of construction are employed in fabricating the vehicle, the attachments, and the leveling means described herein. Ordinarily, steels are preferred in the strong structural parts because of their strength and ready amenability to the various operations; such as welding, milling and casting.
It can be seen that this invention allows providing a more nearly horizontal platform from which to operate a particular attachment than would otherwise be possible. Moreover, because of the articulation in combination with the oscillation, the high degree of maneuverability and flexibility of the vehicle 11 provides a machine that can be used more fully in a wide variety of working conditions and with a wide variety of different attachments.
Thus, it can be seen that the objects delineated hereinbefore are provided by this invention.
While the invention has been described with a certain degree of particularity, it is understood that the present disclosure has been made only by way of example and numerous changes in details of the structure and the combination and arrangement of parts may be resorted to without departing from the spirit and scope of the invention, reference being had to the appended claims for that purpose. | This specification discloses an off-road vehicle that both articulates and oscillates, thereby enabling achieving a highly maneuverable, more nearly level working platform from which attachments can be operated with utmost effectiveness. The vehicle is characterized by front and rear sections, each carried by two wheels and connected at an articulating steering joint with steering rams and steering means; and a mechanism on the front section for leveling the front section. The leveling mechanism includes a front frame member that supplies the main structural support for the front section and is pivotally connected with a front axle, with hydraulic rams disposed on either side of the pivotal connection and connected via control valve with a source of high pressure hydraulic fluid for attaining and holding a predetermined, or substantially level, position. In the preferred embodiments, a lock valve is interposed between the control valve and the hydraulic rams for providing a positive liquid lock to hold a predetermined position. Also disclosed are preferred embodiments. | 1 |
FIELD
[0001] Embodiments described herein relate to radio resource allocation in wireless communications networks.
BACKGROUND
[0002] Radio resource allocation is a process which is employed to manage finite radio resource in an environment in which a wireless communications network is established. In a cellular paradigm, radio resource allocation aims to take account of likely interference impact of adjacent cells, when allocating radio resource. In opportunistic or ad hoc paradigms, gathering information to enable effective radio resource allocation is equally if not more important.
BRIEF DESCRIPTION OF THE DRAWINGS
[0003] FIG. 1 is a schematic representation of a wireless communications network;
[0004] FIG. 2 is a schematic representation of an access point in accordance with a described embodiment;
[0005] FIG. 3 is a graphical representation of a resource block of a communications channel defined in the network;
[0006] FIG. 4 is a schematic representation of a resource allocation coordination manager of the access point of FIG. 3 ;
[0007] FIGS. 5 a and 5 b are schematic geometrical representations of station position examples to aid in understanding of operation of the described embodiment;
[0008] FIG. 6 is a process flow diagram for a list update process of the described embodiment;
[0009] FIG. 7 is an example list of stations produced by the list update process;
[0010] FIG. 8 is a resource allocation process of the described embodiment;
[0011] FIG. 9 is a normal allocation sub-process called by the resource allocation process of FIG. 8 ;
[0012] FIG. 10 is an exclude allocation sub-process called by the resource allocation process of FIG. 8 ;
[0013] FIG. 11 is a list update process of an alternative embodiment;
[0014] FIG. 12 is a resource allocation process of an alternative embodiment;
[0015] FIG. 13 illustrates example lists produced and maintained by the list update process of FIG. 11 ;
[0016] FIG. 14 illustrates sorted allocation lists generated from the lists of FIG. 13 ;
[0017] FIG. 15 illustrates prioritised sorted allocation lists generated from the lists of FIG. 13 ; and
[0018] FIG. 16 is a schematic representation of a portion of the resource block, in the course of an allocation process.
DETAILED DESCRIPTION
[0019] A wireless communications network is illustrated in FIG. 1 .
[0020] In general terms, the embodiment employs a Radio Environment Map (REM), to proactively estimate interference in dense small cell deployments. Embodiments described herein achieve full frequency reuse, i.e. a factor of 1. Embodiments described herein could also exploit white space spectrum opportunities.
[0021] The REM approach, as described in relation to the embodiments, uses a measurement based prediction model of the radio environment in order to estimate the interference to neighbours.
[0022] Conceptually, REM is based on collecting radio related measurements in order to build a statistical map for making radio environment predictions. Dynamic REM (DREM) is considered to be a REM that can perform predictions in short time periods (i.e. at seconds or sub-second resolutions). The DREM approach, used by embodiments described herein, involves an access point performing estimation of interference signal levels, assuming no prior knowledge of the locations of stations capable of communicating with that access point, or locations of other access points.
[0023] The approach then uses these estimates in order to make predictions of the interference levels caused to neighbouring devices. In order to do this, the embodiments make use of received signal power measurements received from participating stations. For example, if the technology specified in the LTE standard is employed, an access point (HeNB) could employ the Reference Signal Received Power (RSRP) measurements reported by UEs. Locations of neighbouring access points are estimated using several accumulated received signal power measurements taken at different positions.
[0024] The described approach does not need prior knowledge of the locations of devices that are deployed. That is, the approach does not rely on position information which could, for instance, be gathered from GPS facilities integrated into devices. While many devices now have such facilities, users may deactivate such facilities for privacy or power consumption reasons, or the facilities may not be available in certain environment (such as indoors).
[0025] Instead, the approach employed by embodiments described herein relies on the collection of measurements made at devices, and makes SIR predictions based on those measurements. The examples disclosed herein make REM predictions of SIR based on RSRP and/or MDT reports, in the context of an LTE based implementation.
[0026] The measurements are accumulated to determine the radio environment. These predictions are used in a constraint policy to determine conflicts. The conflicts are avoided by “excluding” them in a process of assigning radio resource blocks to particular stations in the network.
[0027] Operationally, a characteristic of embodiments described herein is the manner in which the REM is used to collect the measurements in order to make predictions without using location information. Another characteristic is the way in which excluded resource assignments are applied, using the “conflicts” detected by REM SIR estimation. Exclusion is achieved using a sequential “order” of resource block selection. The following description of embodiments will set out an example of a way in which the “order” can be deduced (using the information from REM) and then used to avoid interference.
[0028] The coordinated scheduling scheme of the described embodiments uses the REM predictions of the UE and HeNB SIR (in the context of an LTE implementation) to coordinate RB allocation that attempts to avoid interference. In this approach, interference avoidance is achieved by allocating RBs sequentially as well as avoiding conflicting RB allocations. A SIR threshold (SIRT) is applied to the predicted SIR levels in order to determine whether unacceptable interference may occur. It is also assumed that retransmissions and DL traffic take priority.
[0029] In this scheduling approach the REM user obtains SIR estimates and uses this for restricting the RB scheduling through a constraint policy which identifies the excluded RBs based on these SIR predictions.
[0030] The result of the constraint policy, as laid out in the described embodiments, is the identification of conflicts, which are then assigned resources using the EXCLUDE order in an opposite sequential direction to the normal order, with the direction determined by the respective indices, for instance, with i<j ascending and i>j descending.
[0031] Accordingly, FIG. 1 illustrates a typical wireless communications network 10 , including an access point 110 and numerous wireless communications devices 120 . A neighbouring access point 110 ′ is also illustrated.
[0032] Expected lines of communication are indicated by solid arrows. The access points 110 , 110 ′ provide connection facilities to a wider network (typically referred to as “backhaul”), for example to access communications facilities such as the internet. This can be by, for instance, a physically wired network, such as telephone networks or cable networks, power line communication or fibre optics, or by wireless communications media.
[0033] The present example is concerned with the manner in which the access point 110 manages the allocation of radio resource in establishing communication with the wireless devices 120 .
[0034] As shown in FIG. 2 , the access point 110 is a relatively generic computing device, configured by specific software to implement the described embodiment. To that end, the access point 110 comprises a processor 130 operable to execute computer executable instructions presented to it. A working memory 132 (which would normally comprise volatile and non-volatile memory components) stores program components, such as administrator applications 134 for use by an administrator of the access point and other operating programs, in particular, a communications controller 136 configuring the access point 120 in accordance with the described embodiment.
[0035] A mass storage unit 140 provides bulk data and program storage facilities—normally, mass storage comprises a high volume storage medium which may have relatively slow access speed, certainly in relation to the working memory 132 , and the processor 130 will access data and code stored in the mass storage unit 140 as required, usually storing the same in the working memory 132 for rapid access for convenience.
[0036] A bus 142 provides access by the processor 130 to other components of the access point 120 . In particular, a wireless communications unit 150 is effective to establish radio frequency communication with other devices, in a predetermined band of frequencies specified by a technical standard. In this example, the LTE standard is employed, but the reader will appreciate that this is not essential to an appreciation for the present disclosure.
[0037] A USB port 152 enables connection of the access point 120 to another device, such as a PC based computer, such as to enable wired connection to the services offered by the access point 120 or to enable configuration and control thereof.
[0038] A backhaul interface unit 154 enables connection of the access point to a backhaul facility, such as a cable modem or a telephone line, so that the access point 120 can access facilities offered on such a backhaul installation, for example internet based services.
[0039] FIG. 3 is a representation of the LTE radio frame illustrating resource block structure in TDD (time division duplex) mode. It illustrates the resource available for allocation by the access point.
[0040] As illustrated, each radio frame is a two-dimensional array of resource blocks defined by ten subframes (denoted TRB#), numbered from 0 to 9, covering twelve frequency subcarriers (FRB#) numbered from 0 to 11.
[0041] Within the radio frame, resource blocks in subframes TRB 0 and TRB 5 are reserved for downlink (denoted ‘D’), while resource blocks in subframes TRB 1 and TRB 6 are reserved for synchronisation (denoted ‘S’).
[0042] Each frame is composed of ten subframes, each of which comprise two slots. A resource block is denoted by reference to a slot of a subframe TRB#, carried across the 12 subcarriers FRB#. Within a resource block, resource elements are defined, within which symbols can be transmitted.
[0043] Allocation of these resource blocks as uplink or downlink (except for the reserved resource blocks, as detailed above) is the responsibility of the access point. This allocation is established by way of a process whose architecture is illustrated in FIG. 4 .
[0044] In the embodiment illustrated in FIG. 4 , a resource allocation coordination manager 200 is implemented, for example by firmware or software, including a network information acquisition and storage facility 204 able to gather and store report from stations 130 in the network. Then, an REM manager 202 is operable to process the acquired and stored information, to obtain a radio environment map (REM). The estimated SIR is then passed to a resource block scheduler 206 which generates resource block allocation messages back to the stations 130 .
[0045] Each station 130 reports to the access point 120 on received signals attributable to other stations and access points in the network. For example, in LTE, each station 130 reports Reference Signal Received Power (RSRP) measurements. From this information, candidates can be determined for predictions of signal to interference ratios for signals received around the network. FIG. 5 a illustrates a simple example of this, for a situation where a station (with index i) is positioned at a position with coordinates (x i. , y i ) and another (with index j) at (x j. , y j ) can be in receipt of signals from two access points (with indices 1 and 2 respectively). The two access points are positioned with coordinates (−c,0) and (c,0), respectively, on a nominal two dimensional reference frame. The reader will appreciate that a two dimensional reference frame is used here, but that this analysis would be extendable to a three dimensional reference frame without difficulty.
[0046] As shown in FIG. 5 a , b i , and d i represent distance between the station at (x i. , y i ) and the respective access points. RSRP levels are collected by the station for signals received from the two access points, these levels are denoted z 1,i and z 2,i respectively. The quantity c is the separation between the access points and a midway reference point (0,0).
[0047] A working assumption in this analysis is that this midway point is that point where the same RSRP would be received from each access point (assuming equal transmit power). The validity of this assumption could be tested with accumulation of data over time.
[0048] Thus, the location of the station can be computed as follows:
[0000] b i =√{square root over ( y i 2 +( c+x i ) 2 )} and d i =√{square root over ( y i 2 +( c−x i ) 2 )}
[0049] Assuming b i /c=r i and d i /c=s i ;
[0000] then
[0000]
x
i
=
c
(
r
i
2
-
s
i
2
)
4
and
y
i
=
c
s
i
2
-
[
1
-
(
r
i
2
-
s
i
2
)
4
]
2
[0000] where r i and s i are defined as relative distances from the respective access points to the station, as a ratio to half the access point separation c, which is estimated by determining the midway reference point (0,0), where the measured signal levels are z 0,i .
[0050] This is useful, as the evaluation of r i and s i does not require absolute measurements, but rather as ratios, respectively, of z 1,i and z 2,i to z 0,i . Further, if the measured signal levels are reported on a logarithmic scale, then ratios are re-expressed as differences, and the computational effort required to derive r i and s i is further eased, so:
[0000] 10α log( r i )= z 1,i −z 0,i and
[0000] 10α log( s i )= z 2,i −z 0,i
[0051] In each of these cases, no knowledge is required of the transmit powers of the access points. α is a path loss exponent. This can be estimated by numerical methods as more data is collected, although it may also be possible to start with a working assumption based on past experience.
[0052] From this analysis, it therefore follows that the download Signal to Interference Ratio (SIR), at any station (UEi) for a signal from one access point (AP1) interfered by a signal from another access point (AP2), is given by:
[0000] HeNB SIR 1,2 =10α log( b i /d i )=10α log( r i /s i )= z 1,i −z 2,i
[0000] and evidently vice versa by:
[0000] HeNB SIR 2,1 =10α log( d i /b i )=10α log( s i /r i )= z 2,i −z 1,i
[0000] where i denotes the index of the station (UE).
[0053] Likewise for any two selected UE locations (i.e. denoted by index 1 and 2 associated with AP1 and AP2 respectively), as shown in FIG. 5 b , the expression for the uplink SIR resulting from the signal from one UE (UE2) on the signal from another (UE1) is given by:
[0000] UL SIR 1,2 =10α log( d 2 /d 1 )=10α log( s 2 /s 1 )= z 2,2 −z 2,1
[0000] and evidently vice versa by:
[0000] UL SIR 2,1 =10α log( b 1 /b 2 )=10α log( r 1 /r 2 )= z 1,1 −z 1,2
[0054] Further, for time division duplex (TDD) communications, it is also important to consider the effect of interference when the uplink and downlink are not aligned. For example, an arrangement could be contemplated where two stations are associated with respective access points and use resource blocks at the same time as the access points. The stations are positioned at points (x 1 , y 1 ) and (x 2 , y 2 ) denoted by UE1 and UE2 respectively. Indexing the distances between the stations and the access points in the same way as is illustrated in FIG. 5 b , the SIR for a signal, received at a location UE1 (associated with the AP1), with respect to interference from UE2, is:
[0000]
UE
SIR
1
,
2
=
10
log
α
(
(
y
1
±
y
2
)
2
+
(
x
1
-
x
2
)
2
d
1
)
=
10
log
α
(
(
y
1
±
y
2
)
2
+
(
x
1
-
x
2
)
2
cs
1
)
[0055] Likewise for the SIR for a signal, received at a location UE2 (associated with the AP2), with respect to interference from UE1 is:
[0000]
UE
SIR
2
,
1
=
10
log
α
(
(
y
1
±
y
2
)
2
+
(
x
1
-
x
2
)
2
b
2
)
=
10
log
α
(
(
y
1
±
y
2
)
2
+
(
x
1
-
x
2
)
2
cr
2
)
[0056] Using the equal power assumption, therefore, the reference distance c can be cancelled, implying that the actual positions of access points is not required for this analysis.
[0057] The reader will note that the geometric analysis as laid out above can give rise to plural results, because of the dual solutions to quadratic problems, as represented by the use of the ±operator above.
[0058] However, this can be resolved over time. It will be appreciated that, in many cases, stations would be expected to move over time, but not so quickly that they cannot be tracked between one measurement opportunity and the next. Using successive reports, the acquisition of information can lead to certain candidate solutions being rejected, as being inconsistent, and for other candidate solutions to be retained in favour. Thus, as time progresses, the resultant radio environment map (REM) will resolve into SIR and station position information with high degrees of confidence associated therewith.
[0059] FIG. 6 then illustrates a process by which this information, built into a REM, can be harnessed to allocate resource in the wireless communications system 100 in which resource blocks are defined in time and frequency.
[0060] Reports are received from time to time from stations 120 . In this process, it is assumed that reports are received periodically, but other arrangements may be provided depending on the implementation. In the first step S 1 - 2 of the process, therefore, reports are acquired from each station associated with an access point. These reports, containing signal measurement vectors z (or relative values), are then used, in step S 1 - 4 , to update the REM. REM computes the SIR estimates using the data collected from all of the stations 120 .
[0061] Each access point 110 pair and each station pair 120 is then tested against a rule in step S 1 - 6 and is designated as belonging to one or more EXCLUDE groups on the basis of that test. In this embodiment, a typical rule for each node (denoted i and j) is:
[0000] IF {HeNB SIR i,j <SIR T } THEN EXCLUDE j
Likewise for each UE 120 pair, denoted (i,j) the typical rule is:
IF {UL SIR i,j <SIR T } OR {UE SIR i,j <SIR T } THEN EXCLUDE i,j
Alternative rules are:
IF {UL SIR i,j <SIR T } OR {UE SIR i,j <SIR T } THEN EXCLUDE j
IF {UL SIR i,j <SIR T } OR {UE SIR i,j <SIR T } THEN EXCLUDE i
where the SIRT threshold margin is a constant selected according to the desired target. In one example, SIRT could be 10 dB.
[0062] That is, for any acquired SIR statistic or estimate then, if the SIR of that signal pair is lower than the threshold, the corresponding stations are designated within one of the EXCLUDE groups.
[0063] Thus, for any access point, its associated terminal stations (UE) may be designated within the EXCLUDE groups. These are expressed, in this embodiment, as lists as set out in FIG. 7 . This designation determines the way in which resources are subsequently allocated.
[0064] In step S 1 - 8 , a routine is called to update, store and if necessary distribute the corresponding station lists designated as EXCLUDE using the above rule. This depends on where the lists are generated, which can be centrally or locally within each access point (REM manager, 202 ).
[0065] The aforementioned lists in step S 1 - 10 are used in the resource allocation process of each access point, in an independent manner, as illustrated in FIG. 8 . In this routine, an initialisation step S 2 - 2 starts the normal round robin processing of resource requests, starting with the downlink (DL). If the selected station is on the excluded list, as determined in step S 2 - 4 , the exclude allocation sub process is performed in step S 2 - 8 (according to FIG. 10 ), otherwise the normal allocation sub process is performed in step S 2 - 6 (according to FIG. 9 ).
[0066] The normal allocation sub process, in step S 3 - 2 , initialises corresponding TRB and FRB pointers to the start of the subframe, in time, and at a midway point in frequency respectively. For instance, when there are multiple subframes per frame in time TRB is set to the beginning of the first subframe and resource blocks allocated, in S 3 - 8 , in accordance with the requests, in step S 3 - 4 , providing the sufficient resources are available, as determined in step S 3 - 6 .
[0067] Likewise, if the request under consideration, in step S 2 - 2 , corresponds to a station on the EXCLUDE list, the allocation process called is set out in FIG. 10 . In this case, by contrast, the starting point for allocation of resource requests, in step S 4 - 2 , is half a frame (i.e. a subframe) and half the frequency bandwidth distant to that in S 3 - 2 . This offers improvement of separation of the potential interferers which are contained in the EXCLUDE list. An initialisation step S 4 - 2 implements this on the start of each frame allocation process.
[0068] Then, similar to the earlier described procedure, step S 4 - 4 establishes an allocation process by selecting a resource request corresponding to the station on the EXCLUDE list. This resource request is then tested in step S 4 - 6 to determine if it can be fulfilled. If it can, then in step S 4 - 8 the resource is allocated, and the pointers for next allocation are updated. Step S 4 - 10 acts to remove the resource requests once allocated.
[0069] Step S 4 - 12 is a check to determine if there are more pending resource requests. If there are, the routine returns to step S 4 - 4 otherwise it terminates.
[0070] Following this, and returning to FIG. 8 , a step S 2 - 10 determines if the resource blocks are fully allocated or if all resource requests have been dealt with, returning to step S 2 - 2 if this is not the case, or moves to the uplink phase. If the uplink phase has not already been completed, as determined in step S 2 - 11 , the process proceeds to the uplink (UL) allocation phase, which is initialised in step S 2 - 12 and thence to step S 2 - 2 as before. Once the uplink phase is complete, the process terminates for that frame.
[0071] The reader will appreciate that the resource allocation process laid out above is but one example. The guiding principle, in general terms, is to identify potential interferers using the REM. Then, the EXCLUDE designated resource requests are distinguished, in the resource allocation process to separate, as far as possible, the allocated resource blocks that could cause interference, thereby reducing the possibility of interference.
[0072] In the example above, requests are handled in a round robin manner. This may be desirable in some circumstances, but not in others. Therefore, modifications to the above processes may offer different approaches which provide different prioritisation, while also accommodating the above general principle, which remains unchanged.
[0073] For instance, FIG. 11 illustrates a second example of a resource block allocation process. In this example, steps S 5 - 2 and S 5 - 4 are the same as steps S 1 - 2 and S 1 - 4 described above. However, in step S 5 - 6 , two EXCLUDE lists are generated. In this case, one EXCLUDE list contains station indexes (i) and the other (j), as depicted in FIG. 13 , in which nodes i may suffer interference from nodes j. This enables resources for each pair to be further separated beyond that possible with a single EXCLUDE list. The result of this can best be seen in FIG. 14 , which shows the two sorted EXCLUDE lists which correspond to two separate EXCLUDE resource allocation starting points. These starting points are separated further than previously achieved with a single EXCLUDE list, thus providing more certainty in avoiding interference.
[0074] This approach can be illustrated schematically as two EXCLUDE lists set out in FIG. 13 . For instance with indexes i and j, if i<j it indicates that i should use a start point 1 and j start point 2. Hence, two separate sorted allocation lists are generated from the EXCLUDE lists. The resulting sorted lists are indicated in FIG. 14 . The lists can be further sorted based on a priority order (for instance using the index as an example) as indicated in FIG. 15 and used in the final allocation lists.
[0075] Yet a further approach to this resolution of EXCLUDE lists can be understood from a routine set out in FIG. 12 . The process commences by sorting the exclude lists into allocation lists, as in FIG. 14 or FIG. 15 , in step S 6 - 2 . In this routine, an initial step, S 6 - 2 , is carried out to resolve the two lists into prioritised sorted lists, as set out in FIG. 15 . The principles governing this sort are as follows. Firstly, the priority of requests is respected as an overriding sort criterion for each starting point. For requests with equal priority, if this is possible, the prioritised sort order can be made by the unique station index i and j for the two starting points respectively.
[0076] Other sort approaches would equally be possible.
[0077] Then, the allocation lists are processed, by selecting each allocation list in turn, starting with the downlink in step S 6 - 4 . The first list is designated to starting point 1, and is allocated according to the rules in step S 6 - 8 . If there are still resources available and more entries in the list, as determined in step S 6 - 9 , the process is repeated. This list is designated to starting point 2, and is allocated according to the rules in step S 6 - 10 . If there are still resources available and more entries in the list, as determined in step S 6 - 12 , the process is repeated.
[0078] After that, the uplink phase is started in step S 6 - 16 , if it has not been completed as determined at step S 6 - 14 , in an identical manner to the downlink phase.
[0079] FIG. 16 illustrates the contrast between the NORMAL allocation rule and the EXCLUDE allocation rules with two starting points, according to the examples described above. As can be seen, there will be some pre-allocation of resource to downlink communication by the access point, as indicated by shading. Then, if the NORMAL rule is applied, allocation commences from the mid-spectrum point, and from timeslot 0, while in the one EXCLUDE allocation list the starting point is at the end of the first subframe and the lower edge in frequency, while the other starting point is at the end of the second subframe and the upper edge in frequency.
[0080] In fact, as the reader will appreciate, the exact scheme of the EXCLUDE allocation rules versus the NORMAL allocation rule is immaterial. It is desirable that they are distinctive, to the extent that the resource allocation on one rule differs from the resource allocation on the other, to reduce the possibility of two resource allocations, of potentially interfering stations, being adjacent to each other. No set of rules will completely eliminate the possibility of interference, unless joint scheduling of all access points is performed, but the presently described approach provides mitigation without the need and complexity of joint scheduling.
[0081] While certain embodiments have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. Indeed, the novel methods and systems described herein may be embodied in a variety of other forms; furthermore, various omissions, substitutions, and changes in the form of the methods and systems described herein may be made without departing from the spirit of the inventions. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the inventions. | Radio resource allocation is carried out on the basis of a radio environment map. The radio environment map is constructed based on received reports of signal quality and/or strength. Using history and triangulation, estimates of station positions can be determined, and expectations can be determined for interference between stations and between stations and access points. Resource requests can then be fulfilled on the basis of separate treatment of requests which have little potential for causing interference, and those which have potential to cause interference. | 7 |
This application claims priority to U.S. Provisional Application Nos.: 60/075,966 filed Feb. 24, 1998 and 60/085,474, filed May 14, 1998 which are incorporated herein in their entirety.
TECHNICAL FIELD
The present invention relates to peptide-like compounds, e.g. aminocarboxylic acid amide derivatives, and to methods of using same to stimulate cells of the immune system, bone marrow and other organs. The present compounds can be used to enhance vaccination, increase synthesis of and enhance function of blood cell components and enhance anti-neoplastic effects of various agents. The compounds of the invention can be used to produce a variety of further pharmacologic effects.
BACKGROUND
A variety of polypeptide cytokines, hormones and immune system modulators have been used to stimulate production and activity of bone marrow-derived cells. However, little progress has been made in obtaining the same physiologic activities in culture and in vivo using simple, chemically synthesized small molecules. For example, there are relatively few reports of the use of simple, small molecules in stimulating production and function of various blood components, including, without limitation, red blood cells (RBCs) and white blood cells (WBCs), in stimulating the response to vaccinations, in enhancing differentiation and in the nontoxic treatment of neoplasia. The present invention relates to such methods, as well as others, and to compounds suitable for use in same.
OBJECTS AND SUMMARY OF THE INVENTION
It is an object of the present invention to provide compounds that exert an immunomodulatory effect. It is another object of the invention to provide a method of altering (e.g. stimulating) cellular productivity and vitality and to provide a method of modulating cell growth.
It is a specific object of the invention to provide a method and compositions for modulating immune function, for example, to facilitate vaccination against or treatment of diseases, including infectious and autoimmune diseases, as well as other diseases in which the immune system plays a role.
It is another specific object of the invention to provide a method of effecting blood cell stimulation (including RBCs, WBCs, stem cells, platelets and others).
It is a further specific object of the invention to provide a method of enhancing cell differentiation and cell growth and a method of exerting an anti-senescence effect in vitro and in vivo. It is also a specific object of the invention to provide a method of preserving viability of neurons, natural killer (NK) cells, fibroblasts and other cell types in vivo and in vitro. It is a further specific object of the invention to provide a method of exerting anti-Alzheimer and anti-aging effects and a method of treating genetic diseases related to aging. It is a further object of the invention to provide a method of enhancing bioactivity of cosmetics and compounds to serve as cosmeceuticals.
It is also a specific object of the invention to provide a method and compositions for treating a neoplastic or preneoplastic condition. It is another object of the invention to provide a method of an ameliorating side effects of various anti-neoplastic agents.
It is a further specific object of the invention to provide a method of altering (e.g. stimulating) cellular protein production, including antibody production.
The foregoing objects are met by the present invention which provides aminocarboxylic acid amide derivatives that can be used to produce a variety of biomodulatory effects, both in vivo and in vitro.
Further objects and advantages of the present invention will be clear from the description that follows.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows synthetic reaction schemes.
FIG. 2 shows specific compounds of the invention bearing carbon designations.
FIG. 3 shows specific compounds of the invention.
DETAILED DESCRIPTION OF THE INVENTION
In a first embodiment, the present invention relates to compounds of the formula (I):
wherein:
A is a group of the formula —PO 3 H, —SO 3 H, —OPO—(OH) 2 , —OSO 2 OH, or —SH, or pharmaceutically acceptable salt thereof or physiolocally-hydrolyzable derivative thereof, or disulfide thereof when A is —SH. Suitable salts include sodium, potassium, calcium and zinc. Suitable hydrolyzable derivatizing groups include esters, such as substituted or unsubstituted lower alkyl (e.g. C 1 to C 4 ) or arylalkyl (e.g. benzyl) esters;
R 1 is H, a linear or branched lower alkyl, for example, a C 1 to C 6 alkyl, arylalkyl, for example, wherein the alkyl moiety is C 1 to C 4 alkyl and the aryl moiety is a substituted (e.g. lower alkyl or halogen) or unsubstituted phenyl group, or alkenyl (for example, C 2 -C 6 alkenyl);
R 2 is H, a linear or branched lower alkyl, for example, a C 1 to C 6 alkyl, an alkenyl, for example, a C 2 -C 6 alkenyl, an arylalkyl, for example, wherein the alkyl moiety is a C 1 to C 4 alkyl and the aryl moiety is a substituted (e.g. lower alkyl or halogen) or unsubstituted phenyl group; or an acyl, for example, acetyl, benzoyl, arylsulfonyl (for example, when the aryl moiety is phenyl); a carbonate ester such as alkoxycarbonyl (e.g., C 1 -C 7 alkoxy carbonyl) (for example, —OCOC(CH 3 ) 3 ); allyloxy carbonyl (e.g. —OCOCH 2 CH═CH 2 ); cycloalkoxycarbonyl (e.g. when the ring is C 3 -C 8 (C 5 -C 6 being preferred) and when the alkoxy moiety is C 1 -C 8 ) (for example —OCOCH 2 C 5 H 9 ); or an unsubstituted arylalkoxycarbonyl (for example —OCOCH 2 C 6 H 5 ) or a substituted arylalkoxycarbonyl wherein the substituent is, for example, a halogen, a nitro group, an amino group or a methoxyl group;
alternatively, R 1 and R 2 taken together form, with the nitrogen to which they are attached, a 5 to 7 membered ring (for example, R 1 and R 2 taken together can be —(CH 2 ) 4 —, —(CH 2 ) 5 or —(CH 2 ) 6 —); and
L 1 and L 2 are hydrocarbon linking groups, for example, a linear or branched chain alkyl of the formula —(C n H 2n )— wherein n is, for example, 1 to 8 in the case of L 1 and 2 to 8 in the case of L 2 except when A is —PO 3 H or —SO 3 H in which case n can be 1-8; a cycloalkyl of 3 to 8 carbon atoms, preferably 5 or 6 carbon atoms; or an interphenylene
Advantageously, L 1 and L 2 are —(C n H 2n )— wherein n is 1 to 8 in the case of L 1 or 2 to 8 in the case of L 2 except when A is —PO 3 H or —SO 3 H in which case n can be 1-8 (examples of branched chain alkyls include —CH 2 CHR—, —CH 2 CHRCH 2 —, —CHRCH 2 CH 2 —, and —CH 2 CH 2 CHR— wherein R is an alkyl group and wherein the total number of carbon atoms, including R, does not exceed 8).
A particular group of compounds of the invention is of the formula (I) wherein A, R 1 , R 2 , L 1 and L 2 are as defined above in said first embodiment with the proviso that when A is —SO 3 H or pharmaceutically acceptable salt thereof or physiologically hydrolyzable derivative thereof, one of R 1 and R 2 is H, and L 1 and L 2 are (CH 2 ) 2 , then the other of R 1 and R 2 is not H.
Another particular group of compounds of the invention is of the formula (I) wherein A, R 1 , R 2 , L 1 and L 2 , are as defined above in the first embodiment with the proviso that when A is —SO 3 H or pharmaceutically acceptable salt thereof or physiologically hydrolyzable derivative thereof, one of R 1 and R 2 is H, and L 1 and L 2 are (CH 2 ) 2 , then the other of R 1 and R 2 is not C 6 H 5 CH 2 OCO—.
A further particular group of compounds of the invention is of the formula (I) wherein A is a group of the formula —PO 3 H or —OPO(OH) 2 , more particularly —PO 3 H, or a pharmaceutically acceptable salt thereof or a physiologically hydrolyzable derivative thereof, and wherein R 1 , R 2 , L 1 , and L 2 are as defined above in the first embodiment.
Another particular group of compounds of the invention is of the formula (I) wherein A is a group of the formula —SO 3 H or —OSO 2 OH, more particularly —OSO 2 OH, or pharmaceutically acceptable salt thereof, or physiologically hydrolyzable derivative thereof, and wherein R 1 , R 2 , L 1 and L 2 are as defined above in the first embodiment. The provisos above can apply to this group of compounds as well.
A further particular group of compounds of the invention is of the formula (I) wherein at least one of R 1 and R 2 is an alkyl, advantageously a lower alkyl (e.g. C, to C 6 ), and wherein A, L 1 , L 2 and the other of R 1 and R 2 are as defined above in the first embodiment.
Another particular group of compounds of the invention is of the formula (I) wherein R 1 is an alkyl and R 2 is acyl and wherein A, L 1 and L 2 are as defined above in the first embodiment.
A further particular group of compounds of the invention is of the formula (I) wherein L 1 is —(CH 2 )— and wherein A, R 1 , R 2 , and L 2 are as defined above in the first embodiment.
Yet another particular group of compounds of the invention is of the formula (I) wherein R 1 and R 2 are taken together and form, with the nitrogen to which they are attached, a 5 to 7 membered ring, and wherein A, L 1 and L 2 are as defined above in the first embodiment.
The present compounds can also be present covalently bound to proteins, for example, antigens or other immunologically active proteins, or cell targeting proteins. Such conjugates can be synthesized using techniques known in the art.
The compounds of the present invention can be prepared using, for instance, methods provided in the Examples and in U.S. Pat. Nos. 4,102,948 and 4,218,404, as appropriate.
In another embodiment, the present invention relates to methods of using the above-described compounds in vivo and in vitro to alter (e.g. increase) cellular productivity and vitality and to modulate cellular differentiation, growth and/or function.
In vivo, the compounds can be used to elicit a variety of responses, including simulating bone marrow and platelet production, stimulating erythropoiesis, altering (e.g. increasing) immunogenic responsiveness and treating neoplasia. For example, the present compounds can be used to treat anemia and neutropenia. The compounds of the invention can be used to treat or prevent premature aging and degenerative diseases and to treat inherited metabolic diseases. The compounds of the invention can be used in the treatment of diseases of immune dysfunction including, without limitation, autoimmune diseases such as rheumatoid arthritis, diabetes, thyroiditis, lupus (SLE), connective tissue diseases, multiple sclerosis, sarcoidosis, psoriasis, hepatitis, and kidney diseases. The compounds can be used, for example, in the treatment of genetic diseases of aging (Ataxia telangiectasia, progeria and Werner's syndrome), in accelerated aging (as compared to the ultimate biologic potential of the organism), and in the treatment of Alzheimer's disease. The present compounds can be used to delay sensecence of fibroblasts, neural, lymphoid, epithelial, endothelial, mesenchymal, neuroectoderm, mesothelial and other cells, and to maintain function and health of aged cells and organisms.
The compounds can be used to cause an alteration in the number of cells of a particular cell type (e.g. epithelial cells or mesenchymal cells) (the compounds can be used, for example, to increase the number of red cells or white cells or the numbers of neuronal cells) or to cause an alteration in cellular function (e.g. an increase phagocytic activity of macrophage).
From the standpoint of immunogenic responsiveness, the present compounds can be used to enhance antigen processing, cell to cell communication, cellular immunity, natural immunity, humoral immunity, macrophage function, NK cell function, immune surveillance, immune response and immune killing. Further, the compounds of the invention can be used in conjunction with vaccination protocols to alter (e.g. increase) the response elicited by an antigen or an immunogenic conjugate. The present compounds can be used in vaccinations against infectious, neoplastic, autoimmune and other diseases. Specifically, the present invention can be used to enhance vaccinations to bacterial and viral diseases, for example, pneumonia, meningitis, TB, hepatitis B and HIV and to parasitic diseases. Further examples include bacterial diseases: Pyogenic cocci (staphylococci, pharyngitis, tonsillitis, sinusitis, streptococci, pneumococci, meningococci, gonococci), enteric bacilli ( Escherichia coli, Klebsiella, Salmonella shigella ), cholera, pseudomonas ( Pseudomonas aeruginosa, Pseudomonas mallei ), bacteroides, mycobacteria (tuberculosis), spirochetes ( Treponema pallidum (syphilis)), clostridia, Diphtheria hemophilus and Bordetella bacilli, Granuloma inguinale, brucella, tularemia, anthrax, plague, mycoplasma, listeriosis; rickettsial disorders: typhus group, Rocky Mountain spotted fever, Lyme disease, scrub typhus, Q fever; chlamydial disorders: trachoma and inclusion conjunctivitis, lymphogranuloma venereum, and psittacosis; viral diseases: cutaneous viral infections (chickenpox, herpes zoster, measles), respiratory viral infections, viral diseases of the central nervous system, viral diseases of the liver, viral diseases of the salivary glands, and infectious mononucleosis; fungal diseases: candida albicans, mucor, histoplasmosis, aspergillosis, blastomycosis, coccidioidomycosis, actinomycosis and nocardiosis; and protozoal (parasitic) diseases: pneumocystosis, amebiasis, malaria, toxoplasmosis, leishmaniasis, trypanosomiasis, and giardiasis; helminths diseases (worms): trichinosis, strongyloidiasis, enterobius vermicularis, filariasis, hookworm disease, ascariasis, flukes, cestodes, tapeworms, and trichuriasis; and other diseases: sarcoidosis, cat-scratch disease, legionnaires' disease.
The compounds of the invention can also be used to inhibit the toxicity associated with immunotoxic and carcinogenic agents.
Depending on the effect sought and the clinical situation, the compounds of the invention can be administered before, during or after vaccination. Use of the present compounds can result in more effective injections and/or a reduction in the number of injections necessary for vaccination. The present compounds can also be used to treat infections, including chronic infections.
In a specific embodiment, the invention relates to a method of effecting isotype conversion using the compounds of the present invention. As shown in Example IX, the present compounds can be used to effect rapid induction of immunoglobulin G. These data demonstrate that the present compounds can be used to elicit a rapid response to a vaccine thereby reducing the number of injections necessary and/or increasing the efficiency of the each injection. The compounds of the invention can also focus antibody production of the polysaccharide and thus effect excellent responses to polysaccharide antigens, whether or not conjugated to a protein carrier.
As to neoplasia treatment, the compounds of the invention can be used to treat a variety of preneoplastic and neoplastic conditions, including both soft (e.g. hematolymphoid) and solid tumors (e.g. carcinomas and sarcomas). More specifically, the compounds of the invention can be used to treat breast cancer, prostate cancer, glioblastomas, melanomas, myelomas, lymphomas, leukemias, lung cancer, skin cancer, bladder cancer, kidney cancer, brain cancer, ovarian cancer, pancreatic cancer, uterine cancer, bone cancer, colorectal cancer, cervical cancer and neuroectodermal cancer, and premalignant conditions, including, without limitation, monoclonal gammapothies, dysplasia, including, without limitation, cervical and oral dysplasia. The compounds can also be used to treat conditions associated with altered differentiation (e.g. loss of pigmentation, hair; alteration of skin including psoriasis; alteration of gastrointestinal, kidney, liver, brain, endocrine, immune, lung, connective tissue, cardiac or other organ function).
The compounds of the invention can also be used to inhibit the toxicity associated with immunotoxic and carcinogenic agents. Conventional chemotherapeutic agents are highly toxic and have narrow therapeutic indices. Although conventional anticancer agents exhibit a certain degree of specificity for malignant cells, other rapidly proliferating cells, such as bone marrow cells, spermatogonia and cells of the gastrointestinal crypt epithelium, are very vulnerable to the toxic side effects of these agents. Cytotoxic agents can induce virtually every type of pathology on organ systems. Careful management of toxicity is therefore of paramount importance in managing patient care and there is a great need to diminish the toxicity of known anticancer agents. This is accomplished (i) by decreasing the effective dose of the toxic agent(s) to diminish the side effects without compromising effectiveness, or (ii) by decreasing toxicity where high doses of the agent(s) must be used, or if toxicity occurs over time even with relatively low doses.
It has now been discovered that compounds of Formula I including β-alethine, decrease the toxicity of known anti-cancer agents. Thus, the present invention is directed to new, less toxic anticancer pharmaceuticals which are mixtures that include one or more compounds of Formula I (β-alethine) and one or more known anticancer agents that can be either cell-cycle-specific or cell-cycle-nonspecific, and to methods of preventing or treating cancer by administering these compositions. It has also been discovered that combining compounds of Formula I combined with known anti-cancer agents produces a synergism in treating, preventing, and delaying the clinical appearance of primary cancer or metastatic cancer. One or more of the compounds of Formula I can be combined with one or more chemotherapeutic agents known to be effective in treating cancer, including but not limited to TAXOL™, cyclophosphamide, melphalan, levamisol NAC,5 fluorouracil, Methotrexate, Cisplatin, Carboplatin, Cyclophosphamide and Ifosfamide, Bleomycin, mAMSA, Streptozotocin, hydroxyurea, Etoposide, Doxycoformycin, Fludarabine, Chlorodeoxyadenosine, Doxorubicin and daunorubicin, Paclitaxel, Vincristein, Vinblastine, mAMSA, ThioTEPA, Epirubicin, 5-Fluorouracil, 6-Mercaptopurine, L-Phenylalanine mustard, MDR, MRP, Topoisomerase I, Topoisomerase II, Toxal, Vincristine, Vinblastine, Vindesine, VP-16, VM-26, Dactinomycin, Doxorubicin, Idarubicin, Mithramycin, Mitomycin-C, Bleomycin, Methotrexate, w/leucovorin, Methotrexate, 5-Fluorouracil, 5-Flourouracil w/leucovorin, 5-Fluorodeoxyuridine, 6-Mercaptopurine, 6-Thioguanine, Cytarabine, 5-Azacytidine, Hydroxyurea, Deoxycoformycin, Fludarabine, Cyclophosphamide, Ifosfamide and Mesna, Melphalan, CCNU, MeCCNU, BCNU, Chlorambucil, CBDCA (carboplatin), Aziridinylbenzoquinone (AZQ), DTIC (Dacarbazine), mAMSA, Procarbazine, Hexamethylmelamine, and Mitoxantrone.
This invention is also directed to methods of treating cancer or delaying the clinical appearance of cancer, by administering therapeutically effective amounts of the new β-alethine-containing anticancer mixtures. Cancer is typically treated by combination chemotherapy with the goal of controlling cancer cell proliferation and minimizing tumor burden. To ensure lysis of proliferating and resting cancer cells, combination chemotherapy is typically administered in cycles and drug combinations are chosen which have different mechanisms of action, produce synergy, and possess minimal overlapping toxicity. Chemotherapeutic agents are classified as either cell-cycle-specific agents which include plant alkaloids such as taxanes, or cell-cycle-nonspecific agents which include alkylating agents that alter DNA structure, such as cyclophosphamide and melphalan, antitumor antibiotics and hormones.
The most common dose-limiting side effect of chemotherapy is myelosuppression which, although generally reversible, in some cases causes death due to infection and bleeding complications. TAXOL™ is a well-known cell cycle-specific plant alkaloid agent used tp treat breast cancer. TAXOL™ is highly toxic and causes marked myelosuppression effects including neutropenia and thrombocytopenia, as well as cardiotoxicity. Serious toxic effects also result when the cell cycle-nonspecific agent cyclophosphamide is administered to treat melanoma or breast cancer, and when melphalan is administered to treat myeloma. These drugs are associated with causing moderate to marked myelosuppression, pulmonary toxicity, cardiotoxicity and neurotoxicity. Lippincott's Cancer Chemotherapy Handbook, D. C. Baquiran and J. Gallagher, 1-10, 59-107, 1998.
β-alethine (BT) has been reported to be an effective an anti-cancer agent when administered alone for treatment of all cancers, regardless of cell-lineage or phenotype. It has now been discovered that the addition of β-alethine and structurally or functionally similar compounds of Formula I to one or more other known anti-cancer agents decreases the toxicity observed when an equivalent doses of the anticancer agent(s) is administered alone. Further, β-alethine and structurally and functionally similar compounds of Formula I have a synergistic effect on preventing, treating or delaying the clinical appearance of cancer over administering either β-alethine or the anticancer agent alone. These results have been observed when Formula I compounds are combined anti-cancer agents drawn from both cell-cycle-specific and the cell-cycle-nonspecific categories. The embodiments of the present invention include the administration of compounds of Formula I to promote tumor regression, shorten the time to cure, increase the incidence of complete cures, decrease tumor volume and size prevent or reduce metastasis and protect against a second challenge with cancer.
In one embodiment, β-alethine is administered with the cell-cycle-nonspecific alkylating agent melphalan to treat cancer. In a series of experiments described in detail in Example XI, β-alethine was unexpectedly found to have a synergistic effect in treating the very aggressive MOPC-315 myeloma when combined with melphalan, compared to the administration of an equivalent dose of melphalan alone or β-alethine alone. Melphalan (mp) is the mainstay of human clinical therapy for multiple myeloma which is a chronic, progressive, and fatal disease in humans despite chemotherapy. Although the tumor burden in human patients with myeloma can be dramatically reduced by current chemotherapy and remissions of one to three years in duration are common, true cures are rare and typically associated with serious adverse side effects of mp.
It has been discovered that the combination of β-alethine/mp significantly increased overall survival, produced a five fold increase in the number of cures, prevented reoccurrence of the disease in cured animals even when challenged with a later injection of myeloma cells, promoted tumor regression and shortened the time to cure compared to the administration of an equivalent dose of mp or β-alethine alone. The present invention is also directed to a pharmaceutical composition including an mp in various relative amounts.
In another embodiment of the present invention, was administered together with another alkylating agent, cyclophosphamide (cp), to treat breast cancer in the MT-1 breast cancer xenograft model in mice. The combination of β-alethine/cp decreased the toxicity that was observed with β-alethine alone, and showed a synergistic effect on treating breast cancer over equivalent doses of cp or β-alethine administered alone. See Example XIII.
Mice having advanced MT-1 breast cancer tumors were given cyclophosphamide at doses of 300, 200 or 100 mg/kg, with our without administration of β-alethine 30 minutes earlier at 30 mg/kg. The addition of β-alethine to the very toxic dose of 300 mg/kg cp completely eliminated toxic deaths which occurred at the unacceptably high rate of 25% in the group receiving cp only. Further, the combination of β-alethine and cp caused most individual tumors to decrease in size, while most tumors grew in size in the group receiving cp alone. Therefore, in a preferred embodiment of the present invention, β-alethine is administered together with one or more known anti-cancer agents to reduce toxicity and or to treat or prevent cancer or to delay the clinical appearance of cancer. Another embodiment is a pharmaceutical composition including β-alethine and cp or any other known anti-cancer agent.
In another series of experiments, the combination of β-alethine/cp was used to treat the extremely fast-growing and aggressive solid melanoma B16. See Example XII. The combination was unexpectedly discovered to significantly decrease tumor size, and to result in fewer and smaller lung metastases while completely eliminating metastases to other organs, compared to treatment with an equivalent dose of either cyclophosphamide or β-alethine alone. Thus, in another embodiment of the present invention, a compound of Formula I is administered together with one or more known anti-cancer agents such as cyclophosphamide or melphalan to decrease metastatic cancer. Even in cases where surgery, radiation and chemotherapy are effective in eliminating the primary cancer, it is frequently the case that the patient dies from metastatic disease. The ability of the compounds of Formula I, especially β-alethine, to reduce metastases when administered together with one or more known anti-cancer agents, has immediate and important clinical applications in the treatment of aggressive melanoma and all cancers. A decrease in primary tumor volume was detected just five days after the onset of treatment with the β-alethine/cyclophosphamide mixture in animals with the extremely fats-growing and deadly B16 melanoma. In another preferred embodiment, β-alethine is administered together with cp to decrease, prevent or control metastasis.
In yet another embodiment, it was discovered that the combination of β-alethine significantly reduced the toxicity induced by paclitaxel (TAXOL™, or PAC) administered to non-tumor-bearing athymic mice (NCr-nu). See Example IV. Mice receiving the very toxic dose of 50 mg PAC together with 30 mg BT, suffered less weight loss at all time points, and showed a weight gain on day 21 that is twice the increase in weight gain observed with PAC alone. This indicates lower toxicity and an improvement in general wellness. PAC in an amount of 50 mg/kg is probably a fatal dose in humans.
Importantly, there were fewer toxic deaths when β-alethine was coadministered with either 30 mg or 50 mg paclitaxel. For the group receiving 50 mg PAC/30 mg β-alethine, the survival difference was statistically significant (log rank=6.41, p=0.0113). There were 9 deaths on day 21 with 50 mg PAC alone, and only 2 deaths with the β-alethine/PAC combination.
These results, taken together, demonstrate that compounds of Formula I, including β-alethine, combined with other anticancer agents unexpectedly lowered the toxicity of the anticancer agents with which it was combined. Further, the combination of compound of Formula I with one or more anti-cancer agents was much more effective in treating or preventing the onset cancer than an equivalent amount of the anticancer agent alone, regardless of the type of cancer or the anticancer agent.
The present invention relates to the combination of one or more anti-cancer agents with one or more compounds of Formula I to treat, prevent, or delay the clinical appearance of cancer to treat or prevent metastatic cancers, and/or to reduce the toxicity of other anti-cancer agents.
The amount of a compound of Formula I and other known anticancer agent to be administered to achieve the various embodiments of the present invention, can be determined by routine experimentation. For in vivo applications, the compounds of Formula I can be administered in amounts that vary from fg/kg to the maximum tolerated doses, together with a therapeutically useful, amount of any one or more known anticancer agent. In a preferred embodiment, compounds of Formula I are administered at Nanodrug™ doses of ng/kg to 2 g/kg and doses known in the art of anticancer agents. The compounds of Formula I decrease toxicity, which may permit moderate increases in the doses of the anti-cancer agents with which it is combined to obtain maximum effectiveness without increased risk of toxic death or adverse side effects. In preferred embodiments, the compositions of the present invention include one or more compounds or Formula I and cyclophosphamide, or melphalan, or Taxol™, or platinum containing drugs.
Although it may be generally advantageous to administer β-alethine in the mg/kg dose range along with known anticancer agents, the invention is not so limited. For example, use in ng/kg to fg/kg range may be optimal in certain circumstances such as maintenance chemotherapy or to prevent the clinical appearance of cancer, based on routine testing. Similarly, the amount of the anticancer agent combined with compounds of Formula I will vary with the individual, the type of cancer, and the extent of progress of the disease. For example, significantly lower doses of β-alethine and the anticancer agent may be sufficient for maintenance chemotherapy, for pediatric use, or for periodic administration after a certain period of remission to prevent the reappearance or metastasis of cancer.
The compounds of the invention can be administered topically, orally, rectally, intravaginally intravenously, intraperitoneally, subcutaneously, intramuscularly or intranasally, as appropriate for the effect sought. The compounds can also be administered transdermally using, for example, transdermal patches or transmucosally via sprays or other application.
The compounds of the invention are typically used in the form of a pharmaceutical composition comprising the compound of formula I, or salt or hydrolyzable derivative thereof as described above, together with a pharmaceutically acceptable diluent or carrier. The composition can be present in dosage unit form, for example, as a tablet, capsule or suppository. The composition can be formulated so as to be suitable for topical application (e.g. as a gel, cream, lotion or ointment). Alternatively, the composition can be present as a solution or suspension (e.g. sterile) suitable for administration by injection, inhalation, intranasally or dropwise to the eye or other sites as appropriate. The compound of the invention can be prepared as a slow release formulation appropriate for internal or external use. Using techniques known in the art, the compounds of the invention can also be trapped in or bound to a polymer, a solid support, a liposome or a gel.
Carriers and diluents known in the art can be used and the composition, when, for example, in the form of a tablet or capsule, can be formed with an enteric coating.
The composition of the invention can include active agents in addition to the compounds of formula I. Examples of such additional active agents include cancer chemotherapeutic agents, hormones, vitamins, cytokines, enzyme regulators, regulatory macromolecules, regulatory thiols or other small molecules.
The present compounds also have ex vivo applications including in the growth, maintenance or differentiation of tissue grafts, including bone and vascular grafts, and in the treatment of cells and organs, for example, prior to transplantation or use in the laboratory.
While the compounds of the invention are suitable for therapeutic use in humans, the compounds of formula I are also useful in the veterinary treatment of similar conditions affecting warm-blooded animals, such as dogs, cats, horses, cattle or birds, or fish. For such purposes, the compounds of the formula I can be administered in an analogous amount and manner to those described above for administration to humans. The compounds of the invention also have application to lower organisms, including insects, reptiles, and plankton, microorganisms, or others. They can be used in aqueous environments, including in marine or fresh water settings.
The present compounds are useful in connection with intact animals (particularly, but not exclusively, mammals) cells, tissues and organs.
Cells can be grown or stored in the presence of the present compounds using any of a variety of available techniques, including growth on plastic or glass or other support (e.g. beads or hollow fibers), growth in suspension (e.g. in liquid or semisolid medium), growth in a bioreactor, or storage in a frozen or dried state. Primary cultures or serial cultures, or otherwise, can be used.
The amount of the compound of the invention to be used and the frequency of exposure can be readily determined by one skilled in the art and will vary with the cell type, the compound used and the effect sought. In determining optimum concentrations, appropriate in vitro assays are run in the femtogram/ml to 10's of mg/ml range.
Various aspects of the present invention are described in greater detail in the non-limiting Examples that follow. Certain of the synthetic procedures described below correspond to those described by Knight et al, Cancer Research 54:5623 (1994) or in U.S. Pat. No. 4,218,404, or represent modifications thereof. In addition, the disclosures of WO 92/00955 and PCT/US91/04725 are relevant here, including the portions therein that relate to syntheses, therapeutic regimens and cell culture treatment protocols, those regimens and protocols being applicable to the compounds of the present invention.
EXAMPLE I
Synthesis of N-Carbobenzoxy-β-Alanyl-Taurine Zinc Salt
Method I
Preparation of N,N′-bis(CBZ)-β-Alethine from N-CBZ-β-alanine
To a 250 ml round bottom flask were added a stir bar, N-CBZ-alanine (5.805 g, 26.008 mmol), N-hydroxysuccinimide (2.993 g, 26.008 mmol, 1 eq.), and 1,3-dicyclohexylcarbodiimide (5.366 g, 26.008 mmol, 1 eq.). The flask was sealed with a septum and purged with argon. CH 2 Cl 2 (86 ml) was then added and the mixture stirred overnight at room temperature (rt). All of the solids did not dissolve upon addition of CH 2 Cl 2 . The solids were then removed via vacuum filtration through a pre-argon-purged medium glass fritted buchner funnel. The funnel was equipped with an argon purge funnel and a 500 ml round bottom flask containing a stir bar and cystamine$2HCl (1.464 g, 6.502 mmol, 0.25 eq.). The flask and solids (white) were then rinsed with 3×15 ml CH 2 Cl 2 . The filtrate was colorless to light yellow. The flask was removed from the buchner, sealed with a septum and purged with argon. To the stirring solution was added Et 3 N (2.9 ml, 20.806 mmol, 0.8 eq.). All of the solids did not dissolve. The reaction was stirred overnight at room temperature. The product was then collected using an 11 cm buchner funnel with #541 Whatman filter paper. The flask and solids (white) were rinsed with 3×15 ml CH 2 Cl 2 . The filtrate was colorless to yellow. The solids were placed in a 250 ml round bottom flask and dried under high vacuum overnight. The crude product weight was determined and DMSO (0.3 g/ml) was added and heated to 70° C.-90° C. to dissolve the solids with the aid of stirring. H 2 O (0.12 g/ml) was then added slowly with vigorous stirring. The mixture was cooled to room temperature and collected after 3 hours using an 11 cm buchner funnel with #541 Whatman filter paper. The solids (white) and flask were rinsed 3×15 ml CH 2 Cl 2 H 2 O followed by 2×15 ml EtOAc. The solids were chopped-up with a spatula and dried under high vacuum in a 250 ml round bottom flask. The recovery was 3.568 g corresponding to a 97.5% yield.
Preparation of N-carbobenzoxy-β-alanyl-taurine Zinc Salt from N,N′-bis(CBZ)-β-alethine (Small Additions of ZnO or Ca(OH) 2 )
To a 250 ml erlenmeyer flask were added a stir bar, N,N′-bis(CBZ)β-alethine (2.524 g, 4.486 mmol), dimethylsulfoxide (2.5 ml), N,N-dimethylformamide (2.5 ml), pyridine (3.2 ml), CHCl 3 (75 ml), and H 2 O (150 ml). The mixture was stirred vigorously giving an emulsion (not all solids dissolved). A pH meter was immersed in the aqueous phase. The pH was near 7.3 to 7.7. I 2 (7.97 g, 31.401 mmol, 7 eq.) was then added. Initially the organic phase was red and the aqueous phase was colorless. During the reaction, the color of the aqueous phase darkened to red and the emulsion subsided. The pH dropped to 5.7 within 10 minutes of adding I 2 . ZnO (100-200 mg, 0.3-0.6 eq.) was added in portions to keep the pH between 5.7 and 6.0. After ˜3.5 hours, the pH stabilized and the reaction was allowed to stir for an additional 2 hours (5.5 h total reaction time). The phases were separated (organic was dark red) and the aqueous phase was washed with 10 ml CHCl 3 . The aqueous phase (light red) was extracted additionally with CHCl 3 using a continuous liquid/liquid extractor overnight. The aqueous phase (colorless to very light pink) was separated, partially evaporated on a rotary evaporator to remove dissolved organics, shelf frozen, and lyophilized. The residue (golden brown) was dissolved in 1 ml H 2 O and 3 ml acetonitrile and added to 100 ml acetonitrile. The white precipitate was collected on a #541 Whatman filter paper and rinsed with 40 ml acetonitrile. The recovery was 1.676 g of white solids corresponding to a 52% yield (N-carbobenzoxy-β-alanyl-taurine zinc salt).
Preparation of N-carbobenzoxy-β-alanyl-taurine Zinc Salt from N,N′-bis(CBZ)β-alethine (ZnO Added Initially)
To a 125 ml erlenmeyer flask were added a stir bar, N,N′-bis(CBZ)β-alethine (809 mg, 1.438 mmol), dimethylsulfoxide (0.8 ml), N,N-dimethylformamide (0.8 ml), pyridine (1.0 ml), CHCl 3 (24 ml), H 2 O (80 ml), and ZnO (526 mg, 6.470 mmol, 4.5 eq.). The mixture was stirred vigorously giving an emulsion (not all solids dissolved). I 2 (3.28 g, 12.904 mmol, 9 eq.) was then added. Initially, the organic phase was red and the aqueous phase was colorless. During this reaction, the color of the aqueous phase darkened to red and the emulsion subsided. The mixture was stirred overnight. The phases were then separated (organic was dark red) and the aqueous washed with 20 ml CHCl 3 . The aqueous phase (light red) was extracted additionally with CHCl 3 using a continuous liquid/liquid extractor overnight. The aqueous phase (colorless to very light pink) was separated, partially evaporated on a rotary evaporator to remove dissolved organics, shelf frozen, and lyophilized. The residue (golden brown) was dissolved in 0.5 ml H 2 O and 2 ml acetonitrile and added to 75 ml acetonitrile. The white precipitate was collected on a #541 Whatman filter paper and rinsed with 20 ml acetonitrile. The recovery was 630 mg of white solids corresponding to a 61% yield (N-carbobenzoxy-β-alanyl-taurine zinc salt).
The 13 C NMR spectral data were as follows:
Signal
DMSO solvent:C—H coupled
1
48.4
2
33.8
3
172.2
4
34.6
5
36.4
6
156.4
7
65.4
8
135.0
9
125.8
10
126.5
11
128.0
Method IIa
Preparation of N-carbobenzoxy-β-alanyl-taurine (Free Acid and Zinc Salt) from N-(CBZ)-β-alanine
The N-(CBZ)-β-alanine (563 mg, 2.522 mmol), N-hydroxysuccinimide (290 mg, 2.522 mmol) and DCC (520 mg, 2.522 mmol) were dissolved (no obvious dissolution) in CH 2 Cl 2 (11.5 ml, to make a 0.22 M solution). The reaction was allowed to mix overnight at room temperature. The crude reaction mixture was filtered through a sintered glass funnel to remove the dicyclohexylurea (DCU). The reaction was filtered “anhydrously” into a flask containing 316 mg (2.522 mmol) taurine. The filter cake was washed with 3, 5 ml volumes of CH 2 Cl 2 . After adding 316 μl Et 3 N (1 eq), the reaction was allowed to mix at room temperature. The reaction was allowed to mix until complete by NMR. The crude reaction mixture was purified by trituration with MeCN. The crude reaction mixture was dissolved in 14 ml CH 2 Cl 2 (0.2 M) and 1 eq of triflic acid was added. The reaction was allowed to mix overnight at room temperature although the reaction appeared complete after mixing for only 15-20 minutes. The reaction mixture was filtered and the filter cake washed with CH 2 Cl 2 . The filter cake (the free acid) was divided into two portions. One portion (305 mg) and 0.5 eq Zn(OH) 2 were dissolved in 5 ml H 2 O and allowed to mix for 1 hour and then it was concentrated by lyophilization to give 340 mg as a white solid (66% based on starting N-(CBZ)-β-alanine). The other portion was purified and characterized as the free acid (190 mg). NMR data were obtained on both the free acid and the Zn salt, the Zn salt being the more pure.
The 1 H NMR spectral data were as follows:
Signal
D 2 O solvent
a
2.99(t, J=12.8Hz, 2H)
b
3.48(t, J=12.8Hz, 2H)
c
not seen due to hydrogen bonding
d
2.38(t, J=12.4Hz, 2H)
e
3.35(m, 2H)
f
not seen due to hydrogen bonding
g
5.07(m, 4H)
The 13 C NMR spectral data were as follows:
Signal
DMSO solvent
1
51.1
2
36.1
3
170.2
4
36.4
5
37.7
6
156.6
7
65.7
8
137.8
9
128.3
10
128.9
11
128.9
Method IIb
Preparation of N-carbobenzoxy-β-alanyl-taurine (Free Acid and Zinc Salt) from N-(CBZ)-β-Alanine (Scale Up)
In a three-neck 1L flask was placed CBZ-β-alethine (48.2 g, 215.9 mmol) under N 2 . To this was added freshly distilled methylene chloride (750 mL), followed by N-hydroxysuccinimide (24.85 g, 215.9 mmol). To the resulting suspension was added 1,3-dicyclohexylcarbodiimide (DCC, 44.54 g, 215.9 mmol). At this scale the reaction generated a noticeable exotherm, sufficient to reflux the CH 2 Cl 2 . The reaction mixture was stirred under N 2 for 5 hours at which point the mixture was filtered through a sintered glass buchner funnel. The filter cake was washed with CH 2 Cl 2 (3×100 mL). To the filtrate was added taurine (27.03 g, 215.9 mmol) and triethylamine (33.1 mL, 237.5 mmol). The reaction was stirred under N 2 and monitored by 1 H-NMR analysis. The reaction mixture was vacuum filtered through a buchner funnel using Whatman #542 filter paper. The filtrate was stripped to an oil using reduced pressure, then placed on high vacuum. The “oil” was triturated with acetonitrile with one drop of water to quench any unreacted DCC. The mixture was filtered and the MeCN was stripped off under reduced pressure then placed on high vacuum. The resulting oil was dissolved in water (50 mL). A curdy white precipitate formed, more water (150 mL) was added and the resulting solid was filtered off. In the filtrate an oil precipitated out of solution. 1 H-NMR spectra were obtained to determine the location of product. The product was in the aqueous layer as expected. The aqueous phase containing the product was then eluted through a H+ ion exchange column. Fractions (225 mL) were collected and spotted on TLC. The desired product was found in fractions 2-7. These fractions were combined and the water removed under reduced pressure. To the resulting oil was added MeCN (1L) and the solution was stirred. The remaining water was removed by azeotropic distillation with the MeCN. The resulting solid was collected by vacuum filtration and washed with MeCN. The solid was vacuum dried in a 1L round bottom flask then transferred to a tared 4 oz. amber bottle. Final package weight was 38.89 g (117.7 mmol, 54.5% yield). The zinc salt was prepared by treatment with Zn(OH) 2 in H 2 O, followed by lyophilization. The spectral data for the product matched exactly a standard sample of N-carbobenzoxy-β-alanyl-taurine zinc salt.
EXAMPLE II
Synthesis of β-Alanyl-Taurine (Free Acid and Zinc Salt)
N-carbobenzoxy-β-alanyl-taurine (1.00 g, 3.4 mmol) was slurried in 23 ml glacial AcOH. To the mixture was added 3.4 mL HBr in AcOH (30 wt %) to result in a clear solution. The reaction was heated to 40° C. and allowed to mix overnight. The product precipitated out of solution and acetonitrile was added to force the precipitation. The mixture was filtered, the filter cake washed and the product collected. The crude Br salt was loaded onto an ion exchange column (Dowex AG1-XB8). The column was eluted with H 2 O. The product cut was collected and lyophilized to give 583 mg of β-alanyl-taurine (87.3%). The zinc salt was prepared by treatment with Zn(OH) 2 in H 2 O, followed by lyophilization.
The 1 H NMR spectral data were as follows:
Signal
D 2 O solvent
a
3.09(t, J=12Hz, 2H)
b
3.59(t, J=12Hz, 2H)
c
not seen due to hydrogen bonding
d
2.66(t, J=12Hz, 2H)
e
3.25(t, J=12Hz, 2H)
The 13 C NMR spectral data were as follows:
Signal
DMSO solvent
1
50.8
2
36.2
3
169.6
4
33.1
5
36.2
For comparison, β-alanyl-taurine zinc salt prepared using the method of Knight et al, Cancer Research 54:5623 (1994) gave the following 1 H NMR spectra:
Signal
D 2 O solvent
a
2.93(t, J=12Hz, 2H)
b
3.42(t, J=12Hz, 2H)
c
not seen due to hydrogen bonding
d
2.50(t, J=12Hz, 2H)
e
3.10(t, J=12Hz, 2H)
EXAMPLE III
Preparation of N-Carbobenzoxy-β-Alanyl-Ethanolamine Phosphate (Free Acid and Zinc Salt) from N-(CBZ)-β-Alanine
N-(CBZ)-β-alanine (274 mg, 1.23 mmol), N-hydroxysuccinimide (141 mg, 1.23 mmol) and dicyclohexylurea (DCC, 253 mg, 1.23 mmol) were dissolved in tetrahydrofuran (THF, 4.1 mL). The reaction was allowed to mix at room temperatore overnight before being filtered to remove the dicyclohexylurea (DCU). To the filtrate, a solution of 2-aminoethyl dihydrogen phosphate (1.23 mmol) in H 2 O (0.5 ml) was added. To the reaction mixture was added 2.1 molar equivalents of triethylamine. The reaction was allowed to mix for three days before the THR was removed under vacuum. The remaining aqueous phase was filtered and loaded onto a prepared ion exchange column (Dowex AG 50W-X8). The column was eluted with water. The product fractions were collected and lyophilized. The crude solid (260 mg) was treated with 1.0 molar equivalents of Zn(OH) 2 in H 2 O to make the salt. The crude solid (after lyophilization) was triturated with acetronile and collected (50 mg).
EXAMPLE IV
Synthesis of N-Carbobenzoxy-β-Alanyl-Aminoethylphosphonic Acid (Free Acid and Zinc Salt) from N-(CBZ)-β-Alanine
N-(CBZ)-β-alanine (301 mg, 1.35 mmol), N-hydroxysuccinimide (155 mg, 1.35 mmol) and dicyclohexylurea (DCC, 278 mg, 1.35 mmol) were dissolved in tetrahydrofuran (THF, 4.5 ml). The reaction was allowed to mix at room temperature overnight before being filtered to remove the dicyclohexylurea (DCU). To the filtrate, a solution of 2-aminoethylphosphonic acid (1.35 mmol) in H 2 O (0.5 ml) was added. To the reaction mixture was added 2.1 molar equivalents of triethylamine. The reaction was allowed to mix for three days before the THF was removed under vacuum. The remaining aqueous phase was filtered and loaded onto a prepared ion exchange column (Dowex AG 50W-X8). The column was eluted with water. The product fractions were collected and lyophilized. The crude solid (270 mg) was treated with 1.0 molar equivalents of Zn(OH) 2 in H 2 O to make the salt. The crude solid (after lyophilization) was triturated with acetonitrile and collected (50 mg).
EXAMPLE V
In Vitro Simulation of Differentiation and Production of Differentiated Product by N-Carbobenzoxy-β-Alanyl-Taurine Zinc Salt
Hybridoma cells (ATCC #CRL-8014, OKT-8, secreting an IgG2 anti-human T-cell subset antibody) were growth with or without N-carbobenzoxy-β-alanyl-taurine zinc salt in T25 culture flasks. Cells were inoculated at a density of 10,000 cells/ml and maintained below 500,000 cells/ml in 5 mls of protein-free media containing HyQ-PF-MAB from Hyclone. Aliquots were assayed for Mab production by a sandwich ELISA. Aliquots were diluted to be within the standard range and added to plates precoated with goat anti-mouse IgG by incubating two hours at room temperature. Wells were washed and reacted with diluted supernatants, then washed and detected with peroxidase labeled anti-mouse antibodies. The results are shown in Table 1.
TABLE 1
Altered Production of Monoclonal Antibodies from Hybridomas
Drug
lgG, μg/ml
IgG, ρg/cell
0 - control
12
41.7
N-carbobenzoxy-β-alanyl-taurine 200 ρg/ml
50
80.6
Increase
316%
93%
EXAMPLE VI
Stimulation of Protein Production from Mammalian Cells
CHO cells containing a cloned gene for tissue plasminogen activator (tPA) were obtained from ATCC as #CRL-9606. The tPA gene had been introduced by transfection of a plasmid pETPFR. The cells were propogated in T-25 flasks in Ham's F-12 medium with 10% fetal bovine serum. The cell cultures were innoculated by adding 5 ml of cells at 2×10 4 cells/ml into T-25 flasks.
The effect of N-carbobenzoxy-β-alanyl taurine zinc salt on the production of tPA was tested by adding this compound to the growth medium, and maintaining the indicated levels of the compound over many (e.g. 6) passages of the cells.
At the end of log phase growth, the cultures were harvested by trypsinization. One ml was centrifuged to remove cells and the supernatant assayed for tPA in the IMUBIND total tPA Stripwell ELISA from American Diagnostica Inc.
The results shown in Table 2 demonstrate that the compound (N-carbobenzoxy-β-alanyl taurine zinc salt, #'s 1, 2 and 3 in Table 2) alters the per-cell production of tPA by about 2 fold. The cell numbers per milliliter were determined by direct counting of trypan-blue stained cells on a hemacytometer.
TABLE 2
ELISA
Supernatant
Optical
Concentration
Culture Cell
Picograms tPA
Compound
Density
nanograms/ml*
Density
per cell
Control
0.177
424.6
2.2 × 10 5
1.93
#1
0.332
1,492.8
4.0 × 10 5
3.73
1 ρg/ml
[3.5 × control]
[1.9 × control]
#2
0.317
1,389.4
4.8 × 10 5
2.89
1 ρg/ml
[3.3 × control]
[1.5 × control]
#3
0.422
2,113.0
5.2 × 10 5
4.06
1 ρg/ml
[5.0 × control]
[2.1 × control]
*The standard curve is “Abs = 0.1154 + .029* Concentration”, with a correlation coefficient of 0.9977.
EXAMPLE VII
In Vivo Coordinated T Cell Dependent Response Delayed Type Hypersensitivity
In order to test an in vivo coordinated T cell dependent response, delayed type hypersensitivity (DTH) was measured. DTH is the test used clincially to determine if a person has mounted an immune response to many antigens. The most frequent application is measurement of DTH in response to tuberculosis called a PPD or tine test. It is also used to determine if a patient, such as a cancer patient, has had a failure of the immune system and become anergic.
In the laboratory this test involves the generation of a specific response to a oxazalone (OX) in mice and measurement of the response. The generation of the response (sensitization or initial exposure) was caused by the application of OX to the shaved abdomen of the animal (50 μl of 1.2% OX in olive oil). Measurement of the response occurred 24 and 48 hours following application of OX (5 μl 1.2%) to the right ear of the animal. In the experiment performed, sensitization occurred on day 0; challenge occurred on day 4. On days five and six, the thickness of the ear was measured and the thickness before challenge was subtracted. The doses of OX used were chosen so that some normal untreated animals had a perceptible but moderate response to the OX at 24 hrs.
In order to measure the effect of N-carbobenzoxy-β-alanyl-taurine zinc salt, various doses were injected iv on Day -2, 0, +2 and +4.
Ten animals were used per group. Drug dilutions are made up and coded at one facility and an independent contract facility (Midlantic Research) performed all procedures in a “blind” fashion. In no case did control ears (those either not sensitized or not challenged) have swelling over 40μ. Animals with 50μ to 99μ swelling were rated as having moderate swelling. Three control (saline injected) animals mounted a moderate response on at 24 hrs as expected. N-carbobenzoxy-β-alanyl taurine altered the response rate to eight of ten in two different treatment groups (this is above the 95% confidence bounds for an altered response by relative risk measure). All groups of animals receiving between 1 fg/kg and 1 mg/kg had more moderate responders than the saline injected group.
Those animals with 100μ or greater swelling were rated as having major immune responses. No saline injected animal had major immune response at 24 hours while a total of 14 N-carbobenzoxy-β-alanyl-taurine treated animals had major immune response. One non drug treated animal had a major response at either 24 or 48 hours post challenge, while 21 N-carbobenzoxy-β-alanyl-taurine treated animals had a major response at one of these times. The data are presented in Table 3.
Dose/kg >
0
1 fg
32 fg
1 pg
32 pg
1 ng
1 μg
1 mg
Moderate DTH at
30
70
60
50
80*
80*
40
70
24 hrs
Major DTH at 24
0
20
20
10
10
20
10
50*
hrs
Major DTH at 48
0
20
20
10
10
20
10
50
hrs.
Major DTH at
10
20
20
10
40
20
30
60
either 24 or 48
hrs.
*Relative Risk (RR) compared to control exceeds 1 even at lowest end of 95% confidence bounds. RR not tested at 48 hours
EXAMPLE VIII
Blood Cell Stimulation
A 96-well-based suspension culture system (Warren et al, Stem Cells 13:167 (1995) for human hematopoietic progenitor cells was used to monitor the commitment and differentiation of CD34+ cells in vitro. Expression of maturation and lineage markers on the cells in culture were measured by ELISA. The CD34+ cells were isolated from umbilical cord blood (90% purity) and grown in liquid culture in 96-well plates (2000 per well) for 10 days. A combination of growth factors was added that stimulates the expression of the appropriate lineage markers. The culture consisted of: IMDM plus 15% FBS, 0.5 ng/ml IL-3, 20 ng/ml SCF, 1 unit/ml EPO, 1 ng/ml GCSF and the indicated concentrations of test compounds. The cells were then fixed with a glutaraldehyde-paraformaldehyde mixture, attaching the cells firmly to the plastic. An ELISA was performed (Warren et al, Stem Cells 13:167 (1995)), using appropriate primary antibodies directed against cell surface markers. The expression of three different lineage markers was measured: CD14 (monocyte), CD15 (neutrophil), and glycophorin A (erythroid). The results are presented in Table 4.
TABLE 4
Increase in Blood Cell Production
Percent difference (relative to control)
Study 1: 1 ng/ml compound
Study 2: 1 ug/ml
Compound
monocytes
neutrophils
red blood cells
CD34 cells
monocytes
RBC
Taurox-BP
18
14
1
0
2
4
Taurox-BOP
18
21
0
33
9
55
Taurox-SB
15
0
0
not tested
Taurox-S
47
55
50
not tested
Taurox-BP = N-carboxybenzoxy-β-alanyl aminoethylphosphonic acid
Taurox-BOP = N-carboxybenzoxy-β-alanyl-ethanolamine phosphate
Taurox-SB = N-carboxybenzoxy-β-alanyl-taurine
Taurox-S = β-alanyl-taurine
Study 2: same, expect 1700 cells per well
EXAMPLE IX
Immune Stimulation
BALB/c female mice (4-5 weeks of age) were pre-bled, then injected ip with 0.1 mls of indicted compounds on day −7, day −5, day −3, and day 0. On day 0, they received soluble polysaccharide antigen Pn14-Tetanus Toxin, 10 μg in 0.1 mls, given ip. Two other groups received Pn14-TT, 10 μg in 0.1 mls of a 60% emulsion of complete Freund's adjuvant (CFA) on Day 0, given subcutaneously above the hind leg, just off the midline. The two CFA groups were treated identically. All mice were bled on Day 4 and Day 14. On Day 84, mice were bled and boosted with 5 μg Pn14 (not conjugated to TT) and either the experimental compound or incomplete Freund's adjuvant (for those previously given CFA). Mice were bled on day 94. Sera at 1:1000 were analyzed by ELISA for anti-Pn14 antibodies. Prebleed values were subtracted.
TABLE 5
Mean Change in O.D. (Optical density, indicating presence of antibody)
Change from pretest to 4
Change from pre-boost
& 14 days after injection
10 days after boost with
with antigen
UNCONJUGATED
Compound (per kg)
Day 4
Day 14
polysaccharide
CFA (control)
−0.6
672
−256
CFA (control)
−1.0
367
not tested
Taurox-BP, 5 ng
15.5
1399
not tested
Taurox-BP, 5 ug
6.5
616
not tested
Taurox-BP, 5 mg
3.3
924
187
Taurox-BOP, 5 ng
5.4
877
not tested
Taurox-BOP, 5 ug
1.8
515
not tested
Taurox-BOP, 5 mg
0
366
not tested
Taurox-SB, 5 ng
6.2
705
not tested
Taurox-SB, 5 ug
3.9
483
not tested
Taurox-SB, 5 mg
1.1
697
139
Taurox-S, 5 ng
13.1
681
204
Taurox-S, 5 ug
3.6
671
not tested
Taurox-S, 5 mg
2.9
697
not tested
Notes
1. Values are the mean of 3 animals per drug/dose group.
2. Doses were 5 ng per kilogram of animal, 5 ug/kg, and 5 mg/kg of test compounds given prior to and with conjugated antigen, indicated above as “ng”, “ug”, and “mg”.
3. CFA—Complete Freund's adjuvant, the current “gold standard” vaccine adjuvant, but approved only for animal uses due to its toxicity. Two groups of 3 animals were used. Published data indicate CFA stimulates response 10× compared to saline.
Discussion
a. Only in animals treated with a compound of this invention is a 4-day response seen.
b. Only in animals treated with a compound of this invention is a response to unconjugated polysaccharide seen.
c. The 14-day response is greater with treatment.
EXAMPLE X
Syntheses
Synthesis of N-Carbobenzoxy-β-Alanyl-Ethanolamine Sulfate—Taurox BOS
To a THF solution of N-(CBZ)-β-alanine and N-hydroxysuccinimide, add DCC. The reaction is mixed overnight at room temperature. The crude reaction mixture is filtered through a sintered glass funnel into a round bottom flask to remove the DCU that is formed. The activated ester should remain in solution. After concentrating and redissolving in solvent, ethanolamine or an alcohol protected derivative can be added as a solution to the solution containing the activated ester. Triethylamine can also be added. Workup of the reaction and purification results in formation of N-carbobenzoxy-β-alanyl-ethanolamine. The free alcohol can be sulfated by a variety of methods to result in formation of N-carbobenzoxy-β-alanyl-ethanolamine sulfate.
Synthesis of β-Alanyl-Ethanolamine Sulfate (from N-Carbobenzoxy-β-Alanyl-Ethanolamine Sulfate)—Taurox OS
In a similar fashion to the conversion of N-carbobenzoxy-β-alanyl-taurine to β-alanyl-taurine, N-carbobenzoxy-β-alanyl-ethanolamine sulfate can be converted to β-alanyl-ethanolamine sulfate. The conversion can be effected by slurrying the N-carbobenzoxy-β-alanyl-ethanolamine sulfate in glacial AcOH. To the mixture, HBr in AcOH (30 wt %) is added. The reaction can be heated and allowed to mix for a period of not less than 1 hour. The product can be isolated by usual workup and precipitation.
Synthesis of β-Alanyl-Ethanolamine Phosphate (from N-Carbobenzoxy-β-Alanyl-Ethanolamine Phosphate)—Taurox OP
In a similar fashion to the conversion of N-carbobenzoxy-β-alanyl-taurine to β-alanyl-taurine, N-carbobenzoxy-β-alanyl-ethanolamine phosphate can be converted to β-alanyl-ethanolamine phosphate. The conversion can be effected by slurrying the N-carbobenzoxy-β-alanyl-ethanolamine phosphate in glacial AcOH. To the mixture, HBr in AcOH (30 wt %) is added. The reaction can be heated and allowed to mix for a period of not less than 1 hour. The product can be isolated by usual workup and precipitation.
Synthesis of β-Alanyl-Aminoethylphosphonic Acid (from N-Carbobenzoxy-β-Alanyl-Aminoethylphosphonic Acid)—Taurox P
In a similar fashion to the conversion of N-carbobenzoxy-β-alanyl-taurine to β-alanyl-taurine, N-carbobenzoxy-β-alanyl-aminoethylphosphonic acid can be converted to β-alanyl-aminoethylphosphonic acid. The conversion can be effected by slurrying the N-carbobenzoxy-β-alanyl-aminoethylphosphonic acid in glacial AcOH. To the mixture, HBr in AcOH (30 wt %) is added. The reaction can be heated and allowed to mix for a period of not less than 1 hour. The product can be isolated by usual workup and precipitation.
EXAMPLE XI
β-alethine Combined with Melphalan MOPC-315 Myeloma
Published studies with the slow-growing, relatively nonaggressive NS-1 myeloma (Cancer Research, 1994, 54: 5636-5642) showed that β-alethine (BT) was 100% effective in causing NS-1 inoculated animals to survive. In this series of experiments, the effect of BT alone or in combination with melphalan (mp) was tested in Balb/c mice against the more aggressive MOPC-315 myeloma which grows from 1 million cells to 2 cm in 10 days and kills at a rate of nearly 100% in another 10 days if not treated. A suboptimal dose of 1.25 mg/kg melphalan was chosen for this study because it was expected to cure about half of the animals. The amount of β-alethine varied from study to study, but the amount of melphalan remained constant.
In six separate studies mice were treated with the chemotherapeutic agent melphalan (mp), BT alone, BT and mp, or vehicle, following s.c. administration to the host mouse of myeloma cells, either 1 million cells (high tumor burden) or 3×10 5 cells (low tumor burden). There were ten mice in each group. All drugs were injected i.p. Date of death and tumor size or complete disappearance of tumor were monitored. In this model, it is accepted that disappearance of tumor correlates positively with long term cure. Table 6 presents survival data for all six studies.
TABLE 6
MOPC-315 Myeloma - Survival Study
Dose per kg
Animals Surviving on Each Test Day
day:
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
26
27
29
31
#1 β-alethine ip day 2 (1 × 10 6 tumor cells)
Vehicle
10
10
10
9
7
5
5
4
3
3
1
1
1
1
0
BT
30
fg
10
10
10
8
5
3
3
3
2
2
0
0
Alone
3
ng
10
10
10
9
8
7
6
4
3
3
2
0
100
μg
10
10
10
10
7
6
6
5
3
3
1
0
3
mg
10
10
10
10
7
4
4
3
2
2
1
1
1
1
0
Dose per kg
Animals Surviving on Each Test Day
day
10
11
12
13
14
15
16
17
18
19
20
21
22
23
25
26
27
29
31
#2 β-alethine ip day 10 (1 × 10 6 tumor cells)
Vehicle
10
10
7
7
5
4
4
2
0
BT
30
fg
10
10
9
7
5
5
1
1
0
Alone
3
ng
10
10
10
10
7
5
5
4
1
1
1
0
100
μg
10
9
6
5
5
5
4
4
1
1
0
3
mg
10
9
6
5
5
5
4
4
1
1
0
Dose per kg
Animals Surviving on Each Test Day
day
10
11
12
13
14
15
16
17
18
19
20
21
22
23
25
26
27
29
31
#3 β-alethine ip day 0 (3 × 10 5 tumor cells)
Vehicle
10
10
10
10
6
6
3
0
BT
100
ng
10
10
10
10
7
7
4
0
Alone
3
μg
10
10
9
9
9
9
4
0
100
μg
10
10
10
10
8
8
3
2
0
3
mg
10
10
10
10
10
10
8
3
3
0
Dose per kg
Animals Surviving on Each Test Day
day
10
11
12
13
14
15
16
17
18
19
20
21
22
23
25
26
27
29
31
#4 Melphalan + β-alethine ip day 10 (1 × 10 6 tumor cells)
Vehicle
10
10
7
7
5
4
4
2
0
mp
1.25
mg
10
8
5
4
3
3
3
3
3
3
3
3
3
3
3
3
3
3
1
mp + BT
30
fg
10
10
9
9
9
9
8
7
6
6
3
1
1
1
1
1
1
1
1
3
ng
10
10
8
7
7
7
7
7
6
6
6
4
4
3
3
3
3
3
3
100
μg
10
9
9
9
9
9
8
7
7
7
6
5
4
4
4
4
4
4
4
3
mg
10
10
9
9
9
9
8
8
8
8
7
5
5
5
5
5
5
5
5
Dose per kg
Animals Surviving on Each Test Day
day
10
11
12
13
14
15
16
17
18
19
20
21
22
23
25
26
28
29
31
#5 Melphalan (mp) + β-alethine ip day 9 (1 × 10 6 tumor cells)
mp
1.25
mg
10
10
10
10
10
10
10
10
10
10
9
9
9
8
8
8
7
7
7
mp + BT
100
μg
10
10
10
10
10
10
10
10
10
10
8
8
8
8
8
8
7
7
7
1
mg
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
mg
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
9
9
9
100
mg
9*
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
Dose per kg
Animals Surviving on Each Test Day
day
10
11
12
13
14
15
16
17
18
19
20
21
22
23
25
26
27
29
31
#6 β-alethine ip starting day 9, 10 or 11; 75 mg/kg mp ip day 10. (1 × 10 6 tumor cells)
mp d 10
1.25
mg
20
20
20
20
20
20
19
19
19
19
19
15
9
9
7
4
3
2
2
mp + BT
day 9
75
mg
10
10
10
10
10
10
10
10
10
9
9
9
5
5
3
2
2
1
1
day 10
75
mg
10
10
10
10
10
10
9
9
9
8
8
8
7
7
7
5
4
3
2
day 11
75
mg
10
10
10
10
10
9
9
7
7
7
5
5
5
4
3
2
1
1
1
*In Study #5, in the 100 mg group, one of the 10 mice died for reasons unknown and it not included in the analysis.
Effects of β-alethine Alone on High Tumor Burden Animals
Studies #1-3 tested β-alethine given alone.
In the first two studies [Table 6, #1 & 2], BT was administered to high tumor burden animals that had been injected with 1 million melanoma cells. BT administered to groups of 8 mice each at doses of 30 femtograms/kg to 3 milligrams/kg on day 2 or day 10 after myeloma cell injection had no effect on survival when administered to these high tumor burden animals.
In a third study, BT (0.1 mg to 3 mg/kg) was administered alone to animals with a lower tumor burden. In this experiment, BT was injected simultaneously with a lower dose of melanoma cells (3×10 5 cells). Only the highest dose of BT (3 mg/kg) significantly increased length of survival (survival analysis p=0.007) in these animals. The results in Table 6, #3 show that 3 mg/kg beta-alethine prolonged survival from 16 days in control animals, to 18 days. This difference is meaningful given the generally rapid fatality in the murine MOPC-315 model.
Effects of the Combination BT and Melphalan on High Tumor Burden Animals
Three additional studies [4-6] tested the anticancer effects of different doses of BT in combination with 1.25 mg/kg melphalan against mice having received a high tumor burden of 1 million cells. One injection of B-alethine was given; amounts ranged from 30 fg/kg to 100 mg/kg.
In the first of the three studies (#4), treatment was initiated 10 days after myeloma cell injection into the host. The doses of BT were 30 fg/kg to 3 mg/kg. Mp was only given at a dose of 1.25 mg/kg, which is a sub-optimal dose expected to cure up to half of the animals. All drugs were given on day 10.
In study #4, survival was increased in the groups receiving combination therapy at three doses of BT, relative to controls having no drugs at all, and to the group receiving melphalan only. The highest dose of 3 mg/kg BT was the most effective. The difference in survival between 3 mg/kg BT with 1.25 mg/kg mp, and mp alone, was statistically significant (survival analysis p=0.03). The first occurrence of cure was observed 11 days after treatment when BT (3 mg/kg) was administered together with melphalan; five of the ten mice in this group were completely cured by day 16. The cured animals remained tumor-free for over 50 days and survived without recurrence even when challenged with additional myeloma cells. Four animals survived in the group receiving 100 ug/kg BT with the mp. By contrast, only one animal in ten was cured by melphalan alone, and this cure occurred 19 days after treatment began. The addition of 3 mg/kg BT to melphalan dramatically increased the number of apparent cures five-fold over melphalan alone. Further, the combination drug also decreased the time to cure and the number of deaths. Thus, adding BT to melphalan produced a synergistic anticancer effect that was much greater than the anticipated additive effects of these compounds. Beta-alethine alone even at a very high dose, was ineffective in treating animals having a high tumor burden (see Study #2 above). Studies #2 and #4 were parallel and used the same control group.
Table 7 compares tumor size in groups receiving the highest BT dose (3 mg/kg) either alone or with mp in these two studies. Melphalan alone had only one fifth the cures observed with the combination, and displayed a longer time before the first cure was observed than with the combination drug.
TABLE 7
Mean Tumor Size (in mm) in 2 Studies Treating on Day 10
day 10
day 14
day 17
day 21
day 29
#2
3 mg
21.5
24
24
(dead)
BETATHINE
BT
as Single
alone
Agent Therapy
saline
20
25
26
(dead)
#4
mp & 3
23
22
15.5
12
0
Combination
mg BT
Therapy
mp
22.5
19
17
22
28
alone
Since a dose-response relationship was observed in #4, higher doses of BT (0.1, 1, 10 and 100 mg/kg BT) were administered with or without mp in study #5. Treatment was also started one day earlier, i.e. on day 9. Most mice survived and were cured in all groups. All the mice (either 9 or 10 per group) survived when given the combination having either 1 or 100 mg/kg BT. At 10 mg/kg BT with mp, 9 of 10 survived. By contrast, only 7 of 10 survived in the control group receiving 1.25 mg/kg mp alone (p=0.08 for survival difference). Although there were relatively good responses to all therapies, the tumors regressed more quickly (based on tumor size) in the 100 mg/kg BT/mp combination group. Due to the small sample size, this difference was significant only on day 16 (p=0.05). The tumor sizes are presented in Table 8.
TABLE 8
Effect of Beta-alethine and Melphalan on
MOPC-315 Myeloma Tumor Size (mm): Treatment on Day 9
day after tumor inoculation
13
16
20
23
27
1.25 mg/kg mp
20.4
19.2
17.0
10.2
0
100 mg/kg BT & 1.25 mg/kg m
18.6
15.0
12.9
6.4
0
In the third study with the combination [#6], all tumors grew unusually rapidly and no therapy was effective for most animals, however, there was a small advantage in the groups receiving BT on the same day as the melphalan. All groups received 1.25 mg/kg mp on day 10, 75 mg/kg BT was administered on day 9, 10 or 11, i.e, 1 day prior to mp (day 9), the same day (day 10), or the following day (day 11). There were 10 animals in each combination group and 20 in the mp-only group. Despite the rapid tumor growth, a decreased tumor size (21 vs. 26 mm) and an increased cure rate (2/10 vs. 2/20) were seen in the group receiving combination therapy where BT and mp were given on the same day (day 10), compared to melphalan alone; however, these results were not statistically significant. (See Table 9.) Overall in this third study, BT was able to improve the effects of melphalan, even when the tumor was so aggressive that all therapies were inadequate. Further, the addition of beta-alethine to mp permitted an optimal effect at what are clinically suboptimal doses of mp if mp were administered alone. This means that the amounts of mp can be reduced thereby decreasing toxicity effects associated with mp without sacrificing clinical efficacy.
TABLE 9
Deaths and Tumor Size (mm) in Mopc-315 Myeloma Treated with
Combination of mp on Day 10 and BT on Day 9, 10, or 11
mp on day 10 + BT on:
prior day (9)
same (10)
next (11)
none
day 21 tumor size (mm)
27.7
21
26.2
25.8
number in group
10
10
10
20
deaths day 21
1
2
5
5
cures day 21
1
2
1
2
day half are dead
22
25
20
22
To summarize, these studies show that treatment with BT alone increases survival even with a highly aggressive myeloma if the tumor burden is relatively low, such as occurs in the early to moderate stages of myeloma. Unexpectedly, the combination of BT together with melphalan produced a synergistic anticancer effect over the effect observed with either BT or melphalan alone. The combination of BT/melphalan dramatically increased survival and total cures in a highly aggressive form of myeloma even when the tumor burden was high. Importantly, combination therapy prevented recurrence in cured animals even when challenged with a second injection of myeloma cells.
EXAMPLE XII
BT Produces a Synergism When Combined with Cyclophosphamide to Treat Melanoma
Eight female BDF1 mice, six to seven weeks old, were implanted in the foot on day 0 with an experimental skin cancer, B16 melanoma, that is extremely fast-growing and aggressive (solid melanoma). They were subsequently treated 2 days after implantation (day 2) with either a single s.c. injection of the alkylating agent cyclophosphamide (cp), a standard chemotherapeutic agent used in the treatment of melanoma, at a dose of 200 mg/kg, or a combination of BT/cp. The primary tumor was removed on day 17. (5 days after starting combination therapy) The size of the primary tumor and the presence of metastasis on day 42 was measured. Table 10 presents tumor size.
A statistically significant reduction of the size of primary tumor was observed on day 7 in animals treated with the combination of BT (30 mg/kg) 3× times a week starting on day 2 and cp (200 mg/kg) on day 1 compared to no treatment or cp alone. See Table 10. This reduction in tumor size persisted through day 17 when the experiment ended. Statistical significance of this difference was p=0.015 at day 17, measured using the Mann-Whitney U test. By contrast, 200 mg/kg cp alone did not significantly reduce the size of the primary tumor until day 10, and this reduction was temporary, lasting only until day 14. Further, the reduction in tumor size by 200 mg/kg mp was always much less than that caused by the combination.
The T/C ratio for medium tumor volume on day 17 was 52.5% for the combination and 82.3% for cp alone. (T/C is the ratio of the treatment value to the control value, where 100% is no difference. RTV is defined as the change in tumor volume from day 0, RTV can be used to calculate the T/C ratio). These findings indicate that BT greatly enhanced the anticancer properties of cyclophosphamide, producing an earlier, larger, and longer lasting effect on reducing the size of the primary tumor than cp alone.
TABLE 10
Primary Tumor Size (Median RTV) on B16 Melanoma:
day 0
4
7
10
14
17
Saline control
1
1.0
2.7
6.8
17.9
36.9
BT 30 mg/kg alone
1
1.7
3.3
7.5
23.2
34.8
BT 30 ug/kg alone
1
1.0
1.3
5.5
16.6
30.4
BT 30 ng/kg alone
1
1.0
3.1
8.1
15.7
32.4
BT 30 pg/kg alone
1
1.0
1.8
6.0
17.3
62.0
BT 30 fg/kg alone
1
1.7
2.4
7.0
16.1
41.6
cp 200 mg BT 30 mg
1
1.0
1.1
2.3
7.5
19.4
cp 200 mg/kg alone
1
1.0
2.4
3.5
12.9
32.6
TABLE 11
Statistically Significant Effect on Reducing Tumor Volume
TREATMENT
DAY 7
DAY 10
DAY 14
DAY 17
Cyclophosphamide (cp)
No
Yes
Yes
No
Cp + BT
Yes
Yes
Yes
Yes
The combination of BT/cp also drastically reduced metastases in these animals. The number and site of metastases in these animals, measured at autopsy, were recorded for each animal. As seen in Tables 12 and 13, the control group receiving cp alone had dozens of metastatic lesions in the lungs and frequently had cancer in other organs. By contrast, combination therapy with 30 mg/kg BT and 200 mg/kg cp resulted in fewer and smaller lung metastases (p=0.08). Further, no metastasis to organs other than the lungs was observed with combination therapy. Thus, the combination of BT/cp helped control the spread of the primary tumor to a greater degree than did cp alone. None of the animals treated with the combination had greater than 10 metastatic lesions, while two-thirds of untreated controls and half of the Cp-treated animals had 10 or more metastatic lesions.
TABLE 12
Beta-alethine plus cp Effect on Metastasis
Percent of Animals with Greater than 10 Metastases
Control
66.7
Cp 200 mg/kg
50
Cp 200 mg/kg + BT 30 mg/kg
0
TABLE 13
Number of Metastases on Day 42
Number
over 30
of Metastases
0-10
11-20
21-30
(full of metastases)
Saline
5
3
2
5
Cp 200 mg/kg
4
3
0
1
Cp 200 mg/kg and
10
0
0
0
BT 30 mg/kg
EXAMPLE XIII
Beta-alethine and Cyclophosphamide in MT-1 Breast Cancer
β-alethine was evaluated in a breast cancer xenograft model (MT-1) in male nude mice in four experiments. Fragments of tumor, 3-4 mm in diameter were subcutaneously inoculated. In the first experiment, BT (30 fg/kg to 30 mg/kg) was administered alone via intra-peritoneal (i.p.) injection either 3× week or on days 13, 27 and 41 after subcutaneous tumor inoculation. Animals were observed over a period of 45 days after tumor cell injection. Injection of BT at a dose of 30 ng/kg injected every 14 days produced a tumor growth inhibition comparable to or greater than that achieved in previous studies with known clinical cytostatics including mitoxantrone and cyclophosphamide, and greater than those for optimal doses of doxorubicin, vincristine, 5-fluorouracil, tamoxifen, and cisplatin. (Fichtner, I et al, in Arnold, W, et al. (Eds.), Immunodeficient Animals: Models for Cancer Research. Contrib. Oncology, Basel, Karger, 1996, volume 51; Naundorf, H, et al., Breast Cancer Research and Treatment, 23, 87-95, 1992.) Importantly, treatment with BT did not produce any toxic effects as could be measured by changes in body weight or blood parameters.
Statistically significant differences were observed within one week of a single injection of BT, and increased throughout the experiment. (At day 45, for the Mann-Whitney U test, p=0.003.) As seen in Table 14, tumors in all groups started at about 0.1 cm 3 . By day 38, control tumors were almost 2 cm 3 and they reached almost 3 cm 3 by day 45. In contrast, the optimally treated BT group receiving 30 ng/kg never exceeded the 0.4 cm 3 size reached on day 38. Injecting every other week was more effective than administering the same dose 3× week. The T/C ratio (treated vs. control median relative tumor volume) was 29% at 45 days following 3 injections of 30 ng/kg BT.
TABLE 14
Median Tumor Size (cm 3 ) in MT-1 Breast Cancer Study BT Treatment Every 14 days
per kg
day 13
16
20
23
27
30
34
38
41
45
Saline
0.106
0.192
0.385
0.566
0.839
1.070
1.588
1.875
2.303
2.902
30 ug
0.055
0.095
0.180
0.193
0.325
0.408
0.410
0.607
0.696
0.743
30 ng
0.080
0.104
0.176
0.202
0.250
0.294
0.298
0.426
0.429
0.419
30 fg
0.104
0.128
0.213
0.253
0.442
0.637
1.062
1.241
1.464
1.911
TABLE 15
RTV in MT-1 Breast Cancer Study
day 13
16
20
23
27
30
34
38
41
45
Saline
1
1.7
3.7
4.9
7.0
8.1
12.5
13.9
17.7
20.7
30 ug
1
1.4
2.6
3.0
4.3
5.2
6.0
9.1
11.5
14.0
30 ng
1
1.4
2.1
2.3
2.8
3.4
3.8
4.5
4.9
6.0
30 fg
1
1.6
3.4
4.4
7.6
9.3
11.9
16.1
18.2
19.8
In the second experiment with MT-1 breast cancer, BT was administered on day three only, at doses of 30 fg/kg to 3 micrograms/kg. The T/C ratio of treated vs. control median RTV was measured on day 28. RTV in the group receiving 3 ug/kg BT was 32%; for 300 ng/kg BT, the T/C ratio was 42%. The most effective dose of BT was 3 ug/kg which is a higher dose than was required in the first experiment. The other doses of BT (30 ng, 3 ng, 0.3 ng, and 0.03 ng) alone were not effective in this experiment. See Table 16. These observations of RTV were made only through day 28.
TABLE 16
Median RTV for MT-1 Tumors Treated with BT on Day 3
day:
8
14
21
28
saline
1.160
2.333
5.721
7.908
300 ng/kg
1.105
1.243
2.532
3.317
3 ug/kg
1.012
0.955
1.756
2.526
In a parallel experiment, a low dose of 30 ng of BT was injected directly into the tumor on days 3, 17 and 31. The T/C for RTV measured on day 35 was 50%.
TABLE 17
Median RTV for MT-1 Tumors Treated on Day 3 by Intratumor injection
day
8
11
14
17
21
24
28
31
35
Saline
1.29
1.66
2.35
3.35
6.11
8.22
10.01
13.43
17.79
BT 30
1.27
1.40
1.77
2.61
3.74
4.34
4.93
6.37
8.01
ng
In the fourth experiment, animals with advanced (day 42) tumors were given cp at doses of 300, 200 or 100 mg/kg, with or without 30 mg/kg BT (a single dose of BT was administered 30 minutes prior to cp). Beta-alethine given alone was not effective. At the lowest dose of 100 mg/kg, BT significantly improved the anti-tumor effect over an equivalent dose of cp alone as was measured by median tumor volume. Thus, the combination of BT/cp has a synergistic effect on treating breast cancer.
TABLE 18
BT/cp Combination Study on Advanced MT-1 Breast Cancer
A. Median Relative Tumor Volume
day 42
46
49
53
59
Saline
1
1.30
1.77
1.89
2.29
300 mg/kg cp
1
1.34
1.14
1.15
1.14
200 mg/kg cp
1
1.15
1.11
1.21
1.15
100 mg/kg cp
1
1.37
1.54
1.50
1.85
30 mg/kg BT & 300 mg/kg cp
1
1.12
1.29
1.19
0.95
30 mg/kg BT & 200 mg/kg cp
1
1.30
1.30
1.25
0.99
30 mg/kg BT & 100 mg/kg cp
1
1.16
1.17
1.13
1.85
B. Tumor Size, Body Weight and Blood Parameters
Δ
Thrombo-
weight,
T/C RTV
WBC d 46
cytes (10 6 /
Dose
d 42-49
d 49
d 59
(10 6 /mL
mL) d 46
control
0%
16.0
765
BT
30 mg/kg
0.01
72%
165%
14.4
789
Cp +
100 mg/kg
−7%
87%
81%
10.3
756
BT
30 mg/kg
6%
66%
81%
8.5
774
Cp +
200 mg/kg
−18%
63%
50%
5.5
505
BT
30 mg/kg
10%
74%
43%
5.9
604
Cp +
300 mg/kg
−20%
65%
50%
5.6
425
BT
30 mg/kg
−16%
73%
42%
1.5
949
Table 19 shows data from a study in which eight animals having advanced tumors received 300 mg/kg cp with 30 mg/kg BT and eight animals received 300 mg/kg cyclophosphamide alone. A dose of 300 mg/kg exceeds the maximum tolerated dose (MTD). The cp-only group experienced 25% toxic deaths, while the group receiving the combination drug of the present invention had 0% toxic deaths. Thus, the addition of 30 mg/kg BT to a highly toxic dose of 300 mg/kg cyclophosphamide completely eliminated the toxic deaths caused by cyclophosphamide alone. Frequently, the effective dose of a chemotherapeutic agent approaches the toxic dose, therefore, there is a great need for a way to reduce toxicity without reducing the therapeutic effectiveness of the chemotherapeutic agent. Adding BT to a highly toxic dose of a chemotherapeutic agent provides a safety margin by reducing the toxicity of the agent.
Most tumors grew in size in the group receiving 300 mg of cp alone, indicating progression of the disease. Median tumor size increased 25%. By contrast, there was a 14% decrease in median tumor size in the BT/cp groups, and no progression of the disease. The increase in tumor size was statistically significant (chi-square p value for tumor regression=0.04, 1-tailed). Finally, the last two readings in the BT/cp group indicated tumor regression in 75% of the animals while only 12% showed regression in the Cp-only group.
TABLE 19
MT-1 Human Breast Cancer
BT Increases Tumor Regression and Decreases Toxic Deaths
Status of Individual Mice at Final Two Tumor Readings
Cp 300 mg/kg &
Status
Cp 300 mg/kg
BT 30 mg/kg
Died of toxic effects
25%
0%
Last 2 readings indicate progression
12%
0%
Last reading indicates progression
25%
0%
Last 2 readings stayed the same
0%
12%
Last reading indicates regression
25%
12%
Last 2 readings indicate regression
12%
75%
Group median tumor size change
increase 25%
decrease 14%
(measured on day 17)
Table 19 is based on change at last two readings (difference from day 7 to day 11 and from day 11 to day 17). When the last two readings are different, the final reading is used. The categories are mutually exclusive and include all 8 mice in each group. Values were rounded to two decimal places.
EXAMPLE IV
Beta-alethine Reduces the Toxicity of Taxol
The effect of combining BT with paclitaxel (PAC, or TAXOL™) on the toxicity of paclitaxel was investigated. In a first study, groups of 10 female non-tumor-bearing athymic (NCr-nu) mice were administered paclitaxel i.v. at doses of 50 and 30 mg/kg/dose on a qld×5 schedule, which means once each day for five days. Paclitaxel (PAC) was in 12.5% cremophor/12.5% ethanol/75% saline alone, or in combination with 30 mg/kg BT (first dissolved in saline) and delivered as a single i.v. injection (0.1 cc/10 gm body weight). BT was also administered on a qld×5 schedule. Body weights were measured twice a week and survival data was recorded daily. The study was terminated on day 21.
The results, summarized in Table 20 below, show that less weight was lost in the group receiving 50 mg PAC/30mg BT at all time points, and there was an increase in weight gain on day 21 that is twice the increase with PAC alone. The addition of BT to 30 mg PAC decreased the amount of weight lost by days 7 and 10, but did not increase weight on days 14 and 21 over levels observed with 30 mg PAC alone. Weight loss values reflect the lowest recorded weight, which was on day 7 for all groups. Importantly, there were fewer deaths when BT was coadministered with either 30 mg or 50 mg paclitaxel.
For the group receiving 50 mg paclitaxel, the survival difference was statistically significant (log rank=6.41, p=0.0113). There were 9 deaths on day 21 with 50 mg PAC alone, but only 2 deaths when 30 mg BT was administered with 50 mg PAC. When BT was coadministered with 30 mg PAC there was only 1 death on day 21, which was due not to toxicity, but to a technician error. By contrast, there were 2 toxic deaths with 30 mg PAC alone.
TABLE 21
Effect of the Combination β-alethine (BT)/paclitaxel (PAC)
On Mean Body Weight and Mortality
Group
Outcome
Day 1
7
10
14
21
PAC. 50 mg
mean weight (gm)
19
13
12
14
21
BT 0 mg
% weight change
—
−31.6
−36.8
−26.3
+10.5
deaths (cummul.)
0
1
9
9
9
PAC. 50 mg
mean weight (gm)
19
14
17
19
23
BT 30 mg
% weight change
—
−26.3
−10.5
0
+21.1
deaths (cummul.)
0
2
2
2
2
PAC. 30 mg
mean weight
19
14
15
18
23
BT 0 mg
% weight change
—
−26.3
−21.1
−5.3
+21.1
deaths
0
1
2
2
2
PAC. 30 mg
mean weight
19
16
19
20
23
BT 30 mg
% weight change
—
−15.8
0
+5.3
+21.1
deaths
0
0
0
1*
1*
*due technician error that caused immediate death which was not due to toxicity which would have caused death after a delay of several days.
In the second study, groups of 10 female non-tumor-bearing athymic (NCr-nu) mice were administered PAC i.v. (40 mg/kg/dose) or dexamethasone i.p. (10 mg/kg/inj.) once a day for 5 days. PAC was in 10% cremophor/90% saline. PAC and dexamethasone were injected i.v. either alone or thirty minutes after administering either 30 or 100 mg/kg/doses BT (first dissolved in saline) injected i.p. Body weights were measured daily through day 14, then twice weekly through day 29 when the study was terminated. Deaths were also observed daily.
The results shown in Table 22 show greater recovery from PAC-induced weight loss when 30 mg/kg BT was coadministered with PAC. There was little weight loss with BT alone or in combination with dexamethasone, and no changes with dexamethasone alone. There were no toxic deaths in this study, however a total of 7 mice died due to an embolic reaction to the PAC injection in the BT combination groups.
TABLE 22
Percent Body Weight Loss* From Day 0
day
1
5
6
7
8
9
10
11
12
13
21
saline
2.7
4.6
5.2
6.9
4.8
5.7
5.1
7.4
4.6
3.9
2.6
Taxol 40 mg/kg IV
3.8
10.7
11.0
15.2
17.2
17.5
14.6
11.8
10.4
7.8
−1.2
BT 100 mg IP
4.2
0.4
2.6
2.5
3.8
5.8
4.6
5.6
6.3
3.2
3.4
BT 30 mg IP
1.2
1.1
−0.9
0.1
2.8
3.4
4.6
7.2
6.8
7.7
0.7
Taxol & BT 100 mg/kg
1.7
6.6
13.0
15.6
16.5
15.1
15.5
13.0
12.1
7.4
−6.2
Taxol & BT 30 mg/kg
3.9
12.0
14.2
13.9
10.2
9.9
7.2
2.9
6.5
1.0
−3.5
DEX.10 mg IP
3.0
4.6
2.8
3.4
2.4
3.6
2.8
1.3
3.7
2.1
0.1
DEX.10 mg & BT 30 mg
3.1
7.3
6.9
4.5
5.7
4.1
2.6
1.9
−1.9
−0.3
−6.1
*weight gain indicated by negative numbers
Thus, two studies with different procedures showed similar beneficial effects of administering 30 mg/kg BT to decrease paclitaxel-induced toxicity.
All documents cited above are hereby incorporated in their entirety by reference. The entire contents of U.S. Provisional Appln. No. 60/005,336, filed Oct. 17, 1995; and Nos. 60/075,966 and 60/085,474, are also incorporated herein in their entirety.
One skilled in the art will appreciate from a reading of this disclosure that various changes in form and detail can be made without departing from the true scope of the invention. | The present invention relates to peptide-like compounds, e.g. aminocarboxylic acid amide derivatives, and to methods of using same to stimulate cells of the immune system, bone marrow and other organs. The present compounds can be used to enhance vaccination, increase synthesis of and enhance function of blood cell components and enhance anti-neoplastic effects of various agents. The compounds of the invention can be used to produce a variety of further pharmacologic effects. | 0 |
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This is a continuation-in-part application taking priority from Ser. No. 10/952,090 filed on Sep. 28, 2004, which takes priority from Ser. No. 10/862,527 filed on Jun. 7, 2004, now U.S. Pat. No. 6,942,424.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates generally to routing drainage and more specifically to modular drainage components, which provide different modular components for routing drainage.
[0004] 2. Discussion of the Prior Art
[0005] There are two different types of ditch liners. The first type of ditch liner is an open ditch liner. An example of an open type of ditch liner is found in U.S. Pat. No. 3,854,292 to Nienstadt. Nienstadt uses a relatively light plastic resin that is retained with a quantity of stakes. The second type of ditch liner is a closed ditch liner. The closed ditch liner includes a substantially U-shaped trough with a cover. The cover may have openings formed therethrough. Three examples of closed type ditch liners are found in U.S. Pat. No. 5,226,748 to Barenwald et al., U.S. Pat. No. 5,443,327 to Akkala et al., and U.S. Pat. No. 5,522,675 to Gunter. The Barenwald et al. and Gunter patents disclose using relatively complicated connecting devices to retain each liner section in tight connection to each other.
[0006] Accordingly, there is a clearly felt need in the art for modular drainage components, which route drainage and which may be secured to each other with a connection key.
SUMMARY OF THE INVENTION
[0007] The present invention provides a modular ditch liner that does not require complicated installation and assembly. An open modular ditch liner includes a plurality of open liner sections and at least one alignment key. The cross section of each open liner section includes a substantially concave shape formed on a top thereof. The plurality of open liner sections are preferably fabricated from cement block on a cement block casting machine. Casting cement blocks is a cost effective manufacturing process relative to cast iron or open cast molding. A key slot is formed on at least one side of each open liner section to receive a single alignment key. However, the at least one key slot may be replaced with at least one key opening. Each key opening is formed through a length of the open liner section, near a side thereof. The key opening is sized to receive an alignment key.
[0008] A closed modular ditch liner includes a plurality of closed liner sections, a plurality of covers, and at least one alignment key. The cross section of each closed liner section includes at least one trough contour and a single cover retention lip formed on a top end of each side thereof. The plurality of closed liner sections and covers are preferably fabricated from cement block on a cement block casting machine. Each cover is laterally retained between the two cover retention lips. A key slot is formed on at least one side of the closed liner section to receive a single alignment key. However, the at least one key slot may be replaced with at least one key opening. Each key opening is formed through a length of the closed liner section, near a side thereof. The key opening is sized to receive an alignment key.
[0009] The key slot may also include a positive taper or an interference fit. The key slot with an interference fit may have the shape of a negative taper or a substantially rounded shape. The key slot with an interference slot would provide an interference fit to an alignment key. The alignment key includes a block embodiment or an extruded embodiment. The block alignment key would be preferably used in the positive taper key slot. The length of a block alignment key would preferably be as long as an open liner section. Each block alignment key would engage two adjacent open liner sections. The extruded alignment key would be fabricated from an extruded material and preferably retained in an interference fit key slot.
[0010] An alignment key may be replaced by a riser section. The riser section includes a side member and an alignment key projection. The length of the riser section is preferably the same as that of the open liner section. The side member constrains the flow of fluid relative to the open liner section. The alignment key projection is sized to be received by one of the key slots of the open liner section. Further, the open liner sections may be formed as a trapezoid to allow the open liner sections to fit curved drain ditch applications. At least one end of the open liner section is angled.
[0011] A channel alignment key may be used to connect two adjacent open liner sections. An inside width of the channel alignment key is sized to receive the thickness of the two adjacent open liner sections. An erosion barrier insert may be placed between the ends of two adjacent open liner sections. Each erosion barrier insert has substantially the same cross section, as the open liner section, with the exception of a top portion. The top portion of the erosion barrier insert exceeds the height of the substantially concave shape in the open liner section. A radius liner insert includes a cross section that is the same as that of the open liner section. The radius liner insert is placed between the ends of two adjacent open liner sections to help create a radius with a plurality of open ditch liner sections.
[0012] A width expandable modular ditch liner includes a plurality of open liner sections, a plurality of side connection keys and a plurality of expandable liner sections. A pear shaped slot is formed in each side of each open liner section. The pear shaped slot is formed in at least one side of each expandable liner section. A pitch expandable liner section includes a trapezoidal cross section, which enables expandable liner sections to extend from the open liner section at some predetermined angle. A single pear shaped slot is formed in each side of the pitch expandable liner section. Side and end adjacent liner sections are attached to each other with at least one side connection key. Each side connection key includes a tubular body and two rod inserts. Each tubular body includes a first pear shaped side and a second pear shaped side. Each pear shaped side includes a rod opening. Each rod opening is sized to receive a single rod insert.
[0013] A mitered width expandable modular ditch liner includes a plurality of open liner sections, the plurality of side connection keys and a plurality of expandable liner sections. A pear shaped slot is formed in each side of each mitered open liner section. The pear shaped slot is formed in at least one side of each expandable liner section. Either at least one side of each open liner section may be mitered and/or at least one side of each mitered expandable liner section is mitered to provide an angle between each open liner section and the expandable liner section. Side and end adjacent liner sections are attached to each other with at least one side connection key. A flow restrictor liner section may be substituted for the expandable liner section.
[0014] A liner section spacer is preferably placed between each end of two adjacent liner sections. The liner section spacer includes a pear shaped slot that is sized to be received by one of the tubular bodies of the side connection key. The liner section spacer is fabricated from a resilient material, such as rubber. If the liner section spacer is fabricated from rubber, the rubber preferably has a hardness of 30-60 durometer.
[0015] A tapered alignment key may be used to connect the ends and sides of adjacent liner sections. The tapered alignment key may also be tubular. A positive taper key slot is formed in at least one side wall of each liner section. Each end of the tapered alignment key is sized to fit in a single positive taper key slot such that a gap is left between an end wall of the positive taper key slot and an end of the tapered alignment key. Contact between the tapered walls of the positive taper key slot and tapered surfaces of the tapered alignment key provide some positive locking to prevent the tapered alignment key from moving within the positive taper key slot.
[0016] A modular curb liner includes a plurality of curb liner sections. At least one alignment key is preferably used to retain the plurality of curb liner sections, adjacent to each other. A key slot is formed in at least one side of each curb liner section to receive the at least one alignment key. One side of each curb liner section includes a raised edge. The other side of each curb liner section is placed, adjacent a road and the one side is placed, adjacent a strip of land.
[0017] A culvert receiver includes a liner end and a culvert end. A cross section of each open liner section includes a substantially concave shape formed on a top thereof. The liner end of the culvert receiver is sized to interface with an open liner section. The substantially concave shape preferably matches that of the open liner section. Each side of the culvert receiver preferably flares outward from substantially the liner end to the culvert end. The flare on each side may be straight, curved or any other appropriate shape. The culvert end of the culvert receiver is sized to interface with a culvert. The substantially concave shape flares outward, substantially parallel to each side. At least one alignment key is preferably used to retain a single ditch liner section relative to the liner end of the culvert receiver. A key slot is formed in at least one side, at the liner end of each culvert receiver to receive the at least one alignment key.
[0018] A secondary flow connector includes a first end extension, a second end extension and a side extension. The first end extension, the second end extension and the side extension are sized to interface with an open liner section. A cross section of the first end extension, the second end extension and the side extensions each include a substantially concave shape formed on a top thereof. The substantially concave shape continues through a middle of the secondary flow connector. At least one alignment key is preferably used to retain a single open liner section relative to one of the extensions. A key slot is preferably formed in at least one side of each extension to receive the at least one alignment key.
[0019] A trapezoidal ditch liner includes at least one end being nonperpendicular to a side thereof. The cross section of each trapezoidal ditch liner includes a substantially concave shape formed on a top thereof. At least one alignment key may be used to retain adjacent trapezoidal ditch liners relative to each other. A curved ditch liner includes a ditch liner with two curved sides and two nonparallel ends. The cross section of each curved ditch liner includes a substantially concave shape formed on a top thereof. A plurality of curved or trapezoidal ditch liners may be placed end to end to form a radius of curved ditch liners.
[0020] Accordingly, it is an object of the present invention to provide a modular ditch liner that is fabricated from a heavy, yet economical material.
[0021] It is a further object of the present invention to provide a modular ditch liner that utilizes an uncomplicated connection device.
[0022] It is yet a further object of the present invention to provide a modular ditch liner that does not require the creation of a perfect trench for installation.
[0023] It is yet a further object of the present invention to provide a modular curb liner that may be used to keep drainage off grass, adjacent a roadway.
[0024] It is yet a further object of the present invention to provide a culvert receiver that may be used as an interface between a ditch liner section and a culvert.
[0025] It is yet a further object of the present invention to provide a secondary flow connector that may be used to connect a main plurality of ditch liner sections with a secondary plurality of ditch liner sections.
[0026] Finally, it is another object of the present invention to provide a plurality trapezoidal or curved ditch liner sections that may be used to form a radius
[0027] These and additional objects, advantages, features and benefits of the present invention will become apparent from the following specification.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] FIG. 1 is a perspective view of an open modular ditch liner in accordance with the present invention.
[0029] FIG. 2 is a perspective view of an open liner section with two key openings formed therethrough in accordance with the present invention.
[0030] FIG. 3 is a side view of an open modular ditch liner in accordance with the present invention.
[0031] FIG. 4 is a cross sectional view of a trench with an open modular ditch liner contained therein in accordance with the present invention.
[0032] FIG. 5 is a side cross sectional view of a trench with an open modular ditch liner contained therein in accordance with the present invention.
[0033] FIG. 6 is a perspective view of a closed modular ditch liner in accordance with the present invention.
[0034] FIG. 7 is a perspective view of a single closed liner section with two key openings formed therethrough in accordance with the present invention.
[0035] FIG. 8 is a side view of a closed modular ditch liner in accordance with the present invention.
[0036] FIG. 9 is a cross sectional view of a trench with a closed modular ditch liner contained therein in accordance with the present invention.
[0037] FIG. 10 is a side cross sectional view of a trench with a closed modular ditch liner contained therein in accordance with the present invention.
[0038] FIG. 11 is a perspective view of a closed modular ditch liner having two trough contours in accordance with the present invention.
[0039] FIG. 12 is a partial end view of an open liner section with a positive taper key slot of an open modular ditch liner in accordance with the present invention.
[0040] FIG. 13 is a partial end view of an open liner section with a negative taper key slot of an open modular ditch liner in accordance with the present invention.
[0041] FIG. 14 is a partial end view of an open liner section with a substantially round key slot of an open modular ditch liner in accordance with the present invention.
[0042] FIG. 15 is a partial perspective view of an extruded alignment key of an open modular ditch liner in accordance with the present invention.
[0043] FIG. 16 is a perspective view of a plurality of block alignment keys engaged with a plurality of open liner sections of an open modular ditch liner in accordance with the present invention.
[0044] FIG. 17 is a perspective view of a plurality of riser blocks engaged with a plurality of open liner sections of an open modular ditch liner in accordance with the present invention.
[0045] FIG. 18 a is a top view of an open liner section with one angled end of an open modular ditch liner in accordance with the present invention.
[0046] FIG. 18 b is a top view of an open liner section with two angled ends of an open modular ditch liner in accordance with the present invention.
[0047] FIG. 19 is a perspective view of a channel alignment key attached to two adjacent open liner sections of an open modular ditch liner in accordance with the present invention.
[0048] FIG. 20 is a perspective view of an erosion barrier insert retained between to adjacent open liner sections of an open modular ditch liner in accordance with the present invention.
[0049] FIG. 21 is a perspective view of a radius liner insert retained between to adjacent open liner sections of an open modular ditch liner in accordance with the present invention.
[0050] FIG. 22 is a perspective view of a width expandable modular ditch liner in accordance with the present invention.
[0051] FIG. 23 is a perspective view of a mitered width expandable modular ditch liner in accordance with the present invention.
[0052] FIG. 24 is an end view of a mitered width expandable modular ditch liner in accordance with the present invention.
[0053] FIG. 25 is a perspective view of two liner section spacers retained on a side connection key in accordance with the present invention.
[0054] FIG. 26 is a perspective view of a tapered alignment key and tubular tapered alignment key retained in an open liner section in accordance with the present invention.
[0055] FIG. 27 is an end view of a mitered width expandable modular ditch liner retained together with a tapered alignment key and a tubular tapered alignment key in accordance with the present invention.
[0056] FIG. 28 is a perspective view of a plurality of curb liner sections positioned next to each other in accordance with the present invention.
[0057] FIG. 28 a is a perspective view of a plurality of curb liner sections positioned next to each such that water seeps between adjacent curb liners in accordance with the present invention.
[0058] FIG. 29 is an end view of a curb liner section in accordance with the present invention.
[0059] FIG. 30 is a top view of a culvert receiver in accordance with the present invention.
[0060] FIG. 31 is an end view of a liner end of a culvert receiver in accordance with the present invention.
[0061] FIG. 32 is an end view of a culvert end of a culvert receiver in accordance with the present invention.
[0062] FIG. 33 is a top view of a secondary connector in accordance with the present invention.
[0063] FIG. 34 is a top view of a secondary connector with a side extension that is nonperpendicular to an axis of main flow in accordance with the present invention.
[0064] FIG. 35 is an end view of a secondary connector in accordance with the present invention.
[0065] FIG. 36 is a side view of a secondary connector in accordance with the present invention.
[0066] FIG. 37 is a top view of a plurality of trapezoidal ditch liners in accordance with the present invention.
[0067] FIG. 38 is an end view of a trapezoidal ditch liner in accordance with the present invention.
[0068] FIG. 39 is a top view of a plurality of curved ditch liners in accordance with the present invention.
[0069] FIG. 40 is an end view of a curved ditch liner in accordance with the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0070] With reference now to the drawings, and particularly to FIG. 1 , there is shown a perspective view of an open modular ditch liner 1 . With reference to FIGS. 2-4 , the open modular ditch liner 1 includes a plurality of open liner sections 10 and at least one alignment key 12 . The cross section of each open liner section 12 includes a substantially concave shape 14 formed on a top thereof. Preferably, a tapered surface 16 terminates each end of the substantially concave shape 14 . The tapered surfaces 16 are structured to align with the inclines of each side of a ditch 100 . Preferably, a key slot 18 is formed on at least one side of each open liner section 10 to receive a single alignment key 12 . An alignment key with a square cross section is shown, but the cross section of the alignment key 12 may be other shapes, such as round. The alignment key 12 retains at least two open liner sections 10 in vertical and horizontal alignment to each other. If the base under one of the open liner sections sinks, the alignment key 12 in the adjacent open liner sections will retain the one open liner section in vertical alignment with the adjacent open liner sections.
[0071] The key slot 18 may be replaced with a key opening 20 . Each key opening 20 is formed through a length of the open liner section 10 ′, near an end thereof. The key opening 20 is sized to slidably receive the inner alignment key 22 . The plurality of open liner sections 10 are preferably fabricated from cement block on a cement block casting machine. Casting cement blocks is a cost effective manufacturing process relative to cast iron or open cast molding. When the open liner sections 10 are placed in the ditch 100 , ends of each liner section 10 preferably do not contact each other; a small gap “A” is left between the ends thereof. The value of gap “A” is preferably between 0.01-0.25 inches. It is beneficial for a small amount of water to drain into the ground below the ditch 100 . However, the minimum value of gap “A” may also be defined by what gap (space) allows water to seep between adjacent open liner sections 10 .
[0072] The open modular ditch liner 1 is preferably installed in a ditch 100 with a two inch gravel base 102 . A bottom of the substantially concave shape 14 is preferably aligned with the opening of a culvert 104 placed adjacent to the open modular ditch liner 1 . With reference to FIG. 5 , water 106 that flows through the culvert 104 or drops directly on to the plurality of open liner sections 10 will seep through the gaps between the open liner sections 10 to the gravel base 102 . The gaps prevent standing water from forming in the open modular ditch liner 1 . The open modular ditch liner 1 is preferably for residential use.
[0073] With reference to FIGS. 6-9 , a closed modular ditch liner 2 includes a plurality of closed liner sections 26 , a plurality of covers 28 , and at least one alignment key 30 . The cross section of each closed liner section 26 includes a trough contour 32 and a single cover retention lip 34 formed on a top end of each side thereof. Preferably, the cover 28 is sized to be received between the cover retention lips 34 . The height of the cover 28 is preferably substantially the same as the height of the cover retention lips 34 . Each cover 28 fits over at least one closed liner section 26 . The trough contour 32 is preferably U-shaped with two tapered side surfaces 36 .
[0074] Preferably, a key slot 38 is formed on at least one side of each closed liner section 26 to receive a single alignment key 30 . Alignment keys with round and square cross sections are shown, but the cross section of the alignment keys may have other shapes, such as being triangular. The alignment key 30 retains at least two closed liner sections 26 . If the base under one of the closed liner sections sinks, the alignment key 12 in the adjacent closed liner sections will retain the one closed liner section in vertical alignment with the adjacent closed liner sections.
[0075] The key slot 38 may be replaced with a key opening 42 . Each key opening 42 is formed through a length of the closed liner section 26 ′, near an end thereof. The key opening 42 is sized to slidably receive the inner alignment key 44 . The plurality of closed liner sections 26 and the covers 28 are preferably fabricated from cement block on a cement block casting machine. A channel 110 is dug deep enough in a bottom of a ditch 108 to allow the top edges of the closed modular ditch liner 2 to be flush with the tapered sides of the ditch 108 .
[0076] With reference to FIG. 10 , when the closed liner sections 26 are placed in the channel 110 , ends of each liner section 26 preferably do not contact each other; a small gap “B” is left between the ends thereof. The value of gap “B” is preferably between 0.01-0.25 inches. It is beneficial for a small amount of water to drain into the ground below the ditch 108 . However, the minimum value of gap “B” may also be defined by what gap (space) allows water to seep between adjacent closed liner sections 26 . The ends of the covers 28 preferably do not contact each other to allow water to drain into the plurality of closed liner sections 26 . A gap “C” is left between the covers to allow water 106 to drain into the plurality of closed liner sections 26 . The value of gap “C” is preferably between 0.01-0.25 inches. However, the minimum value of gap “C” may also be defined by what gap (space) allows water to seep between adjacent covers 28 .
[0077] The closed modular ditch liner 2 is preferably installed in a ditch 108 with a two inch gravel base 102 . A bottom of the trough contour 32 is preferably aligned with the opening of a culvert 104 placed adjacent to the closed modular ditch liner 2 . Water 106 flows through the culvert 104 or seeps through the gaps between the plurality of covers 28 , will seep through the gaps between the closed liner sections 26 to the gravel base 102 . The gaps prevent standing water from forming in the closed modular ditch liner 2 . The closed modular ditch liner 2 is preferably for residential use.
[0078] FIG. 11 shows a closed modular ditch liner 3 where each closed liner section 46 has two trough contours 48 . The closed modular ditch liner 3 includes a plurality of closed liner sections 46 , a plurality of covers 50 , and at least one alignment key 52 . The cross section of each closed liner section 46 includes the two trough contours 48 and a single cover retention lip 54 formed on a top end of each side thereof. A support pedestal 56 is formed between the two trough contours 48 to support at least one cover 50 . Preferably, the cover 50 is sized to be received between the cover retention lips 54 . The height of the cover 50 is preferably the same as the height of the cover retention lips 54 .
[0079] Each cover 50 fits over at least one closed liner section 46 . The plurality of covers 50 may be placed perpendicular or in parallel to a length of the plurality of closed liner sections 46 . The trough contour 48 is preferably U-shaped with one tapered side surface 58 and a straight side formed by one side of the support pedestal 56 . Preferably, a key slot 60 is formed on at least one side of each closed liner section 46 to receive a single alignment key 52 . An alignment key with a square cross section is shown, but the cross section of the alignment key 52 may be other shapes, such as round. The alignment key 52 retains at least two closed liner sections 46 .
[0080] The key slot 60 may be replaced with a key opening as shown in FIG. 6 . The plurality of closed liner sections 46 and the covers 50 are preferably fabricated from cement block on a cement block casting machine. The closed modular ditch liner 3 is positioned in a ditch such that the top edge is flush with the tapered sides of the ditch 102 as shown in FIG. 8 . The closed liner sections 46 preferably do not contact each other, a small gap “D” is left between the ends thereof. A small gap “E” is preferably maintained between each cover 50 . The value of gaps “D” and “E” are preferably between 0.01-0.25 inches. It is beneficial for a small amount of water to drain into the ground below a ditch. However, the minimum value of gap “D” and “E” may also be defined by what gap (space) allows water to seep between adjacent closed liner sections 46 and covers 50 . The open modular ditch liner 3 is preferably for residential use.
[0081] With reference to FIG. 12-14 , the key slot may also include a positive taper or an interference fit. At least one positive taper key slot 62 is formed in an open liner section 10 . The at least one positive taper key slot 62 may be formed on one wall of the open liner section 10 or on both walls. An angle “A” of one wall preferably has a range of between 0.5 to 5 degrees, but other angles may also be used. An angle “B” of the other wall preferably has a range of between 0.5 to 5 degrees, but other angles may also be used. An alignment key is received by the at least one positive taper key 62 in at least two adjacent open liner sections 10 .
[0082] The key slot with an interference fit may have the shape of a negative taper or a substantially rounded shape. However, other shapes of interference key slots may also be used, besides the negative taper or substantially round. The key slot with an interference slot would provide an interference fit to an alignment key. At least one negative taper key slot 64 is formed in the open liner section 10 . The taper may be formed on one wall of the negative taper key slot 64 or on both walls. An angle “C” of one wall preferably has a range of between 0.5 to 5 degrees, but other angles may also be used. An angle “D” of the other wall preferably has a range of between 0.5 to 5 degrees, but other angles may also be used. An interference alignment key 66 may be compressed to be inserted or removed from the negative taper key slot 64 . The interference alignment key 66 must be fabricated from a resilient material to allow compression thereof. However, the interference alignment key 66 could also be inserted from an end of the open liner section 10 .
[0083] At least one substantially round key slot 68 is formed in an open liner section 10 . The substantially round key slot 68 is sized to receive the interference alignment key 66 . The interference alignment key 66 may be compressed to be inserted or removed from the substantially round key slot 68 . The interference alignment key 66 could also be inserted from an end of the open liner section 10 .
[0084] The alignment key may also include an extruded embodiment or a block embodiment. With reference to FIG. 15 , an extruded alignment key 70 preferably includes a key base 72 and at least one key projection 74 extending from the key base 72 . At least one substantially round key slot 68 is formed in the open liner section 10 to receive the at least one key projection 74 . However, other shapes of interference key slots and key projections may also be used, besides substantially round. The extruded alignment key 70 must be fabricated from a resilient material to allow the at least one key projection 74 to be compressed for insertion into the at least one substantially round key slot 68 . The extruded alignment key 70 may also be inserted from an end of the open liner section 10 . The extruded alignment key 70 is preferably long enough to retain a plurality of open liner sections 10 .
[0085] With reference to FIG. 16 , a block alignment key 76 includes a block base 78 and a key projection 80 extending from the block base 78 . A key slot 18 is disposed in the open liner section 10 . The block alignment key 76 preferably has the same length “L” as the open liner section 10 . Each block alignment key 76 is positioned to engage two adjacent open liner sections 10 . A block alignment key 76 ′ does not have the same height as the open liner section 10 .
[0086] With reference to FIG. 17 , an alignment key may be replaced by at least one riser section. A first riser section 82 includes a first side member 84 and a first key projection 86 extending from the first side member 84 . The first riser section 82 may also include at least one key slot 88 for receiving at least one second key projection of a second riser section 90 . The second riser section 90 includes a second side member 92 and the at least one second key projection (not shown) extending from the second side member 92 . Lengths of the first and second riser sections are preferably the same as that of the open liner section 10 . The first side member 84 constrains the flow of fluid relative to the open liner section 10 . The second side member 92 constrains the flow of fluid relative to the first side member 84 .
[0087] With reference to FIGS. 18 a and 18 b , an open liner section section may be formed as a trapezoid (viewed from a top) to allow the open liner sections 10 ′, 10 ″ to fit curved drain applications. One end of an open liner section 10 ′ is terminated with an angle “E.” One end of an open liner section 10 ″ is terminated with an angle “E” and the other end of the open liner section 10 ″ is terminated with an angle “F.”
[0088] The length “L” of any open liner section 10 , 10 ′, 10 ,″ preferably has a value of between 7-14 inches. The length of any block alignment key 76 , 76 ′, preferably has a value of between 7-14 inches. The length of any riser block 82 , 90 , preferably has a value of between 7-14 inches. The modular ditch liner 1 - 3 may be used in other drainage applications, such as swales. It is preferable that adjacent open liner sections 10 , 10 ′, 10 ″ be arranged to have a gap therebetween for drainage.
[0089] With reference to FIG. 19 , a channel alignment key 94 is used to connect two adjacent open liner sections 10 . The channel alignment key 94 includes a base leg 95 and a first retention leg 97 extending from one end of the base leg 95 and a second retention leg 99 extending from the other end of the base leg 95 . An inside length between the first and second retention legs is sized to receive the thickness of the two adjacent open liner sections 10 . Use of the channel alignment key 94 eliminates the need for a key slot in each open liner section 10 . A channel alignment key could also be used to retain a width (instead of thickness of two adjacent open liner sections 10 .
[0090] With reference to FIG. 20 , an erosion barrier insert 96 is placed between the ends of two adjacent open liner sections 10 . Each erosion barrier insert 96 has substantially the same cross sectional area as the open liner section 10 , with the exception of a top portion 98 . The top portion 98 of the erosion barrier insert 96 extends above a lowest portion 15 of the substantially concave shape 14 in the open liner section 10 . The erosion barrier insert 96 reduces the rate of flow through a plurality of open liner sections 10 .
[0091] With reference to FIG. 21 , a radius liner insert 120 includes a cross section that is preferably the same as that of the open liner section 10 . One end of the radius liner insert 120 has a dimension X and the other end of the radius liner insert 120 has a dimension Y, where X>Y. The radius liner insert 120 is placed between the ends of two adjacent open liner sections 10 to help create a radius with a plurality of open ditch liner sections 10 .
[0092] With reference to FIG. 22 , a width expandable modular ditch liner 122 includes a plurality of open liner sections 124 , a plurality of side connection keys 126 and a plurality of expandable liner sections 128 . The plurality of open liner sections 124 do not require a substantially concave shape 125 formed on a top thereof. The top of the plurality of open liner sections 124 may be flat, when used in a width expandable modular ditch liner 122 . A pear shaped slot 130 is formed in each side of each open liner section 124 . The pear shaped slot 130 is formed in at least one side of each expandable liner section 128 . A pitch expandable liner section 132 includes a trapezoidal cross section, which enables the expandable liner section 128 to extend from the open liner section at a predetermined angle. The predetermined angle is created by a side angle created on at least one side of the trapezoidal cross section. A single pear shaped slot 130 is formed in each side of the pitch expandable liner section 132 .
[0093] Side and width adjacent liner sections are attached to each other with the single side connection key 126 . Each side connection key 126 includes a tubular body 134 and two rod inserts 136 . Each tubular body 134 includes a first pear shaped side 135 and a second pear shaped side 137 . Each pear shaped side includes a rod opening 138 . Each rod opening 138 is sized to receive a single rod insert 136 . The tubular body 134 is first inserted into a plurality of adjacent liner sections. A single rod insert 136 is then inserted to each rod opening 138 . The pitch expandable liner section 132 , the expandable liner section 128 and the side connection key 126 allow a width of the opening liner section 124 to be expanded in one or both directions.
[0094] With reference to FIGS. 23-24 , a mitered width expandable modular ditch liner 140 includes a plurality of open liner sections 142 , the plurality of side connection keys 126 and the plurality of expandable liner sections 128 . The plurality of open liner sections 142 ′ do not require a substantially concave shape 143 formed on a top thereof. The top of the plurality of open liner sections 142 ′ may be flat, when used in a mitered width expandable modular ditch liner 140 . The pear shaped slot 130 is formed in each side of each open liner section 142 ′. The pear shaped slot 130 is formed in at least one side of each expandable liner section 128 . At least one side 143 of each mitered width expandable liner section 142 ′ may be mitered to provide an angle between each open liner section 142 ′ and the expandable liner section 128 ′.
[0095] At least one side 129 of each open liner section 128 ′ may be mitered to provide an angle between each expandable liner section 128 ′ and the open liner section 142 ′. Side and end adjacent liner sections are attached to each other with at least one side connection key 126 . A flow restrictor liner section 144 may be substituted for the expandable liner section 128 . The flow restrictor liner section 144 includes an additional height to slow down the flow velocity of water flowing through the mitered width expandable modular ditch liner 140 .
[0096] With reference to FIG. 25 , a liner section spacer 146 may be placed between two adjacent liner sections. The liner section spacer 146 includes a pear shaped slot 148 that is sized to be received by one of the pear shaped sides of the tubular body 134 of the side connection key 126 . The liner section spacer 146 is fabricated from a resilient material, such as rubber. If the liner section spacer 146 is fabricated from rubber, the rubber preferably has a hardness of 30-60 durometer.
[0097] With reference to FIGS. 26-27 , a tapered alignment key 150 is used to connect the ends and sides of adjacent liner sections. The tapered alignment key 150 is preferably fabricated from concrete, but other materials may also be used. A tubular tapered alignment key 152 is preferably fabricated from an extruded plastic material, but other materials may also be used. The tapered alignment key 150 , 152 may be characterized as a side connection key. A first side of the tapered alignment key 150 , 152 includes a first tapered surface 153 and a second tapered surface 155 . A second side of the tapered alignment key 150 includes a first tapered surface 157 and a second tapered surface 159 . A positive taper key slot 154 is formed in at least one side wall of the open liner section 10 ′ and expandable liner sections 156 , 158 . When the open liner section 10 ′ is used with at least one expandable liner section 156 , 158 , the substantially concave shape 14 does not have to be formed in a top thereof. The tapered key slot 154 includes a first tapered wall 160 , a second tapered wall 162 and an end wall 164 .
[0098] An angle “A” of the first tapered wall 160 preferably has a range of between 0.5 to 5 degrees, but other angles may also be used. An angle “B” of the second tapered wall 162 preferably has a range of between 0.5 to 5 degrees, but other angles may also be used. A gap “G” preferably exists between an end of the tapered alignment key 150 , 152 and the end wall 164 , when the tapered alignment key 150 , 152 is fully inserted into the tapered key slot 154 . The gap “G” has a preferably width of at least 0.03 inches. Contact between the tapered walls 160 , 162 of the positive taper key slot 154 and tapered surfaces 153 , 155 , 157 , 159 of the tapered alignment key 150 , 152 provide some positive locking to prevent the tapered alignment key 150 , 152 from moving within the positive taper key slot 154 .
[0099] With reference to FIGS. 28-29 , a modular curb liner 4 includes a plurality of curb liner sections 166 . At least one alignment key 168 is preferably used to retain the plurality of curb liner sections 166 , adjacent to each other. A key slot 164 is preferably formed in at least one side of each curb liner section 166 to receive the at least one alignment key 168 . One type of alignment key is shown FIGS. 28-29 , but other types of alignment keys may also be used, such as those previously disclosed in this application. One side of each curb liner section 166 includes a raised edge 172 . A gradual slope 174 smoothly joins a top of the curb liner section 166 with the raised edge 172 . The gradual slope 174 may be curved, straight or any other appropriate contour. The one side of the plurality of curb liner sections 166 are placed adjacent a strip of land 300 and the other side of the plurality of curb liner sections 166 are placed adjacent a road 302 .
[0100] When the curb liner sections 166 are placed in a channel 304 , ends of each curb liner section 166 preferably do not contact each other; a small gap (space) “H” is left between the ends thereof. The value of gap “H” is preferably at least 0.01 inches. It is beneficial for a small amount of water to drain into the ground below the ditch 100 . However, the minimum value of gap (space) “H” may also be defined by what gap (space) allows water to seep between adjacent curb liner sections 166 .
[0101] With reference to FIGS. 30-32 , a culvert receiver 176 includes a liner end 178 and a culvert end 180 . A cross section of each open liner section includes a substantially concave shape 182 formed on a top thereof. The liner end 178 of the culvert receiver 176 is sized to interface with an open liner section. The substantially concave shape 182 preferably matches that of the open liner section. Each side of the culvert receiver flares outward from substantially the liner end 178 to the culvert end 180 . A shape of the flare on each side may be straight, curved or any other appropriate shape. The culvert end 180 of the culvert receiver is sized to interface with a culvert. The substantially concave shape 182 flares outward, substantially parallel to each side. At least one alignment key 168 is preferably used to retain a single open liner section relative to the liner end 178 of the culvert receiver 176 . The key slot 164 is preferably formed in at least one side of each culvert receiver 180 at the liner end 178 to receive the at least one alignment key 168 . One type of alignment key is shown in FIGS. 30-32 , but other types of alignment keys may also be used, such as those previously disclosed in this application.
[0102] With reference to FIGS. 33-36 , a secondary flow connector 184 includes a first end extension 186 , a second end extension 188 and a side extension 190 . The first end extension 186 , the second end extension 188 and the side extension 190 are sized to interface with an open liner section. A cross section of the first end extension 186 , the second end extension 188 and the side extension 190 each include the substantially concave shape 182 formed on a top thereof. The substantially concave shape 182 continues through a middle of the secondary flow connector 184 . The at least one alignment key 168 is preferably used to retain a single open liner section relative to one of the extensions. The key slot 164 is formed in at least one side of each extension to receive the at least one alignment key 168 . One type of alignment key is shown FIGS. 33-36 , but other types of alignment keys may also be used, such as those previously disclosed in this application. The side extension 190 extends substantially perpendicularly from the secondary flow connector 184 . However, the side extension 190 may also extend from the secondary flow connector 184 ′ at a nonperpendicular angle, as shown in FIG. 34 .
[0103] With reference to FIGS. 37-38 , a trapezoidal ditch liner 192 includes at least one end being nonperpendicular to a side thereof. Angles A and B are preferably equal to each other and less than 90 degrees. The cross section of each trapezoidal ditch liner 192 includes the substantially concave shape 182 formed on a top thereof. A plurality of trapezoidal ditch liners 192 may be placed end to end to form a radius of ditch liners. With reference to FIGS. 39-40 , a curved ditch liner 194 includes a ditch liner with two curved sides and two nonparallel ends. The cross section of each curved ditch liner 194 includes the substantially concave shape formed 182 on a top thereof. A plurality of curved ditch liners 194 may be placed end to end to form a radius of curved ditch liners 194 .
[0104] While particular embodiments of the invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from the invention in its broader aspects, and therefore, the aim in the appended claims is to cover all such changes and modifications as fall within the true spirit and scope of the invention. | Modular drainage components include a curb liner section, a culvert receiver, a secondary connector, a trapezoidal ditch liner section and a curved ditch liner section. A plurality of curb liner sections are inserted between a roadway and a strip of land to block overflow from the roadway. The culvert receiver is placed between a open ditch liner section and a culvert. The secondary connector provides a flow path for secondary flow to or from a primary flow. A plurality of trapezoidal ditch liner sections or a plurality of curved ditch liner sections may be placed end to end to form a radiused path of flow. | 4 |
[0001] The present application is a Continuation of U.S. patent application Ser. No. 14/147,732, filed on Jan. 6, 2014 and claims priority thereto under 35 U.S.C. 120. The disclosure of the above-referenced parent U.S. patent application is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates generally to electronic interface operation, and more particularly, to interfaces that are reconfigurable during or after a calibration phase that measures performance of bit-lanes.
[0004] 2. Description of Related Art
[0005] Interfaces within and between present-day integrated circuits have increased in operating frequency and width. In particular, in multiprocessing systems, both wide and fast connections are provided between many processing units. Data width directly affects the speed of data transmission between systems components, as does the data rate, which is limited by the maximum frequency that can be supported by an interface. Calibration routines performed during system initialization, when an interconnect problem is detected, or periodically for maintenance purposes, automatically test the interconnect and may adjust parameters of the interface circuits in order to align bit-lanes and improve overall performance.
[0006] Present-day systems interconnect designs may provide fault-tolerance by including spare bit-lanes that are either unused unless needed, i.e., when a failed bit-lane is detected. However, the spare bit-lanes add cost and require physical space to implement. In some systems, spare bit-lanes are used to provide alternate communications paths for information such as checkbits or parity bits.
[0007] It is therefore desirable to provide a method that leverages the presence of spare bit-lanes to improve performance and/or reliability of a system that includes a bus interface.
BRIEF SUMMARY OF THE INVENTION
[0008] The above-mentioned objective of providing improved performance and/or reliability of a bus interface is provided in an interface method.
[0009] The method measures performance of the interface while operating the interface at a frequency for which performance margins specified for the interface are violated for a number of the bit-lanes. The bit-lanes that do not meet the performance margins are allocated as spare bit-lanes and the remainder of the bit-lanes of the interface are set as the operational bit-lanes, and the interface is operated using the operational bit-lanes. When an operating bit-lane fails, one of the spare bit-lanes is allocated as a replacement and the operating frequency of the interface is reduced to meet the performance margins. The measuring can be performed repeatedly while increasing the operating frequency of the interface until only the required number of bit-lanes still meet the performance margins and that frequency can be used as the operating frequency of the interface during subsequent operation. Alternatively, or in combination, the operating frequency of the interface can be dynamically increased and decreased while measuring performance margins, so that the interface operating frequency can be maximized while meeting the performance margins for all of the operating bit-lanes.
[0010] The foregoing and other objectives, features, and advantages of the invention will be apparent from the following, more particular, description of the preferred embodiment of the invention, as illustrated in the accompanying drawings.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0011] 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 objectives, and advantages thereof, will best be understood by reference to the following detailed description of the invention when read in conjunction with the accompanying Figures, wherein like reference numerals indicate like components, and:
[0012] FIG. 1 is a block diagram of a computer system in which techniques in accordance with embodiments of the invention are implemented.
[0013] FIG. 2 is a block diagram of an interface connecting two processing blocks in the computer system of FIG. 1 .
[0014] FIG. 3 is a block diagram of an interface unit within the interface of FIG. 2 .
[0015] FIG. 4 is a waveform diagram illustrating an eye diagram measurement within the interface of FIG. 2 .
[0016] FIG. 5 is a flowchart showing a method in accordance with an embodiment of the present invention.
[0017] FIG. 6 is a flowchart showing a method in accordance with another embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0018] The present invention encompasses bus interface management techniques that determine the performance margins of the bit-lanes making up the bus interface and allocate the bit-lanes having worst performance as spares. The techniques can then adjust the interface frequency upward in order to take advantage of any additional performance available from the bus interface due to variations between the bit-lanes, either in the design, due to fabrication variation, or due to environmental conditions. The techniques are embodied in a method that is generally implemented by a processor executing program instructions, such as a service processor, and by a computer program product embodying the program instructions. The operating frequency may also be additionally selected according to utilization and/or power savings schemes, so that an increased operating frequency is attempted only upon demand and/or a lowered operating frequency may be commanded when power savings are required.
[0019] Referring now to FIG. 1 , a processing system in which techniques in accordance with an embodiment of the present invention are practiced is shown. The depicted processing system includes a number of processors 10 A- 10 D, each coupled to a memory controller/bridge 15 A, 15 B in conformity with an embodiment of the present invention. The depicted multi-processing system is illustrative, and processing system in accordance with other embodiments of the present invention include uni-processor systems that are interconnected by interface buses. Processors 10 A- 10 D are identical in structure and include cores 20 A- 20 B and a cache/local storage 12 , which may be a cache level, or a level of internal system memory. Processors 10 A- 10 B are coupled to a main system memory 14 A by memory controller/bridge 15 A, a storage subsystem 16 , which includes non-removable drives and optical drives, for reading media such as a CD-ROM 17 forming a computer program product and containing program instructions implementing operating systems and other software for execution by processors 10 A- 10 D. The illustrated processing system also includes input/output (I/O) interfaces and devices 18 such as mice and keyboards for receiving user input and graphical displays for displaying information. Processors 10 C- 10 D are similarly coupled to a main system memory 14 B, storage subsystem 16 , which includes non-removable drives and optical drives, for reading media such as CD-ROM 17 , by memory controller/bridge 15 B. While the system of FIG. 1 is used to provide an illustration of a system in which the interface architecture of the present invention is implemented, it is understood that the depicted architecture is not limiting and is intended to provide an example of a suitable computer system in which the techniques of the present invention are applied.
[0020] With reference now to the figures, and in particular with reference to FIG. 2 , a bus interface is depicted between two processors 10 A and 10 B. While processors 10 A and 10 B are used to illustrate and support the data connection of two units, the techniques of the present invention extend to address, control and other signal types, as well as connection of memories, peripherals and other functional units within a computer system or other electronic device. The interface between processors 10 A and 10 B is made by a physical connection of output signals 21 A from processor 10 A to inputs of processor 10 B and output signals 21 B from processor 10 B to inputs of processor 10 A, however the techniques of the present invention extend to non-physically connected (wireless) interfaces having multiple datapaths and to bi-directional interfaces, as well.
[0021] Within processors 10 A and 10 B, input signals are received by elastic interface (EI) units 25 A and 25 B, features of which may include features as described in detail in U.S. Pat. No. 8,050,174 entitled “SELF HEALING CHIP-TO-CHIP INTERFACE”, U.S. Pat. No. 7,117,126 entitled “DATA PROCESSING SYSTEM AND METHOD WITH DYNAMIC IDLE FOR TUNABLE INTERFACE CALIBRATION” and in U.S. Pat. No. 7,080,288 entitled “METHOD AND APPARATUS FOR INTERFACE FAILURE SURVIVABILITY USING ERROR CORRECTION.” The disclosures of the above-referenced U.S. patents are incorporated herein by reference. Signals on output signals 21 A and 21 B are received by elastic interface (EI) units 25 A and 25 B, which include receivers 24 A and 24 B that provide signals to selectors 20 C and 20 B. In the interface depicted in FIG. 2 , some of the bit-lanes provided by output signals 21 A and 21 B are not used for operational communications, but rather are provided as spares. The present invention is directed toward selection of the particular bit-lanes to allocate as spares and which bit-lanes to use as operating bit-lanes, as will be described in further detail below. Another pair of selectors 20 A and 20 D route data from the outputs of EI units 25 A and 25 B respectively, to driver circuits 22 A and 22 B, respectively according to which of the bit-lanes are selected as operating bit-lanes. Selectors 20 A- 20 D may be implemented as described in the above-incorporated U.S. patent “SELF HEALING CHIP-TO-CHIP INTERFACE.”
[0022] At the opposing ends of the bus interface, receivers 24 A and 24 B receive the output signals provided from driver circuits 22 A and 22 B, respectively. The spare bit-lanes may or may not be active, but the data transmitted between processor 10 A and processor 10 B is carried by the operating bit-lanes, which are in a subset of output signals 21 A and 21 B. The signals from the operating bit-lanes are routed to the appropriate inputs of elastic interface units 25 A, 25 B by selector circuits 20 B and 20 C, respectively. EI units 25 A, 25 B contain control logic and buffers that permit operation of the bus interface over a wide frequency range, e.g., a range of 1.25:1. The outputs of EI units 25 A and 5 B are then provided to error checking and correction (ECC) decode units 26 A and 26 B that are capable of detecting 2-bit errors and correcting single bit errors. The present invention uses ECC decode units 26 A and 26 B to not only correct dynamic bit errors as ECC units are typically employed to correct, but to maintain interface operation when a bit-lane has completely failed or when the frequency of the interface has been adjusted such that errors occur before the frequency is decreased to maintain safe operating margins as described below. Output drivers 22 A and 22 B are preferably provided on-chip (but could be located off-chip) and receive ECC encoded data from ECC encode units 28 A and 28 B that provide the proper correctable bit patterns for transmission between processors 10 A and 10 B over interface connections 21 A and 21 B. The interface depicted in FIG. 2 will generally also include the static wire test logic described in the above-incorporated U.S. patent “METHOD AND APPARATUS FOR INTERFACE FAILURE SURVIVABILITY USING ERROR CORRECTION”, the details of which are omitted herein for clarity. The result of the DC wire tests further inform the selection of spare bit-lanes, so that a completely failed bit-lane, e.g., due to an open connection or shorted wire, will be selected as a spare bit-lane and remain unused.
[0023] Eye measurement circuits 14 A and 14 B evaluate the edge positions of the received data so that the program that controls the frequency of the interface and the allocation of spare bit-lanes is enabled to determine whether performance margins are met for current operating conditions. Eye measurement circuits 27 A and 27 B are also used to evaluate each of the bit-lanes during initialization and calibration of the interface for selecting which of the spare bit-lanes will be allocated as spares and which will be allocated as operating bit-lanes. JTAG Interfaces 23 A and 23 B provide a mechanism for controlling and checking the results of the tests performed by eye measurement circuits, as well as other control, maintenance and test functions within processors 10 A and 10 B, such as the selection of the operating bit-lanes by programming selectors 20 A- 20 D. JTAG Interfaces 23 A and 23 B are each coupled to one of service processors 19 A and 19 B (which may be alternatively the same shared service processor) for controlling test operations such performance margin evaluations described below, according to program instructions that carry out one or more of the methods as described herein. Alternatively control logic in the form of a state machine may provide the selection and measurement control functions. Service processors 19 A and 19 B include memories for storing the program instructions and data, such as tables of the bit-line performance margins vs. operating frequency that are obtained from laboratory or real-time measurements as described in further detail below. EI units 25 A and 25 B include delay lines and control logic to support an interface that is aligned at initialization via an Interface Alignment Procedure (IAP) that tunes the input delay of EI units 25 A and 25 B to achieve the best attainable position (delay) of the input signals with respect to the clock used to latch or sample the input values. The interface may also be periodically recalibrated so that optimal operation of EI units 25 A and 25 B is maintained. The delay lines used to implement EI units 25 A and 25 B are sensitive to both supply voltage and temperature, so periodic recalibration provides for operation of the interface at higher frequencies and/or lower error rates than could otherwise be attained without recalibration.
[0024] Referring now to FIG. 3 , details of elastic interface unit 25 A (and similarly elastic interface unit 25 B) are depicted. A set of individual bit delay lines 40 provides for de-skew of data arriving at the inputs of elastic interface unit 25 A (and similarly 25 B elastic interface unit), by adding delays to all bits other than the latest arriving bit signal(s). De-skew is performed only at initialization alignment (IAP) under the control of an elastic interface control logic 46 . After de-skew at initialization and also during periodic recalibration, elastic interface control 46 selects a clock delay for a clock delay line 44 that centers a latch enable provided to bit latches 45 in the center of the eye diagram for the data. Iterative techniques are used by elastic interface control 46 , which contains edge detectors and guard-band logic for determining optimal clock position with respect to the de-skewed data output of delay lines 40 . Elastic interface control 46 tests both edges of the data window for all bits, detecting the first edges of the earliest bit and the last edges of the latest bit and then centers the clock position in the middle of the composite data window by adjusting clock delay line 44 .
[0025] A multiplexer 41 coupled to the provided output data is used to select between system or “mission” output data and sync/AC wiretest/recalibration patterns generated by a sync/PRPG generator 42 for performing IAP/AC wiretest/recalibration in the remotely connected elastic interface unit 25 B (and similarly, the patterns for performing the above-described tests on elastic interface unit 25 A receiver circuits are provided by identical or similar output pattern generation circuits within elastic interface unit 25 B). The output signals from multiplexer 41 are provided to drivers 22 for output on the interface wires. After IAP has been performed using the sync pattern mode of sync/PRPG generator 42 , the AC tests provided by a pattern generation mode of sync/PRPG generator 42 are performed. During periodic recalibration, another PRPG pattern is used that provides a more precise alignment than the sync pattern mode of sync/PRPG generator 42 that generates random patterns simulating actual data transfer. A recalibration is generally forced before actively using the elastic interface, in order to perform more optimal alignment of clock delay line 44 .
[0026] The above-described calibration measures the opening of the eye diagrams for the bitlines (the time t EYE between the latest falling edge and the earliest rising edge) to determine if t EYE meets a minimum specified duration t MIN . The methods disclosed below also produce a table or list of the bit-lanes in order of increasing t EYE and allocate the bit-lanes having the lowest t EYE as spares. Other criteria may be applied in addition to, or in some implementations as an alternative to, the eye diagram opening duration t EYE , for example, the total jitter for each bit-line might be measured, signal voltage levels might add a further criteria, etc. Referring now to FIG. 4 , a waveform diagram with exemplary eye diagrams for a set of bit-lanes is shown in an overlaid configuration, with a bit-lane waveform 49 for a first bit-lane that meets the minimum specified eye window duration t MIN and another bit-lane waveform 48 that does not meet the minimum specified eye window duration t MIN at the current operating frequency. As detailed below, the methods of the present invention trade off bus interface operating frequency for performance margin, so that operating frequency is optimized while ensuring that all bit-lanes not allocated as spares meet the performance margins. The operating frequency that is ultimately chosen is not necessarily an operating frequency for which spare bit-lanes will fail the performance margin test(s), but the bit-lanes allocated as spares are those bit-lanes for which the performance margins are least exceeded. In the methods described below, the circuits that provide performance enhancements may be disabled to determine the operating frequency, e.g., delay lines 40 in FIG. 3 and ECC circuits 26 A- 26 B and 28 A- 28 B in FIG. 2 . The enhancements disabled condition can be removed and performance margin criteria again applied, or the enhancements may be applied only after the spare lanes have been allocated and the bus interface operating frequency determined, so that the enhancements only provide additional performance margin.
[0027] Referring now to FIG. 5 , a first method of operating a bus interface is illustrated in a flowchart. First, the interface is initialized using a base bus interface operating frequency that is determined for the design, or alternatively for the particular unit (step 50 ). During initialization and calibration, and optionally during subsequent calibration intervals that are performed periodically or in response to detecting an error, worst-case traffic is generated and the eye margins for the bit-lanes are measured (step 51 ). The bit-lanes having the weakest (smallest) performance margins are identified (step 52 ) and a list or table of the bit-lanes is generated ordered according to performance margin from weakest to strongest (step 53 ). The weakest bit-lanes are allocated as spare bit-lanes (step 54 ). The remaining bit-lanes are selected as the operating bit-lanes and a table of lowest eye margin vs. operating frequency is built for the operating bit-lanes (step 55 ). While the performance margins for the operating bit-lanes meet the performance requirements (decision 56 ) the interface operating frequency is increased (step 57 ) and the table is populated by repeating steps 51 - 56 . Once an operating frequency is reached for which the performance margins are not met (decision 56 ), a previously successful setting is applied (step 58 ) and the bus-interface is operated at the selected operating frequency until a next calibration cycle.
[0028] Referring now to FIG. 6 , a second method of operating a bus interface is illustrated in a flowchart. First, the interface is initialized using lab-identified settings for the design or for the particular unit (step 60 ). The bit-lanes are monitored for the narrowest historic eye window (or other performance margin) (step 61 ). The bit-lanes having the weakest (smallest) performance margins are identified (step 62 ). From laboratory data and the measured historic performance margins, e.g., by interpolation or from tables, an operating frequency is identified and applied (step 63 ). The operating frequency of the interface is then increased (step 64 ) and the interface continues to monitor the historic lowest eye margin for the bit-lanes (step 65 ). While the eye margins are greater than or equal to the specified margins (decision 66 ) the interface is operated at the selected frequency. When the eye margins fall below the specified margins (decision 66 ) the interface frequency is reset to the normal base frequency and calibration is initiated.
[0029] As noted above, portions of the present invention may be embodied in a computer program product, e.g., a program executed by service processors 19 A- 19 B having program instructions that direct the operations outlined in FIG. 5 or FIG. 6 , by controlling the interfaces of FIG. 2 and FIG. 3 . The computer program product may include firmware, an image in system memory or another memory/cache, or stored on a fixed or re-writable media such as an optical disc having computer-readable code stored thereon. Any combination of one or more computer readable medium(s) may store a program in accordance with an embodiment of the invention. The computer readable medium may be a computer readable signal medium or a computer readable storage medium. A computer readable storage medium may be, for example, but not limited to, an electronic, magnetic, optical, electromagnetic, infrared, or semiconductor system, apparatus, or device, or any suitable combination of the foregoing. More specific examples (a non-exhaustive list) of the computer readable storage medium would include the following: an electrical connection having one or more wires, a portable computer diskette, a hard disk, a random access memory (RAM), a read-only memory (ROM), an erasable programmable read-only memory (EPROM or Flash memory), an optical fiber, a portable compact disc read-only memory (CD-ROM), an optical storage device, a magnetic storage device, or any suitable combination of the foregoing.
[0030] In the context of the present application, a computer readable storage medium may be any tangible medium that can contain, or store a program for use by or in connection with an instruction execution system, apparatus, or device. A computer readable signal medium may include a propagated data signal with computer readable program code embodied therein, for example, in baseband or as part of a carrier wave. Such a propagated signal may take any of a variety of forms, including, but not limited to, electro-magnetic, optical, or any suitable combination thereof. A computer readable signal medium may be any computer readable medium that is not a computer readable storage medium and that can communicate, propagate, or transport a program for use by or in connection with an instruction execution system, apparatus, or device. Program code embodied on a computer readable medium may be transmitted using any appropriate medium, including but not limited to wireless, wireline, optical fiber cable, RF, etc., or any suitable combination of the foregoing.
[0031] While the invention has been particularly shown and described with reference to the preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing and other changes in form, and details may be made therein without departing from the spirit and scope of the invention. | A bus interface selects bit-lanes to allocate as spares by testing the performance margins of individual bit-lanes during initialization or calibration of the bus interface. The performance margins of the individual bit-lanes are evaluated as the operating frequency of the interface is increased until a number of remaining bit-lanes that meet specified performance margins is equal to the required width of the interface. The bit-lanes that do not meet the required performance margins are allocated as spares and the interface can be operated at the highest evaluated operating frequency. When an operating bit-lane fails, one of the spare bit-lanes is allocated as a replacement bit-lane and the interface operating frequency is reduced to a frequency at which the new set of operating bit-lanes meets the performance margins. The operating frequency of the interface can be dynamically increased and decreased during operation and the performance margins evaluated to optimize performance. | 6 |
CROSS-REFERENCE TO A RELATED APPLICATION
[0001] The present invention claims the benefit of U.S. Provisional Application No. 60/218,393 filed Jul. 14, 2000.
FIELD OF THE INVENTION
[0002] The present invention is directed to a method for an entity, e.g., a governmental or business entity, to procure a financial product from a financial institution.
BACKGROUND OF THE INVENTION
[0003] Heretofore, governmental and business entities, who were in need of financial products, were required to seek out financial institutions, who may be willing to provide those financial products, and to request proposals for those products through those institution's varied processes. This procedure is time consuming and expensive. It is time consuming because each financial institution is likely to have similar, but different, information needs to consider the request. The entity, therefore, may have to customize its request for each particular institution. It is expensive because the entity would have to maintain a staff to prepare such requests, and the institution would have to maintain a staff to review, analyze, and respond to those requests. Improvement to this procedure could stimulate competition for financial products offered to such entities.
[0004] To facilitate understanding, the following discussion will be directed to the specific example of a governmental entity, e.g., a municipality, county, agency, nonprofit organization, or the like, and a financial institution, e.g., a bank, insurance company, financing company, of the like.
[0005] When a governmental entity needs a financial product, it may obtain them from a financial institution. The governmental entity usually has a fiduciary duty to the tax-paying public, so it must ensure that it procures the best financial product. To do this, the governmental entity usually sends Request For Proposals (RFP) to several financial institutions. The RFP describes the type of financial product needed and requests a bid for the product, usually by a date certain. All bids received by that date certain are then opened and reviewed by the governmental entity, and the “best” product is chosen. This procedure is, not only, inefficient, in both time and money, it may not provide the governmental entity with the “best” product that would be available, if this procedure was more open and available to a broader market.
[0006] To better understand this procurement procedure, lets consider the participants of the entity and the institution. The entity typically has both a finance officer and a manager, the officer being subordinate to the manager. The officer is responsible for generating the RFP, obtaining bids, reviewing the bids, and making a recommendation about which bid is “best.” The institution typically has a relationship manager, a credit administrator, and a market executive. The relationship manager ensures that the entity receives a sound level of service and that the relationship is enhanced by the institution's opportunity to serve. The credit administrator assesses the soundness of any debt or credit risk associated with the bid and the product offered to the entity, and ensures that the institution receives adequate compensation for the offered product. The market executive ensures that the bid is competitive in the market.
[0007] This procurement procedure is slow and inefficient. For example, it is generally paper-based and document intensive. On the entity side, it requires typing an RFP, generating a mailing list, printing the RFPs and envelopes, mailing RFPs, receiving and answering questions from each financial institution, waiting for bids, reviewing the bids, creating a comparative outline for analyzing the bids, presenting findings and recommendations to the manager and/or board of the entity, and then notifying the financial institution which submitted the “winning” bid. On the financial institution side, it requires finding an underwriter for the request, providing the underwriter with historical and current financial information about the entity, soliciting questions and answers from the entity's finance officer, analyzing the credit of the entity, researching market pricing, agreeing to the underwriter's recommendation, presenting that recommendation to credit administrator, obtaining the credit administrator's approval through justification of both credit and pricing, soliciting market executive's input, coming to final agreement on the package, typing out the bid, and mailing out the bid in time for the date certain. This procedure can often take as many as 15 to 30 days for a governmental entity to be able to source a financial product, and some products are so complex that the governmental entity never even undertakes this procedure, or do so only infrequently (e.g., every three to five years). Further, because this procedure is undertaken so infrequently, the entity has to relearn the procedure each time, thereby wasting tax dollars and further slowing the process.
[0008] This procedure is expensive. For example, the traditional business model used by financial institutions for a commercial entity, i.e., a non-governmental entity, includes a dedicated relationship manager, a credit administrator, and a market executive for each commercial customer and for each request made by that commercial customer. This model is expensive because of the staff needed for the underwriting process, as well as, the interaction required to execute a credit and pricing decision. The model for the governmental entity is usually even more expensive. The higher costs are due to several factors. First, the frequency of receiving RFPs from governmental entities, especially the same governmental entity time after time, is not high enough to warrant a dedicated group at most financial institutions. Second, government entities use fund accounting, to which commercial officers are rarely exposed. These two factors require a learning curve for each time an RFP is made. Third, monetary values are generally high in comparison to commercial customers, thus requiring multiple credit authority levels, which means more individuals than the average commercial decision. Lastly, government requests involve public revenue streams and collateral, which brings some additional legal considerations to the credit decision, thus requiring higher-than-ordinary legal counseling and advice.
[0009] This procedure provides no economies of scale for either the governmental entity or the financial institution. For example, governmental entities are often presented with a limited available market of bids because it is often too costly and cumbersome for financial institutions even to respond to an RFP, especially when the size of such deals may not be large enough to justify much time and energy being devoted to the process. Further, due to the limited staffing common with most smaller governments, the finance officer tends to “wear more hats” and is burdened with a workload that often distracts him from one of his direct responsibilities, namely, obtaining the lowest pricing for financial services.
[0010] Accordingly, there is a need to improve this procurement process.
[0011] U.S. Pat. No. 5,915,209 discloses a bond trading system. This system is used in the business of trading bonds, including municipal bonds. The system provides a remedy to difficulties encountered by municipal bond brokers in obtaining accurate and detailed information on municipal bond lots and sales while the transactions are occurring.
[0012] U.S. Pat. No. 6,161,099 discloses a system for conducting auctions, i.e., municipal bond auctions, over the Internet. The system interconnects, via the Internet, an auctioneer and several bidders, so that an auction may be conducted over the Internet.
[0013] U.S. Pat. No. 6,233,566 discloses an online centralized financial products exchange system. This system is used by a “borrower/consumer-person (homeowner)” to obtain a financial product from a financial institution. Also see www.lendingtree.com.
[0014] Way2bid, Inc. (www.way2bid.com) offers an Internet-based sealed bid auction technology. This system is used by entities, governmental or businesses, to obtain products, but not financial products, from vendors. Also see Advantiv, Inc. (www.advantiv.com) and Decision Director (www.decisiondirector.com).
[0015] Nothing in the prior art solves the problem set out herein.
SUMMARY OF THE INVENTION
[0016] The present invention is directed to a method for an entity, a governmental or business entity, to procure a financial product from a financial institution. The method includes the steps of: posting an entity's request for a proposal (RFP) for the financial product to a website, the RFP having been authorized by an official of the entity; electronically notifying the financial institution that the RFP has been posted; reviewing the RFP by the financial institution; and electronically notifying the entity of a result of the review by the financial institution.
DESCRIPTION OF THE DRAWING
[0017] For the purpose of illustrating the invention, there is shown in the drawing a form which is presently preferred; it being understood, however, that this invention is not limited to the precise arrangements and instrumentalities shown.
[0018] [0018]FIG. 1 is a flow diagram of the present invention.
DESCRIPTION OF THE INVENTION
[0019] Referring to FIG. 1, there is shown a flow diagram setting forth the method of procuring financial products 10 . Method 10 is a web-based solution to the above-mentioned problem. The method 10 is intended to be implemented via a website. The website is preferably a secure website, so that privacy of the member is maintained. Members, e.g., financial product sellers (e.g., financial institutions) and financial product buyers (e.g., entities, governmental or business entities, and preferably excluding individuals) would access the method 10 by logging onto the website 12 . When the members identify themselves at the website, the member may receive messages, which are only retrievable by logging on.
[0020] Each member shall preferably have a profile 14 . The profile contains standard information about the member including, but not limited to, name, address, contact information, key individuals, organizational structure, historical data (e.g., income statements, balance sheets, trend financial summary, ratio analysis, credit rating, product pricing, previous RFP submitted, prior products procured). The member shall have the ability to periodically review and update information 16 in the profile 14 . The profile may also contain preferential information about the member including, but not limited to, preferred business partners (e.g., financial institutions).
[0021] The method is usually initiated by the entity. The entity, after logging on and, if necessary reviewing and modifying their profile, selects the type of financial product (discussed below) desired. Selection may be facilitated by “drop down buttons” that provide financial product choices. Each financial product will have a “deal sheet” 18 . The deal sheet outlines, at least, a minimum amount of information that the financial institution shall require to evaluate the entity's RFP. Some of that information may be available from the entity's profile 14 and could be automatically entered onto the deal sheet. Other information would have to be entered by the entity. After completion of the deal sheet, it may be printed off and reviewed 20 . It is contemplated that completion of the deal sheet is the responsibility of the entity's financial officer.
[0022] The entity may then select 22 which financial institutions that it wishes to receive the RFP.
[0023] The RFP must be approved by the entity before it is released to the financial institutions. After completion of the deal sheet, a notification 24 is sent to the entity, specifically, the official of the entity with oversight responsibility. That official reviews the RFP and authorizes 26 its release to the financial institutions.
[0024] A notification 28 is sent to the financial institution. The notification informs the financial institution that an RFP is available for retrieval at the website. The RFP is, preferably, not sent directly to the financial institution after approval by the official, but instead, it is held and must be retrieved by the financial institution.
[0025] The financial institution logs onto the website 30 , retrieves the RFP and begins its review of the RFP. If after the initial review the financial institution believes that further information is needed to fully evaluate and respond to the entity, it may solicit such additional information 32 . The institution prepares the questions and preferably submits them to the entity via the website. Once the questions are at the website, the entity is notified 34 . The entity responds to the questions 36 , preferably via the website.
[0026] The financial institution builds 38 its bid. After completion of the bid, the institution, pursuant to its internal procedures, approves the bid 40 . Thereafter, the bid is preferably released to the website 42 .
[0027] At the website, the various bids from several financial institutions are preferably assembled 44 in a format to facilitate the entity's review and selection of the various bids. The assembled bids, as well as, the individual bids, are presented 46 to the entity.
[0028] The entity selects the “best” bid, pursuant to its internal procedures. The winner is notified preferably via the website 48 .
[0029] The process outlined below is an example of the inventive method as applied to a Small Issuer Financing RFP. This product is one of the most time consuming and detailed; however, the fundamental process is the same for all types of financing products that could be used with the present invention. The below example compares the traditional process with that of the present invention, not only in steps but also in average amount of time (hours: minutes) for each step.
Full Process Breakdown Crafting and Distributing the RFP (Government)
[0030] [0030] Time Elapsed (average) Traditional Process of the Individual Steps Required Process Present Invention Identify most recent RFP to use as :05 :02 template If not applicable, search for :50 :07 relevant example Edit and update example RFP letter 1:35 :17 Manager received and approved RFP 1:40 :20 Retrieve past mailing list and print 1:50 Automatic enveloped distribution Copy RFP letters for distribution 2:00 Mail letters 2:05 Call city executives to solicit best 2:35 rate Field financial information requests 3:05 TOTAL ELAPSED TIME 1:35 to 4:35 :20
RFP Underwriting & Response (Financial Institutions)
[0031] [0031] Time Elapsed (average) Traditional Process of the Individual Steps Required Process Present Invention Branch manager received RFP letter :01 RFP sits in “to do” file (up to 3 12:01 days) Branch manager searches for 12:21 appropriate officer Appropriate officer receives RFP 36:21 :01 (interoffice vs. email) Officer reads RFP and assesses 36:26 :06 opportunity Officer collects 3 years of 36:56 financial data Officer prepares data spread 37:56 Officer evaluates fund balances 38:01 :11 Officer evaluates cash flow 38:11 :21 Officer evaluates essentiality 38:21 :22 Officer evaluates ratio analysis 38:26 :27 Officer reads financial statement 38:46 :47 notes Officer recommends and sends data 39:16 1:02 to credit credit reviews package and 39:21 1:22 opportunity Credit tests underwriting 39:41 1:32 Credit complies list of questions 39:51 1:42 for officer Officer asks questions of government 40:01 1:47 All questions forwarded to all 1:52 participating banks Officer receives answers and shares 40:16 2:07 with credit Credit obtains latest pricing info 40:31 2:12 Officer assists credit in obtaining 41:01 pricing info Credit and officer negotiate pricing 41:16 2:04 Response letter is typed and sent to 41:36 2:07 government TOTAL ELAPSED TIME 29:36 to 54:36 2:07
Proposal Evaluation and Selection
[0032] [0032] Time Elapsed (average) Traditional Process of the Individual Steps Required Process Present Invention Government holds public openings of :30 :15 RFPs Comparative spreadsheet created 1:15 Bids analyzed, kept or discarded 1:20 :20 Recommendation is made by finance 1:35 :35 officer Recommendation is approved by 1:45 :45 council All bidders are notified 2:15 :46 TOTAL ELAPSED TIME 2:15 :46
[0033] Financial products, as used herein, may refer to many different types of financial products, but are preferably primary transactions (i.e., products sold directly to the end-user by the issuing institution) as opposed to secondary transactions (i.e., products sold from one institution to another institution). Financial products may include: investment products, trustee products, financing products, depository products, employee retirement products, advisory products, and audit products. Investment products refer to products where principal is invested with an expectation of receiving a return. Examples of investment products include, but are not limited to, stocks, bonds, certificates of deposit (CD), government agency paper, annuities, notes (e.g., promissory and collateralized), commercial paper, life insurance, mutual funds, and the like. Preferably, these products include CDs, government agency paper, notes, and commerical paper. Trustee products refer to products or services involving a trustee. Examples of trustee products include, but are not limited to, agreements for safekeeping services (e.g., the trustee takes responsibility for assets (e.g., artwork, stock certificates, documents, notes and the like), and agreements to distribute funds and the associated record keeping. Financing products refer to products where monies are obtained with an expectation to pay for the use of those monies. Financing products may be equity or debt products. Examples of financing products include, but are not limited to, loans, notes (e.g., promissory or collaterized), lines of credit, term loans, commercial paper, bonds, equities, and the like. Preferably, these products include loans, notes (e.g., promissory or collaterized), lines of credit, term loans, commercial paper, and bonds. Depository products refer to agreements to receive monies and pay from those monies on demand, negotiable instruments. Examples of depository products include, but are limited to, checking accounts, savings accounts, treasury management services, and the like. Employee retirement products refer to products related to retirement funds. Examples of employee retirement products include, but are not limited to, 401ks, 457s, SEPs, SIMPLEs, IRAs, pensions, and the like. Preferably, these products include 401ks and 457s. Advisory products refer to products in which a client seeks advise on decisions and/or options related to selection, evaluation, execution of, procuring or investing funds, preferably execution of funds. Audit products refer to services related to auditing of accounting or other business systems, preferably accounting audits. In summary, this process is applicable to any type of financial product offered, where the product requirements must be outlined, credit information must be assessed, and product offerings must be compared and selected. For this reason, it should be obvious that the method of the present invention could be applied to financial products not specifically mentioned herein.
[0034] The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and, accordingly, reference should be made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention. | The present invention is directed to a method for an entity, a governmental or business entity, to procure a financial product from a financial institution. The method includes the steps of: posting an entity's request for a proposal (RFP) for the financial product to a website, the RFP having been authorized by an official of the entity; electronically notifying the financial institution that the RFP has been posted; reviewing the RFP by the financial institution; and electronically notifying the entity of a result of the review by the financial institution. | 6 |
This application is a continuation of U.S. application Ser. No. 07/693,540, filed Apr. 30, 1991, now abandoned.
FIELD OF THE INVENTION
This invention relates to a material useful for improving living environment, and more particularly to a material useful for deodorization for animal breeding or keeping and a process for producing the same.
BACKGROUND OF THE INVENTION
Animal breeding or keeping is accompanied with an offensive smell mainly comprising ammonia, triethylamine, and sulfides. Deodorization in animal breeding or keeping has been effected with adsorbents, such as activated carbon, zeolite, bentonire, and impregnated pulp, and deodorant sprays. In keeping, e.g., cats indoors, since excrements of cats give off an awful smell, zeolite, bentonire, siliceous sand, etc. are used as toilet sand, which is disposed after each use. However, if these non-combustible materials are disposed together with combustible garbage, such would be a cause of obstruction of public facilities of garbage incineration, giving rise to a serious social problem.
Impregnated pulp, which has recently been extending its use because of its combustibility, has poor deodorizing effects. Moreover, since it is easily electrified, it adheres to the paws, making the floor dirty. The same disadvantage also applies to activated carbon.
Deodorant sprays only show a slight masking effect, furnishing no fundamental means of deodorization.
Thus, the problem of smell associated with animal breeding or keeping has not yet come to a satisfactory solution. Besides the problem of domestic animals, in cities of growing population, there is an increasing demand for a solution to the problem of smell of laboratory animals from the standpoint of environmental hygiene in the neighborhood.
SUMMARY OF THE INVENTION
In the light of the above-described situation, an object of the present invention is to provide a material capable of effectively removing bad odors of outputs and excrements of animals and a process for producing such a material.
The inventors have conducted extensive investigations and, as a result, it has now been found that the above object of the present invention is accomplished by a formed article of a pulp and/or polyolefin base material, said formed article having a cation exchange group.
DETAILED DESCRIPTION OF THE INVENTION
The base material which can be used in the present invention comprises pulp and/or a polyolefin, such as paper pulp, regenerated paper, polyethylene, and polypropylene. The base material to be used can be appropriately selected from among them according to the end use. The base material preferably has a fibrous form for assuring a wider surface area, which leads to an increased rate of adsorption of harmful substances, and ease of forming into any desired shape. The fibers preferably have a diameter of from 1 to 50 μm. With the fiber diameter being within this range, graft polymerization takes place uniformly over the cross-section of fibers.
A formed article comprising the base material has an aggregate form, such as mat, non-woven fabric, or a mass of spheres or flakes. For use as a toilet for cats, spherical or flaky formed articles are preferred for making it easy for cats to dig in as their habit. The spherical or flaky formed articles preferably have a size of from 2 to 20 mm. If they have too a large size, it is likely that family animals like cats play with them and bring them out of the toilet.
A reactive monomer is graft-polymerized to the formed article to introduce a cation exchange group. The reactive monomer which can be used in the present invention include those having a cation exchange group or a group capable of being converted to a cation exchange group. Examples of such reactive monomers are glycidyl methacrylate, glycidyl acrylate, styrene, and sodium styrenesulfonate. Examples of suitable cation exchange groups include a carboxyl group, a sulfo group, and a phospho group. The cation exchange group is preferably introduced into the formed article in an amount of from 0.5 to 8 mmol/g.
Graft polymerization of the reactive monomer to the formed article can be carried out, for example, by polymerization in the presence of an initiator, thermal polymerization, irradiation-induced polymerization using ionizing radiation, e.g., α-rays, β-rays, γ-rays, accelerated electron rays, X-rays, and ultraviolet rays. Polymerization induced by γ-rays or accelerated electron rays is suitable for practical use.
The amount of a reactive monomer polymerized on the formed article is expressed in terms of grafting rate (%) obtained from equation: ##EQU1##
In the present invention, a grafting rate preferably ranges from 10 to 150%. If the grafting rate is out of this range, performance properties characteristic of the base material tend to be impaired.
Modes of graft polymerization of a reactive monomer to a formed article are divided into liquid phase polymerization in which a formed article is directly reacted with a liquid reactive monomer and gaseous phase polymerization in which a formed article is brought into contact with vapor or gas of a reactive monomer. Either of these modes of polymerization can be chosen in the present invention according to the end use or purpose.
Substances giving off a bad smell of ammonia, triethylamine, etc. can be removed on neutralization reaction with a strongly acidic cation exchange group. That is, the deodorizing material according to the present invention achieves deodorization predominantly through chemical adsorption without being accompanied by desorption of the smell irrespective of environmental changes, whereas most of conventional inorganic adsorbents conduct deodorization through physical adsorption and are therefore liable to release once adsorbed substances depending on environmental changes. In addition, the deodorizing material of the present invention is easily regenerated by washing or a like means for reuse.
The present invention is now illustrated in greater detail with reference to the following Examples, but it should be understood that the present invention is not construed as being limited thereto. All the percents, parts, and ratios are by weight unless otherwise indicated.
EXAMPLE 1
Regenerated paper pulp flakes having an average diameter of 5 mm were soaked in the same volume of a glycidyl methacrylate solution for 10 minutes. After the excess liquid was removed, the impregnated flakes were placed in an irradiation chamber. After rendering the chamber oxygen-free, cobalt 60 γ-rays were irradiated on the flakes at an absorption dose of 1 Mrad to induce graft polymerization to obtain a graft polymer. The resulting polymer was washed with dimethylformamide and then immersed in a 10% propanol-water solution of sodium sulfite at 80° C. for 5 hours to conduct sulfonation. There was obtained a deodorizing material containing 2.5 mmol of a sulfo group per gram of the base material.
A hundred parts by weight of commercially available toilet sand for cats were mixed with 10 parts by weight of the resulting deodorizing material, and the mixed sand was placed in a room having a floor space of about 10 m 2 where a cat was allowed to excrete. After one day, a pungent smell of the cat's excrements was imperceptible 1 m apart from the toilet sand. At this time, the ammonia concentration in the atmosphere 1 cm apart from the surface of the toilet sand was 0.2 ppm as measured with a gas detector. After 2 weeks, the toilet slightly smelled at 1 m distance. At this time, the ammonia concentration at 1 cm distance from the toilet sand was 0.5 ppm as measured with a gas detector.
For comparison, the same test was carried out using toilet sand containing no deodorizing material of the invention. After 1 day, the cat's excrements irritatingly smelled all over the room, and the ammonia concentration 1 cm distant from the surface of the toilet sand was 2 ppm as measured with a gas detector. After three days, the smell was so irritant that one could not stay any more in that room with all the windows and doors shut. The toilet was moved to another place, but the awful smell still remained in the room event after one night had elapsed. So, 30 g of the above prepared deodorizing material packaged in a net was suspended in the center of the room. One day after the suspension, the room had no bad smell at all.
From these results, the deodorizing material of the present invention was proved to produce remarkable deodorizing effects when used either alone or in combination with conventional toilet sand.
EXAMPLE 2
Polypropylene fibers having a diameter of 20 μm were formed into spheres having an average diameter of 5 mm. Accelerated electron rays were irradiated on the spheres in a nitrogen atmosphere at a dose of 10 Mrad by means of an electron beam accelerator. The irradiated spheres were brought into contact with an oxygen-free acrylic acid solution for 2 hours to conduct graft polymerization, followed by washing with a large quantity of warm water. There was obtained a deodorizing material containing 5.6 mmol of a carboxyl group per gram of the base material.
Thirty grams of the resulting deodorizing material were put in a nest box of hamster. After one day, the ammonia concentration in the box was 0.2 ppm as measured with a gas detector. Even after one week, it was not more than 0.5 ppm.
For comparison, when the same test was conducted without using the deodorizing material of the present invention, the ammonia concentration after one day was 1.2 ppm, clearly demonstrating the adsorptive effects of the deodorizing material of the present invention.
While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be make therein without departing from the spirit and scope thereof. | A deodorizing material for breeding or keeping animals and a process for producing the same are described. The material comprises a formed article of a pulp and/or polyolefin base material, wherein said formed article has a cation exchange group. The material is produced by graft polymerization of a reactive monomer having a cation exchange group to a formed article of a pulp and/or polyolefin base material. The material efficiently adsorbs bad smells of animals' excretions through chemical bonding. | 1 |
CROSS REFERENCE STATEMENT
[0001] This application claims the benefit of U.S. Provisional Application No. 60/410,409, filed Sep. 12, 2002.
BACKGROUND OF THE INVENTION
[0002] This invention relates generally to the preparation of certain Group 4 metal amide complexes by means of an amine elimination process to produce metal complexes. More particularly the present invention relates to a novel process for conversion of initial Group 4 metal amides to the corresponding metal diamide complexes.
[0003] The manufacture of Group 4 metal amide complexes has been previously taught in U.S. Pat. No. 5,312,938, U.S. Pat. No. 5,597,935, U.S. Pat. No. 5,861,352, U.S. Pat. No. 5,880,302, U.S. Pat. No. 6,020,444, and U.S. Pat. No. 6,232,256, and elsewhere. In WO02/38628 Group 4 metal complexes containing “spectator ligands” such as amino-substituted cyclic amine compounds were prepared using such a process in the first step of a two step process. Suitable amide complexes include Group 4 metal tetra(N,N-dialkylamino) compounds, especially titanium-, zirconium- or hafnium-tetrakis(N,N-dimethylamide) compounds. Suitable alkylating agents include trialkylaluminum compounds, especially trimethylaluminum, and alumoxanes.
[0004] A persistent problem of the foregoing processes is the inability to produce the diamide complex in high yield and purity. Because the exchange step is an equilibrium process, complete conversion generally cannot be attained even after resorting to the use of elevated temperatures and/or venting or vacuum removal of amine byproducts. A process in which complexation of the metal by a ligand is facilitated, thereby resulting in the use of lower reaction temperatures, shorter reaction times, and/or characterized by higher yields, is still desired.
SUMMARY OF THE INVENTION
[0005] In accordance with this invention there is provided an improved process for the preparation of Group 4 metal amide complexes comprising a monovalent or divalent Lewis base ligand the steps of the process comprising contacting a Group 4 metal amide with a neutral source of a monovalent or divalent, Lewis base ligand group and a solid, Lewis acid under amine elimination conditions to form a Group 4 metal amide complex containing at least one less initial amide group per metal moiety than the original Group 4 metal amide, and recovering the resulting metal complex.
[0006] The products are highly valuable for use as catalysts in combination with activating cocatalysts such as alumoxanes or cation forming agents in the polymerization of olefins to high molecular weight polymers.
DETAILED DESCRIPTION OF THE INVENTION
[0007] All references to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1999. Also, any references to a Group or Groups shall be to the Groups or Groups reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups. For purposes of United States patent practice, the contents of any patent, patent application or publication referenced herein are hereby incorporated by reference in their entirety, especially with respect to the disclosure of synthetic techniques and general knowledge in the art. The term “comprising” when used herein with respect to a composition, mixture or process is not intended to exclude the additional presence of any other compound, component or step.
[0008] Suitable Group 4 metal amides for use in the present invention correspond to the formula,
M(NR 2 ) m X n ,
wherein M is a Group 4 metal, especially hafnium; R independently in each occurrence is a C 1-20 hydrocarbyl group, a C 1-20 halohydrocarbyl group, or two R groups are joined together thereby forming a divalent derivative, preferably R, each occurrence is C 1-4 allyl; X is an anionic ligand other than an amide group of up to 20 atoms not counting hydrogen or two X groups are joined together thereby forming a divalent derivative, preferably each X group is hydride, halide, or a hydrocarbyl-, silyl-, hydrocarbyloxy- or siloxy-group of up to 10 atoms; most preferably chloride or methyl; m is an integer from 1 to 4 and n is an integer equal to 4-m.
[0013] Preferred Group 4 metal amides are Group 4 metal tetrakis(N,N-dihydrocarbyl)-amides, especially Group 4 metal tetralis(N,N-dimethyl)amides, most especially hafnium tetraks(N,N-dimethyl)amide.
[0014] The foregoing Group 4 metal amides are contacted with a neutral source of the desired Lewis base ligating species thereby generating free amine. Suitable ligand sources are monovalent and divalent compounds of the formula L-H or H-L-H wherein L is a monovalent or divalent Lewis base ligand, in which case the resulting free amine corresponds to the formula NHR 2 . Examples of suitable Lewis base ligating species sources include aliphatic and aromatic diamine compounds, and hydrocarbylamine substituted aromatic heterocyclic compounds.
[0015] In particular, suitable sources of Lewis base ligating species include difunctional Lewis base compounds disclosed in WO 02/38628, especially hydrocarbylamine substituted heteroaryl compounds of the formula
R 1 HN-T-R 2 (I),
wherein
R 1 is selected from alkyl cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, and inertly substituted derivatives thereof containing from 1 to 30 atoms not counting hydrogen; T is a divalent bridging group of from 1 to 20 atoms other than hydrogen, preferably a mono- or di-C 1-20 hydrocarbyl substituted methylene or silane group, and R 2 is a C 6-20 heteroaryl group, especially a pyridin-2-yl- or substituted pyridin-2-yl group.
[0019] Preferred examples of the foregoing difunctional Lewis base compounds correspond to the formula:
wherein
R 1 and T are as previously defined, and R 3 , R 4 , R 5 and R 6 are hydrogen, halo, or an alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, or silyl group of up to 20 atoms not counting hydrogen, or adjacent R 3 , R 4 , R 5 or R 6 groups may be joined together thereby forming fused ring derivatives.
[0022] Highly preferred examples of the foregoing difunctional Lewis base compounds correspond to the formula:
wherein
R 3 , R 4 , R 5 and R 6 are as previously defined, preferably R 3 , R 4 , and R 5 are hydrogen, or C 1-4 alkyl, and R 6 is C 6-20 aryl, most preferably naphthyl; Q 1 , Q 2 , Q 3 , Q 4 , and Q 5 are independently each occurrence hydrogen or C 1-4 alkyl, most preferably Q 1 and Q 5 are isopropyl and Q 2 , Q 3 and Q 4 are hydrogen; and R 7 and R 8 independently each occurrence are hydrogen or a C 1-20 alkyl or aryl group, most preferably one of R 7 and R 8 is hydrogen and the other is a C 6-20 aryl group, especially a fused polycyclic aryl group, most preferably an anthracenyl group.
[0026] The most highly preferred difunctional Lewis base compound for use herein corresponds to the formula:
[0027] Under the reaction conditions of the present invention, it has been discovered that the hydrogen of the 2-position of the naphthyl group substituted at the 6-position of the pyridinyl group is subject to elimination, thereby uniquely forming metal complexes wherein the metal is covalently bonded to both the resulting internal amide group and to the 2-position of the naphthyl group, as well as stabilized by coordination to the pyridinyl nitrogen atom through the electron pair thereof. Accordingly, preferred metal complexes contain 2 less amide groups than the original Group 4 metal amide reagent and a difunctional Lewis base ligand additionally coordinated to the metal by means of an electron pair.
[0028] The foregoing reaction is performed in the presence of the solid Lewis acid. Examples of suitable solid Lewis acids included silica, alumina, clay, aluminosilicates, and borosilicates, preferably alumina. Such reagent uniquely promotes amine elimination by acting as an acceptor or scavenger for the amine. In a preferred embodiment, the scavenger is accessible to volatile amine by-products but the remainder of the reaction mixture does not contact the Lewis acid scavenger. As one example, the Lewis acid may be retained in a column or vessel in operative communication with the headspace of the reactor and the amide groups of the Group 4 metal amide are N,N-dimethylamide groups that form the highly volatile amine, N,N-dimethylamine.
[0029] According to the process, the Group 4 metal amide and Lewis base compounds are employed in approximately stoichiometric amounts, preferably in molar ratios (based on amide compound to Lewis base compound) from 1:2 to 2:1. The quantity of solid Lewis acid compound used is preferably from 2:1 to 10 to 1, more preferably from 4:1 to 6:1 based on Group 4 metal amide compound.
[0030] As an illustration, starting from hafnium tetrakis(dimethylamide) and excess alumina scavenger, the resulting metal complex prepared according to the present invention in high yield and efficiency is:
[0031] The amide elimination conditions used in the present process include moderate temperatures from 0 to 100° C., especially from 25 to 75° C., reduced, atmospheric or elevated pressures from 0 to 100 kPa, preferably atmospheric pressure, times from 1 minute to 10 days, preferably from 10 minutes to 2 hours, and use of an aliphatic or aromatic solvent, preferably toluene or ethylbenzene. The resulting complexes may be recovered by filtration, extraction, precipitation, or other suitable technique.
[0032] The resulting Group 4 metal complexes are activated to form the actual catalyst composition by combination with a cocatalyst, preferably an aluminoxane, a cation forming cocatalyst, or a combination thereof and desirably employed to polymerize olefins or combinations of olefins, especially ethylene, propylene, 1-butene, 1-hexene, 1-octene and mixtures thereof; mixtures of the foregoing monomers with vinylaromatic monomers or conjugated or non-conjugated dienes; and mixtures of all of the foregoing monomers. The process is characterized by low temperatures and pressures, typically from 25 to 50° C. and pressures from atmospheric to 10 MPa.
[0033] Suitable alumoxanes for use herein include polymeric or oligomeric alumoxanes, especially methylalumoxane, triisobutyl aluminum modified methylalumoxane, or isobutylalumoxane; neutral Lewis acid modified polymeric or oligomeric alumoxanes, such as the foregoing alkylalumoxanes modified by addition of a C 1-30 hydrocarbyl substituted Group 13 compound, especially a tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compound, or a halogenated (including perhalogenated) derivative thereof, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially a perfluorinated tri(aryl)boron compound or a perfluorinated tri(aryl)aluminum compound.
[0034] The Group 4 metal complexes may also be rendered catalytically active by combination with a cation forming cocatalyst, such as those previously known in the art for use with Group 4 metal olefin polymerization complexes. Suitable cation forming cocatalysts for use herein include neutral Lewis acids, such as C 1-30 hydrocarbyl substituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compounds and halogenated (including perhalogenated) derivatives thereof, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluorinated tri(aryl)boron compounds, and most especially tris(pentafluorophenyl)borane; nonpolymeric, compatible, noncoordinating, ion forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium-, phosphonium-, oxonium-, carbonium-, silylium- or sulfonium-salts of compatible, noncoordinating anions, or ferrocenium-, lead- or silver salts of compatible, noncoordinating anions; and combinations of the foregoing cation forming cocatalysts and techniques. The foregoing activating cocatalysts and activating techniques have been previously taught with respect to different metal complexes for olefin polymerizations in the following references: EP-A-277,003, U.S. Pat. No. 5,153,157, U.S. Pat. No. 5,064,802, U.S. Pat. No. 5,321,106, U.S. Pat. No. 5,721,185, U.S. Pat. No. 5,350,723, U.S. Pat. No. 5,425,872, U.S. Pat. No. 5,625,087, U.S. Pat. No. 5,883,204, U.S. Pat. No. 5,919,983, U.S. Pat. No. 5,783,512, WO 99/15534, WO99/42467, (equivalent to U.S. Ser. No. 09/251,664, filed Feb. 17, 1999).
EXAMPLES
[0035] The skilled artisan will appreciate that the invention disclosed herein may be practiced in the absence of any component which has not been specifically disclosed. The following examples are provided as further illustration of the invention and are not to be construed as limiting. Unless stated to the contrary all parts and percentages are expressed on a weight basis. The term “overnight”, if used, refers to a time of approximately 16-18 hours, the term “room temperature”, refers to a temperature of about 20-25° C., and the term “mixed alkanes” refers to a commercially obtained mixture of C 6-9 aliphatic hydrocarbons available under the trade designation Isopar E®, from Exxon Chemicals Inc. In the event the name of a compound herein does not conform to the structural representation thereof, the structural representation shall control.
[0036] The synthesis of all metal complexes and the preparation of all screening experiments were carried out in a dry nitrogen atmosphere using dry box techniques. All solvents used were BPLC grade and were dried and deoxygenated before their use.
Example 1
[0037] A metal complex was prepared according to the following reaction scheme:
[0038] To a flask fitted with a condenser column packed with dried alumina in a glovebox was added 100 ml of xylene and 16.25 g (0.029 mol) of (1). Hafnium tetrakis(dimethylamide) (12.12 g, 0.034 mol) suspended in 20 ml xylene was added. The resulting suspension was heated to reflux and maintained in that condition for 4 hours. The mixture was then devolatilized leaving 34 g of crude product. To this material 50 g of pentane was added and stirred overnight. The resulting mixture was filtered and the solids washed twice with 12 ml of pentane. The resulting solid was dried under dynamic vacuum yielding 21.3 g of the desired diamide complex as a pale yellow solid.
[0039] Catalytic activity was confirmed by polymerization of 450 g of propylene monomer in 500 ml hexane in a 2 L polymerization reactor at 90° C. using 1.0 μmole of catalyst and a hexane solution of methyldi(octadecylammoniurn)tetrakis(pentafluorophenyl)borate cocatalyst in 1:1 B:Hf molar ratio. | A process for the preparation of a Group 4 metal amide complex comprising a monovalent or divalent Lewis base ligand the steps of the process comprising contacting a Group 4 metal amide with a neutral source of a monovalent or divalent, Lewis base ligand group and a solid Lewis acid scavenging agent under amine elimination conditions to form a Group 4 metal amide complex containing at least one less amide group per metal moiety than the initial Group 4 metal amide. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to household appliances, and more particularly to cooling systems such as those utilized in refrigerators, freezers and air conditioners.
2. Background Art
In the usual operation of appliances, such as refrigerators, freezers and even air conditioners, ice may build up on the evaporator included within the refrigeration system due to moisture in the air. Such ice build up reduces the efficiency of the system and decreases food preservation time because any act of defrosting causes warming of the air in contact with the melting ice.
In the past, a number of different ways have been utilized to determine the need for defrosting of the appliances. The usual techniques include various sensors on the evaporator to measure for ice presence. Some defrost methods are based purely on total time or run time of the compressor. Others frequently include combinations of the number of door openings, while still others employ a technique of recording how long a previous defrost in the appliance took by sensing the switch and comparing this to an optimum time that the switch should be operated. Such methods typically utilize the sensing of the operation of a bi-metallic switch.
A search of the background art directed to the subject matter of the present invention conducted in the U.S. Patent and Trademark Office disclosed the following U.S. Letters Patent:
U.S. Pat. No. 4,689,965 pertains to a control used in conjunction with a refrigeration system that includes defrosting apparatus for removing a frost load from the evaporator and means for energizing the defrosting apparatus at the end of a cooling cycle to initiate a defrost cycle.
U.S. Pat. No. 5,251,454 teaches the control of a defrost cycle of a refrigerator by placing a thermistor between the fins of the included evaporator. Comparator circuitry compares the temperature between that and a set point within the refrigerator.
U.S. Pat. No. 4,407,138 pertains to a control system for initiating the frost mode of operation in a heat pump wherein the ambient temperature is continuously monitored along with various other temperatures to determine appropriate control.
U.S. Pat. No. 5,257,506 pertains to a method for controlling a defrost cycle for effecting the defrost of an outdoor heat exchanger coil by initiating a defrost cycle as a function of outdoor coil temperature and outdoor air temperature.
U.S. Pat. No. 5,319,943 pertains to a microprocessor based control system for controlling frost accumulated on the outdoor evaporator coil of a heat pump.
U.S. Pat. No. 4,974,417 and 4,974,418 deal again with heat pump defrosting operations. These patents teach microprocessor control and the inclusion of exterior temperature sensors.
Based on a thorough review of the above-identified patents, we believe that none of the above teach, disclose or claim the novel combination of elements and functions found in the improved cooling system taught by the present invention.
SUMMARY OF THE INVENTION
In appliances such as refrigerators, freezers, etc,, when ice builds up inside on the evaporator included therein, thermal transfer of cold temperature from the evaporator to the air inside the refrigerator is reduced. It is this ice build up that slows down thermal transfer making the system inefficient. By measuring the amount of time the air inside a refrigerator compressor takes to change, it is possible to detect the build up of ice and initiate a defrost condition, It is well known that the external temperature of the refrigerator also effects the time the air takes to change and it is this differential that is accounted for,
In a manner similar to that taught by our co-pending application entitled "DETERMINATION OF AMBIENT AIR TEMPERATURE OUTSIDE AN APPLIANCE" filed contemporaneously with the present application, we show testing is done with a refrigerator or similar device in a room of controlled external temperature to obtain reference timing. In this arrangement, a sensor is placed inside the refrigerator, either on the evaporator or somewhere else measuring air temperature. The length of time for the refrigerator to change temperature while the compressor is on is known as the cool down time. This is measured and correlated to external temperatures and different levels of ice build up on the evaporator. The time while the compressor is off is less accurate for determining defrost operations. Typically more ice build up will cause the air temperature to decrease at a slower rate.
With the availability of this information, a device such as a microcontroller may be placed within the refrigerator to utilize the reference information. By having a means to measure both the external temperature and the cool down times, the microcontroller can determine when the ice is too thick. The microcontroller compares stored information with the actual time it takes the evaporator to cool down between two predetermined temperatures. When it takes too long versus the stored information, a defrost cycle needs initiation.
It is also possible to utilize the same information or method to determine how long the defrost operation should occur instead of when to initiate the defrost cycle. Instead of waiting for a specific thickness of ice to build up, the microcontroller would run the compressor for a fixed number of cycles. It would then measure the cool down times, process this and utilize a table within the microcontroller based on reference information to vary the length of time the defrost cycle is actually performed.
Certain other factors could cause the inside temperature to change and thus effect cool down times. Such situations as the opening of the door on the box for a short time, letting in warmer or colder air. Also, the amount of mass of cold or warm objects that may be placed inside the box could cause a change. It is possible for these factors to be accounted for by sensing door openings or noticing a different time-temperature curve change than normally happens within the sealed system.
It is also possible that by measuring the time to get to an intermediate temperature point between two temperatures, the same or extra information might be obtainable. This information could then be utilized to detect openings in the box, or warmer or colder items placed within the box.
It is also possible for the desired inside temperature to be adjusted and changed. This clearly could affect the cool down time and must be compensated for. In each case, the microcontroller can properly adjust the reference times.
Accordingly, it is the object of the present invention to utilize the temperature of the air outside of the refrigerator to change defrost performance and decision times.
Yet another object shall be the measuring of time versus temperature change within the refrigerator or similar device to determine the need for a defrost cycle. This time measured must be the fall time or the time while the compressor is on which will show the differences in ice build up.
BRIEF DESCRIPTION OF THE DRAWINGS
A better understanding of the present invention may be had from consideration of the following detailed description taken in conjunction with the following drawings:
FIG. 1 is an isometric sketch of a refrigerator or similar device employing the teachings of the present invention.
FIG. 2 is a drawing showing the effect of time versus temperature.
FIG. 3 is a table showing time for the compressor to reach a particular temperature at a particular outside temperature.
FIG. 4 is a graph showing compressor time change versus external temperature with ice thickness at 0.4 mm.
FIG. 5 is a chart illustrating the basic decisions employed in the present invention.
FIG. 6 is a block diagram of an appliance equipped with a method of defrost control utilizing ambient air temperature determination employing the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
For a better and more thorough understanding of the present invention it will be described as being embodied into a refrigerator having a freezer compartment, for purposes of illustration. It must be understood, however, the invention is not limited to use only in refrigerators having freezers, but also in other appliances, such as freezers, air conditioners, etc.
As shown in FIG. 1, a temperature sensor 108 is placed inside the freezer compartment 102 as seen in FIG. 1. The compressor 107 operates the evaporator 106 that goes on and off as shown in FIG. 2. A microcontroller or some other similar measuring device (not shown) included within the refrigerator measures the time it takes for a sensor temperature to rise and fall. For this purpose, RC 2 (as shown in FIG. 2) is measured by the sensor and the microcontroller. The microcontroller measures the "on" (T 2 ) and "off" (T 1 ) times as shown in FIG. 2, operating the compressor 107 to provide necessary cold.
To determine the proper operation, the refrigerator is placed in a room with varying temperatures. Data is taken by the microcontroller which correlates to the time the evaporator takes to decrease 8° C. with the room temperature and ice thickness which builds up on the evaporator. This data then becomes the reference time. Then the microcontroller will be placed within the same refrigerator or one of the same size with the microcontroller recording the time the compressor is on, the time the sensor takes to change temperature, and the room temperature of the refrigerator. From this data, comparisons are made to reference times and the microcontroller will decide that it is time to initiate a defrost cycle or to take more data. As may be seen by reference to the information shown in FIGS. 3 and 4, the freezer is placed in a room with controlled temperatures, with the data being recorded for the room temperature, inside freezer temperature, a record of time and monitoring of ice thickness on the evaporator within the freezer. Such recorded information is seen as indicated in FIGS. 3 and 4. FIG. 3 includes a curve showing the compressor on times for change of 8° C. versus evaporator ice thickness at a constant room temperature. While FIG. 4 includes a bar graph portion illustrating compressor on time versus room temperature at ice thickness on t he evaporator of 0.4 mm.
In accordance with the teachings of the present invention, the freezer unit is now placed in a room with varying temperatures. The freezer is set to control the average air temperature at a preset temperature. An included microcontroller monitors the temperature inside and outside of the freezer along with the energization state of the compressor 107. It is desired that the microcontroller operates to start a defrost cycle when the ice is built up to 0.4 mm or greater. Accordingly, the microprocessor is utilized to measure the time when the compressor first turns on to a change in temperature Of the sensor at 8° C. It also measures the outside temperature, which is 29° C. From FIG. 4, there is shown a correlation of a time change at 21 minutes or longer to 0.4 mm thick ice while at an ambient external temperature of 29° C. Again, the microcontroller will now monitor each cool down time of the compressor as it cycles for the desired average set temperature. As may be seen in FIG. 3, the time to change 8° C. takes longer and longer as the ice thickness increases. For each cycle of the compressor, the ice thickness will increase a little more. At some cycle of operation (X+3), the compressor will take 15 minutes to cause an 8° C. change. The microcontroller will then compare this to a reference time of 21 minutes and decides a defrost does not need to begin. With ten compressor cycles later, the 8° C. change time is 21 minutes. The microcontroller will then allow the compressor to stay on until the set temperature is met and then initiate the defrost. In this arrangement, 21 minutes implies that the thermal transfer from the evaporator to air is hindered by 0.4 mm thickness of ice on the evaporator.
The equation is based on a simple algorithm decision which is shown in FIG. 5 taken in connection with the equipment shown in block diagram in FIG. 6.
It should be understood that while the operation of the elements in the present system have been shown in block diagram form, details thereof do not form a portion of the present invention. Rather, it only being required that the individual elements of the system perform in the manner which will be described hereinafter. Such operations all being well known and within the scope of those skilled in the art.
Referring now to FIGS. 5 and 6 in combination, discussion of a software routine for determining control of a defrost cycle will be discussed. Initially, microcontroller 601 determined the temperature setting established by potentiometer 610 to provide an initial ambient temperature to be within the normal ambient range prior to beginning of the cycle controlled program.
At this point in time, the microcontrol let will estimate ambient temperature measuring the on and off times of the cold producing element compressor 604. The information is based on the stored information previously determined and described.
The internal temperature initially established by means of potentiometer 610 within the microcontroller 601 will be modified to adapt to the estimated ambient temperature range. Compressor 604 will now be operated based on the temperature setting established by the controller and sensor information received from sensor 607, The defrost heater 611 will now be operated in response to the microcontroller as required by length of time determined by the microcontroller 601 and by the length of time compressor 604 has been on and the estimated ambient temperature currently stored within the microcontroller 601.
At the conclusion of the defrost time, the program is repeated beginning with the estimation of ambient temperature again utilizing compressor on and off time. As previously indicated, this may change depending upon the build up of ice on the evaporator 106. Thus, accordingly it can be seen that microcontroller 601 is effectively able to estimate by means of monitoring the off and on times of the compressor to provide an indication of the ambient temperature to control defrost cycle of the freezer unit to prevent extensive build up of ice therein,
While but a single form of the present invention has been shown, it will be obvious to those skilled in the art that numerous modifications may be made without departing from the spirit of the present invention which shall be limited only by the scope of the claims appended hereto. | A method for determining the time to begin and end a defrosting cycle of an evaporator included within a refrigeration system. Decisions as to initiate and terminate defrosting operations are predicated on information about the external temperature of the system and measuring differences in the rate of change of temperature drop between non-iced and iced conditions. | 5 |
This invention relates to electrosurgery, and in particular to an electrode especially configured for surgery on the breast of a patient.
BACKGROUND OF THE INVENTION
Electrosurgery is a common procedure for dentists, doctors, and veterinarians. Electrosurgical handpieces are commercially available that will accommodate a wide variety of electrodes shapes and sizes, such as needles, blades, scalpels, balls and wire loops. Also, multi-function electrodes are available. A suction coagulator is described in U.S. Pat. No. 5,196,007, whose contents are herein incorporated by reference. This is an instrument that can be connected to a source of electrosurgical energy and that provides the handpiece in the form of a hollow tube with an exposed tip. By connecting a suction source to the hollow tube end, blood and other liquids as well as vapors and odors at the operative field can be drawn out while simultaneously bleeding capillaries can be coagulated electrosurgically.
The importance of using suction to capture smoke and plume generated during an electrosurgical procedure is also well known in the art. Such procedures involving tissue excision invariably result in the generation of smoke and odors. This causes several problems. Firstly, the smoke interferes with the vision of the surgeon. Secondly, the smoke can be inhaled by the patient or the surgeon. Thirdly, the odors are offensive. See, for example, U.S. Pat. No. 6,001,077, which describes a plume evacuation system employing a novel wand—the fitting used to capture the plume and which is attached to the suction apparatus—whose contents are herein incorporated by reference.
Reconstructive plastic surgery on the breast of a patient, especially breast implants, is a common surgical procedure. See for example the discussion and techniques described in RECONSTRUCTIVE PLASTIC SURGERY, 2 nd ed., Vol. 7, Pgs. 3689–3704, publ. By W.B. Saunders Company. One of the more important steps in performing a successful breast implant is creating the pocket for the implant. Traditionally, the pocket is created using a sharp instrument (scalpel or scissors) to cut and dissect the tissue. The main problem of creating the pocket with a sharp instrument is the bleeding which obscures the surgical site and can reduce the surgeon's accuracy. Bleeding is messy and time consuming to control but if time is not taken to control the bleeding, accuracy is compromised.
Another traditional method used to create the pocket is blunt dissection. Blunt dissection however can tear rather than precisely and cleanly cut the tissue. Tearing and separating tissue with blunt dissection is a blind method and while it is fast it is very traumatic and causes an abundance of bleeding.
While the two traditional methods are easy and fast to learn, the sharp or blunt dissection techniques cause more bleeding and more tissue injury, can tear tissue, and often result in a longer recovery time.
SUMMARY OF THE INVENTION
An object of the invention is an electrosurgical electrode for performing breast surgery causing fewer problems than known procedures.
A further object of the invention is an electrosurgical electrode that ensures that the active end from which suction is active is located close to the operative field.
Another object of the invention is a unipolar electrosurgical electrode configured to carefully dissect and coagulate breast tissue in a breast plastic surgical procedure.
Still a further object of the invention is a suction device integrated with an electrosurgical electrode specifically adapted for use in breast implantology.
In accordance with an important aspect of the present invention, an electrosurgical electrode configured for use in a breast plastic surgical procedure comprises an elongated forceps that is operated as a unipolar electrode.
In accordance with another aspect of the present invention, the electrosurgical electrode is provided with internal channels that can provide suction or fluids at the surgical site when a source of suction or fluid is connected to the electrode.
In accordance with still another aspect of the present invention, the electrosurgical electrode is provided with uniquely configured cutting edges at its distal end for cutting tissue while simultaneously coagulating any bleeding that occurs.
The unipolar electrosurgical forceps of the invention cleanly and precisely cuts tissue and coagulates bleeding vessels at the same time. It becomes possible to produce a very precise pocket in a relatively short time (less than 20–30 min). The result in a procedure for forming a pocket in the breast is a dry pocket, which means more accuracy and better vision for the surgeon. A shorter recovery time is possible for many augmentation patients. Even in sub-muscular pocket dissection, it is possible for the majority of the patients to return to normal life in less than two-three days.
The various features of novelty which characterize the invention are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and specific objects attained by its use, reference should be had to the accompanying drawings and descriptive matter in which there are illustrated and described the preferred embodiments of the invention, like reference numerals or letters signifying the same or similar components.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a perspective view of one form of electrosurgical electrode according to the invention shown electrically connected to electrosurgical apparatus and suction and fluid sources;
FIG. 2 is a top view of the electrosurgical electrode of FIG. 1 ;
FIG. 3 is a perspective view of part of the front end of the electrosurgical electrode of FIG. 2 ;
FIGS. 4A , 4 B, and 4 C cross-sectional views of the electrosurgical electrode of FIG. 2 along the lines 4 — 4 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
U.S. Pat. No. 6,001,077 shows a typical surgical smoke plume evacuation system with a hand-held wand connected via filters and a vacuum hose to a vacuum blower, referred to herein as the suction generator.
The invention described in the present application provides an electrode configuration that is stand alone, meaning that it incorporates the handpiece and is not attached to a standard handpiece as is more common in this art.
FIG. 1 is a perspective view and FIG. 2 is a top view of a unipolar electrosurgical electrode 10 according to the invention. It is made of any electrically-conductive material preferably metal, e.g., stainless steel. It is completely coated with electrically-insulating material, except for the distal working end (explained below), and thus is configured to be handled by the surgeon, with the surgeon holding both arms 12 , 14 of the forceps configuration in the palm of his hand. The two arms 12 , 14 are attached at the proximal end to a common support 16 and are each configured so that they are biased outwardly, like ordinary forceps, so that when the surgeon release his or her pressure on the forceps' arms, they automatically assume the rest position shown in FIG. 2 . The common metal support 16 is in turn connected to an electrical cable 18 connected at its opposite end to a connector (not shown) for plugging into a standard electrosurgical apparatus 20 supplying electrosurgical currents to the electrode 10 . In this embodiment, the surgeon would use the standard foot pedal for activating and inactivating the apparatus 20 . While not shown, it is possible to add to the forceps the kind of fingerswitches commonly found on electrosurgical handpieces to operate the apparatus 20 .
The electrosurgical apparatus 20 preferably is a high frequency (RF) radiosurgical energy source, which operates in the range of about 3.8–4.0 MHz. Studies have shown that the 3.8–4.0 MHz frequency range is the preferred RF energy to incise and coagulate tissue because tissue thermal necrosis is minimal and, when interfaced with the electrosurgical electrode of the invention, provides excellent cutting and hemostasis for virtually all procedures. An example of suitable electrosurgical apparatus is the Model SURGITRON Dual-Frequency electrosurgical unit manufactured by and available from Ellman International, Inc. of Hewlett, N.Y.
Mounted along the inside of each of the forceps' arms 12 , 14 are conduits in the form of narrow tubes 22 , 24 . The distal ends of the tubes 22 , 24 are open 26 . In addition, one of the tubes 22 has an additional opening 28 at the side near the end opening 26 . Each of the tubes 22 , 24 extend along the inside of their respective arm, pass through a an opening at the proximal arm end and terminate in fittings 30 , 32 for receiving flexible tubes (not shown) which under normal operation would be respectively connected to a source of suction and fluid. The suction withdraws smoke at the surgical site and the fluid can be used by the surgeon for irrigating the surgical site, as illustrated by the arrows in FIG. 1 . Fittings 34 are mounted on the common support 16 and are used to support the suction/fluid tubes, respectively. FIG. 3 is an enlarged view of the tube 22 on arm 12 showing the openings 26 , 28 .
At the distal end of each arm is located the working end 36 of the electrode 10 . The working end comprises in this embodiment a short bare metal end that has a triangular configuration with triangle vertices 40 facing inward (and vertices 42 facing downward in the FIG. 2 view) to form on each forceps end a sharp cutter 38 with a flat top 43 . The cutters 38 may have the same configuration. FIG. 4A is a cross-section at the working end and shows the triangular shape 38 . When the forceps' arms are brought together, the vertices 40 on opposite corners abut. Thus, cutting can take place by bringing the forceps arms together using the inner vertices 40 to cut tissue between the forceps' ends, or cutting can take place by bringing together the forceps arms, and moving the forceps as a unit sideways, using the outer vertices 39 opposite to that of the vertices 40 , or downward using the vertices 42 at the bottom. This gives the surgeon complete freedom as to how he or she can use the electrode during a procedure. The triangles are sharp enough to allow cutting or blunt dissection without electrosurgical currents, but in most situations electrosurgical currents will be applied at the same time as cutting to enhance the cutting and achieve hemostasis.
An important feature is the dimensions of the unipolar forceps of the invention. Preferably, it comes as a family in two different lengths for different breast procedures each with different sized working ends. Preferably, the overall length measured from the working end tip to the fittings 34 for one member of the family of electrodes is about 230 mm, and for the other member is about 210 mm. The former is mainly for inframammary approaches and the latter for periareolar approaches. While having both suction/fluid tubings are preferred, it is also possible to omit the fluid tubing for the shorter version for the periareolar approach. The working ends 36 also preferably come in three sizes illustrated at FIGS. 4A , 4 B, and 4 C. The smallest preferably has a transverse dimension 44 of about 1.8 mm and a height 46 of about 1.36 mm. The next largest preferably has a transverse dimension 44 also of about 1.8 mm but a larger height 46 of about 1.8 mm. The largest preferably has a transverse dimension 44 of about 3 mm and a height 46 of about 2.26 mm. The different sized forceps and working ends are useful for surgical procedures on different sized breasts and for different procedures.
In all cases, the complete forceps is completely insulated except for the small bare working end, which is bare from the line 48 to the tip.
In use of the forceps of the invention, with a suction source attached to the tubing 30 , when the suction generator is activated, the reduced pressure is conveyed down the hollow tubing 22 , and escapes via the ports 26 and 28 at the exit of the tubing 22 , which it will be noted is always located very close to the point of origin of the smoke plume, which is where the working electrode end 36 excises the tissue when the electrosurgical apparatus is activated. This allows smoke and airborne contaminants to be captured close to their point of origin, and avoids the need of an additional staff member to hold a separate plume capture device near the excision site. The close proximity of the capture ports 26 , 28 to the plume origin also allows the use of lower reduced pressure and thus lower noise levels. Similarly, when a fluid source is connected to the fitting 32 and activated, irrigating fluid such as saline solution will exit from the port 26 again close to the excision site.
As a result of the relatively simple construction, manufacture is quite simple and low cost, which is important for disposable hospital and office environments.
When RF energy is supplied, it will flow to the sharp vertices of the working end. The RF energy focuses on the sharp corners of the forceps' tip. The RF energy flowing through the sharp edge of the working end allows for dissection and excision of all degrees of breast tissue types, while at the same time effectively coagulating any bleeders that may result.
The RF forceps of the invention enables the surgeon to use one instrument to provide the necessary surgical features of cutting, coagulation and suction, with or without suction or fluids, with RF energy being applied during part or all of the time that the dissection procedure is carried out, with RF energy and blunt dissection, or with blunt dissection, or with suction alone without RF energy being applied. The surgeon would be otherwise required to utilize several different surgical instruments to accomplish what the RF forceps probe alone can accomplish. The changing of instruments during the surgical intervention prolongs the surgery, blood loss and anesthetic time for the patient.
By interfacing the RF breast probe with the ultra-high 3.8–4.0 MHz Radiosurgery apparatus, a number of surgical and clinical advantages, namely: better operative results, due to the high frequency radiosurgery device's ability to significantly reduce tissue necrosis; minimal scarring; reduced surgical pain and post-operative pain; and controlled bleeding and post-operative bleeding.
Precise 3.8–4.0 MHz high frequency/low temperature dissection, using the special monopolar plume suction forceps to cut and coagulate bleeding vessels under direct vision can produce a very precise pocket in short time (less than 20–30 min.). The radiofrequency method dramatically reduces the risk of complications (bleeding, infection, asymmetry, etc). Additionally typically there is less pain and a shorter recovery period.
Other variations in the shape of the electrosurgical electrode working end while retaining its benefits and advantages will be evident to those skilled in the art.
While the invention has been described in connection with preferred embodiments, it will be understood that modifications thereof within the principles outlined above will be evident to those skilled in the art and thus the invention is not limited to the preferred embodiments but is intended to encompass such modifications. | An electrosurgical electrode configured for use in a breast plastic surgical procedure comprises an elongated forceps that is operated as a unipolar electrode. The electrosurgical electrode is provided with internal channels that can provide suction or fluids at the surgical site when a source of suction or fluid is connected to the electrode. It is provided with uniquely configured cutting edges at its distal end for cutting tissue while simultaneously coagulating any bleeding that occurs. It can cleanly and precisely cut tissue and coagulate bleeding vessels at the same time. | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a 371 U.S. National Stage of International Application No. PCT/SE2012/050317, filed Mar. 22, 2012, and claims priority to Swedish Patent Application No. 1150255-6, filed Mar. 22, 2011, the disclosures of which are herein incorporated by reference in their entirety.
TECHNICAL FIELD
The present invention relates to anti-wear and friction-reducing lubricant components comprising selected ionic liquids as well as a lubricant comprising the lubricant component.
BACKGROUND
Improper lubrication may result in high friction and wear losses, which can in turn adversely affect the fuel economy, durability of engines, environment and human health. Developing new technological solutions, such as use of lightweight non-ferrous materials, less harmful fuels, controlled fuel combustion processes or more efficient exhaust gas after-treatment, are possible ways to reduce the economical and environmental impact of machines. The commercially available lubricants are yet not appropriate for lightweight non-ferrous materials.
Ionic liquids (ILs) are purely ionic, salt-like materials that are usually liquid at low temperatures (below 100° C.). Some IL have melting points below 0° C. ILs have already found their diverse applications as catalysts, liquid crystals, green solvents in organic synthesis, in separation of metal ions, electrochemistry, photochemistry, CO 2 storage devices, etc. ILs have a number of attractive properties, such as negligible volatility, negligible flammability, high thermal and chemical stability, low melting point and controllable miscibility with organic compounds and base oils. Recently, it was found that ILs can act as versatile lubricants and lubricant components in base oils and greases for different sliding pairs, see e.g. U.S. Pat. No. 3,239,463; US Patent Application Publication 2010/0227783 A1; US Patent Application Publication 2010/0187481 A1; U.S. Pat. No. 7,754,664 B2, Jul. 13, 2010; US Patent Application Publication 2010/0105586 A1. Due to their molecular structure and charges, ILs can be readily adsorbed on the sliding surfaces in frictional pairs, forming a boundary tribofilm, which reduces both friction and wear at low and high loads.
The choice of cations has an impact on properties of ILs and often, but not always defines their stability. Functionality of ILs is, in general, controlled by a choice of both the cation and the anion. Different combinations of a broad variety of already known cations and anions lead to a theoretically possible number of 10 18 . Today only about 1000 ILs are described in the literature, and approximately 300 of them are commercially available. ILs with cations imidazolium, ammonium and phosphonium and halogen-containing anions, tetrafluoroborates and hexafluorophosphates, are the most commonly used in tribological studies. Alkylimidazolium tetrafluoroborates and hexafluorophosphates have shown promising lubricating properties as base oils for a variety of contacts. However, some ILs with halogen atoms in their structure, for example, with tetrafluoroborates or/and hexafluorophosphates, are very reactive that may increase a risk for tribocorrosion in ferrous and non-ferrous contacts.
Imidazolium and Other ILs with BF 4 Anion:
A literature survey shows that most of the IL lubricants successfully employed during the past decade in various ferrous and non-ferrous tribological contacts are based on boron-based anion, tetrafluoroborate [BF 4 ] − [Ye, C., Liu, W., Chen, Y., Yu, L.: Room-temperature ionic liquids: a novel versatile lubricant. Chem. Commun. 2244-2245 (2001). Liu, W., Ye, C., Gong, Q., Wang, H., Wang, P.: Tribological performance of room-temperature ionic liquids as lubricant. Tribol. Lett. 13 (2002) 81-85. Chen, Y. X., Ye, C. F., Wang, H. Z., Liu, W. M.: Tribological performance of an ionic liquid as a lubricant for steel/aluminium contacts. J. Synth. Lubri. 20 (2003) 217-225. Jimenez, A. E., Bermudez, M. D., Iglesias, P., Carrion, F. J., Martinez-Nicolas, G.: 1-N-alkyl-3-methylimidazolium ionic liquids as neat lubricants and lubricant components in steel aluminum contacts. Wear 260 (2006) 766-782. Yu, G., Zhou, F., Liu, W., Liang, Y., Yan, S.: Preparation of functional ionic liquids and tribological investigation of their ultra-thin films. Wear 260 (2006) 1076-1080.]
Zhang et al. have reported that nitrile-functionalized ILs with BF 4 − anion have considerably better tribological performance in steel-steel and steel-aluminium contacts than ILs with NTf 2 − and N(CN) 2 − anions [Q. Zhang, Z. Li, J. Zhang, S. Zhang, L. Zhu, J. Yang, X. Zhang, Y. J. Deng. Physicochemical properties of nitrile-functionalized ionic liquids. J. Phys. Chem. B, 2007, 111, 2864-2872.] It has been suggested that the BF anion has excellent tribological performance but unfortunately the detailed mechanism was not described.
A comparison of the film formation properties of imidazolium ILs based on BF 4 − and PF 6 − anions in rolling-sliding steel-steel contacts using mini-traction machine (MTM) revealed that BF 4 − anion develop thicker tribofilm and provides lower friction (μ=0.01) compared to PF 6 − (μ=0.03) [H. Arora, P. M. Cann. Lubricant film formation properties of alkyl imidazolium tetrafluoroborate and hexafluorophosphate ionic liquids. Tribol. Int. 43 (2010) 1908-1916.] The same family of ILs in titanium-steel contacts has shown that BF 4 anion-based IL fails above room temperature while PF 6 — anion-based IL perform better up to 200° C. [A. E. Jimenez, M. D. Bermudez. Ionic liquids as lubricants of titanium-steel contact. part 2: friction, wear and surface interactions at high temperature. Tribol. Lett. 37 (2010) 431-443.] In steel-aluminium contacts, phosphonium IL with BF 4 − anion showed superior tribological properties including friction-reducing, antiwear and load carrying capacity to conventional imidazolium IL based on PF 6 − anion [X. Liu, F. Zhou, Y. Liang, W. Liu. Tribological performance of phosphonium based ionic liquids for an aluminum-on-steel system and opinions on lubrication mechanism. Wear 261 (2006) 1174-1179.] Similarly, phosphonium IL with BF 4 − anion exhibited excellent tribological performance at 20° C. and 100° C. in steel-steel contacts as compared to imidazolium-PF 6 − and conventional high temperature lubricants such as X-1P and perfluoropolyether PFPE [L. Wenga, X. Liu, Y. Liang, Q. Xue. Effect of tetraalkylphosphonium based ionic liquids as lubricants on the tribological performance of a steel-on-steel system. Tribol. Lett. 26 (2007) 11-17.]
However, the sensitivity of [BF 4 ] − anion to moisture make such ILs undesirable in tribological and other industrial applications. During the past few years, efforts have been made by researchers to design and synthesize hydrolytically stable halogen-free boron-based ILs with improved performance.
Pyrrolidinium ILs with Halogenated Anions:
The lubricating properties of pyrrolidinium ILs with [BF 4 ] − anion are not reported yet. However, pyrrolidinium IL with other halogenated anions are reported in literature as excellent lubricants and lubricant components for various tribological applications. Recently, pyrrolidinium ILs with halogenated anions have shown excellent lubrication performance in microelectromechanical systems (MEMS) [J. J. Nainaparampil, K. C. Eapen, J. H. Sanders, A. A. Voevodin. Ionic-Liquid Lubrication of Sliding MEMS Contacts: Comparison of AFM Liquid Cell and Device-Level Tests. J. Microelectromechanical Systems 16 (2007) 836-843.]
1-Butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, as is known to possess promising lubricating properties in non-ferrous coatings interfaces such as TiN, CrN and DLC [R. Gonzalez, A. H. Battez, D. Blanco, J. L. Viesca, A. Fernandez-Gonzalez. Lubrication of TiN, CrN and DLC PVD coatings with 1-Butyl-1-Methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate. Tribol. Lett. 40 (2010) 269-277.]
Cholinium ILs with Halogenated Anions:
Choline is biological molecule in the form of phosphatidylcholine (liposome), a major constituent of synovial fluid surface active phospholipids, are natural additives for cartilage lubricants in human beings [G. Verberne, A. Schroeder, G. Halperin, Y. Barenholz, I. Etsion, Liposomes as potential biolubricant components for wear reduction in human synovial joints. Wear 268 (2010) 1037-1042.] These molecules are widely used in effective biolubricants for friction and wear reduction in human synovial joints [S. Sivan, A. Schroeder, G. Verberne, Y. Merkher, D. Diminsky, A. Priev, A. Maroudas, G. Halperin, D. Nitzan, I. Etsion, Y. Barenholz. Liposomes act as effective biolubricants for friction reduction in human synovial joints. Langmuir 26 (2010) 1107-1116.]
Cholinium ILs, choline chloride, has recently shown excellent friction reducing performance in steel-steel contacts comparable to fully formulated engine oil (SAE 5W30 grade) [S. D. A. Lawes, S. V. Hainsworth, P. Blake, K. S. Ryder, A. P. Abbott. Lubrication of steel/steel contacts by choline chloride ionic liquids. Tribol. Lett. 37 (2010) 103-110.] These ILs are believed as green lubricants and have been known to have excellent corrosion inhibition properties [C. Gabler, C. Tomastik, J. Brenner, L. Pisarova, N. Doerr, G. Allmaier. Corrosion properties of ammonium based ionic liquids evaluated by SEM-EDX, XPS and ICP-OES. Green Chem. 13 (2011) 2869-2877.]
US 2009/0163394 discloses a number of ionic liquids, for instance Methyl-n-butylbis(diethylamino)-phosphonium bis(oxalato)borate. It briefly mentions that lubrication oils as a general application for ionic liquids. One drawback of the compounds that are disclosed is that the direct P—N bonds in cations of described phosphonium based ionic liquids are sensitive to hydrolysis, which is critical in many important applications including most of commercial lubricants with unavoidable presence of traces of water. Compounds with P—N bonds are very sensitive to hydrolysis and may hydrolyze to produce reactive species. Therefore, phosphonium cations with one and more P—N chemical bonds will be prone to hydrolysis in the presence of traces of water in a lubricant. Stability of a lubricant placed in a contact with water is a very important technical characteristics.
The most widely studied ionic liquids in tribological applications usually contain tetrafluoroborate (BF 4 − ) and hexafluorophosphate (PF 6 − ) anions. Probably, the reason is that both boron and phosphorus atoms have excellent tribological properties under high pressure and elevated temperature in the interfaces. However, BF 4 − and PF 6 − anions have high polarity and absorb water in the system. These anions are very sensitive to moisture and may hydrolyze to produce hydrogen fluoride among other products. These products cause corrosion by various tribochemical reactions, which can damage the substrate in the mechanical system. In addition, halogen-containing ILs may release toxic and corrosive hydrogen halides to the surrounding environment.
One major drawback of ionic liquids, which are known for lubrication purpose is that the halogens make them undesired for instance from an environmental perspective. Further corrosion may be a problem for some currently used ionic liquids in particular for hydrophilic ionic liquids.
Therefore, the development of new hydrophobic and halogen-free anions containing ILs is highly desired.
SUMMARY OF THE INVENTION
It is an object of the present invention to obviate at least some of the disadvantages in the prior art and provide an improved lubricant component as well as a lubricant comprising the component.
In a first aspect there is provided a lubricant component characterized in that it comprises: a) at least one anion selected from the group consisting of a mandelato borate anion, a salicylato borate anion, an oxalato borate anion, a malonato borate anion, a succinato borate anion, a glutarato borate anion and an adipato borate anion, and b) at least one cation selected from the group consisting of a tetraalkylphosphonium cation, a choline cation, an imidazolium cation, a borronium cation and a pyrrolidinium cation, wherein said at least one cation has at least one alkyl group substituent with the general formula C n H 2n+1 , wherein 1≦n≦80.
In one embodiment 1≦n≦60.
In one embodiment the anion is selected from the group consisting of a bis(mandelato)borate anion, a bis(salicylato)borate anion, and a bis(malonato)borate anion, and wherein the cation is a tetraalkylphosphonium cation.
In one embodiment the anion is bis(oxalato)borate and wherein the cation is a tetraalkylphosphonium cation.
In one embodiment the anion is a bis(succinato)borate anion and wherein the cation is a tetraalkylphosphonium cation.
In one embodiment the anion is selected from the group consisting of a bis(glutarato)borate anion and a bis(adipato)borate anion and wherein the cation is a tetraalkylphosphonium cation.
In one embodiment the only cation is tetraalkylphosphonium with the general formula PR′R 3 + , wherein R′ and R are C n H 2n+1 .
In one embodiment R′ is selected from the group consisting of C 8 H 17 and C 14 H 29 , and wherein R is selected from the group consisting of C 4 H 9 and C 6 H 13 .
In one embodiment the lubricant component comprises at least one selected from the group consisting of tributyloctylphosphonium bis(mandelato)borate; tributyltetradecylphosphonium bis(mandelato)borate; trihexyltetradecylphosphonium bis(mandelato)borate, tributyloctylphosphonium bis(salicylato)borate, tributyltetradecylphosphonium bis(salicylato)borate, trihexyltetradecylphosphonium bis(salicylato)borate, tributyltetradecylphosphonium bis(oxalato)borate, trihexyltetradecylphosphonium bis(oxalato)borate, tributyltetradecylphosphonium bis(malonato)borate, trihexyltetradecylphosphonium bis(malonato)borate, tributyltetradecylphosphonium bis(succinato)borate, trihexyltetradecylphosphonium bis(succinato)borate, tributyltetradecylphosphonium bis(glutarato)borate, trihexyltetradecylphosphonium bis(glutarato)borate, tributyltetradecylphosphonium bis(adipato)borate, trihexyltetradecylphosphonium bis(adipato)borate, choline bis(salicylato)borate, N-ethyl-N-methylpyrrolidinium bis(salicylato)borate, N-ethyl-N-methylpyrrolidinium bis(mandelato)borate, 1-ethyl-2,3-dimethylimidazolium bis(mandelato)borate, 1-ethyl-2,3-dimethylimidazolium bis(salicylato)borate, 1-methylimidazole-trimethylamine-BH 2 bis(mandelato)borate, 1,2-dimethylimidazole-trimethylamine-BH 2 bis(mandelato)borate, 1-methylimidazole-trimethylamine-BH 2 bis(salicylato)borate, and 1,2-dimethylimidazole-trimethylamine-BH 2 bis(salicylato)borate.
In one embodiment the lubricant component comprises trihexyltetradecylphosphonium bis(mandelato)borate.
In one embodiment the lubricant component comprises trihexyltetradecylphosphonium bis(salicylato)borate
In one embodiment the lubricant component comprises trihexyltetradecylphosphonium bis(oxalato)borate.
In one embodiment the lubricant component comprises trihexyltetradecylphosphonium bis(malonato)borate.
In a second aspect there is provided a lubricant comprising 0.05-100 wt % of the lubricant component described herein. The lubricant component can both be used in pure form and as an additive to other lubricants. If the lubricant component is used in pure form the lubricant component itself is the sole lubricant.
In one embodiment the lubricant comprises 0.05-20 wt %, of the lubricant component as described herein. In one embodiment the lubricant comprises 0.1-5 wt %, of the lubricant component. In one embodiment the lubricant comprises 0.5-5 wt %, of the lubricant component.
In a third aspect there is provided use of the lubricant component as described herein for at least one selected from reducing wear and reducing friction.
In a fourth aspect there is provided a method for reducing friction comprising use of a lubricant with the lubricant component as described herein.
There is also provided a method for reducing wear comprising use of a lubricant with the lubricant component as described herein.
Advantages of the invention include that the replacement of BF 4 − , PF 6 − and halogen containing ions with more hydrophobic and halogen-free anions will avoid corrosion and toxicity.
Halogen-free boron based ionic liquids, (=hf-BILs) with these novel halogen-free boron-based anions make a lubricant hydrolytically stable. This will aid to avoid the formation of hydrofluoric acid (HF) in the lubricant in the course of exploitation of machines. HF is produced by the most commonly used anion (BF 4 − ) and (PF 6 − ) in ILs. The formation of HF from ionic liquids is one of the main limitations of such lubricants, because HF is highly corrosive towards metals. The present novel hf-BILs according to the invention do not have such limitations.
Based on tribological studies of ionic liquids with imidazolium, pyrrolidinium and cholinium (as cations) and halogen-based anions, we suggest that ionic liquids according to the invention, i.e. ionic liquids with tetraalkylphosphonium, imidazolium, pyrrolidinium and cholinium (as cations) and halogen-free orthoborate anions will have good tribological performance in addition to their advantage as being halogen-free. Some examples of these halogen-free orthoborate anions are bis(mandelato)borate, bis(salicylato)borate, bis(oxalato)borate, bis(malonato)borate, bis(succinato)borate, bis(glutarato)borate and bis(adipato)borate. An outstanding antiwear and friction-reducing effect for steel-aluminium contacts has been proven for orthoborate based tetraalkylphosphonium ionic liquids and the “key” role is orthoborate anions in ILs as lubricants regarding these technical effects.
SHORT DESCRIPTION OF DRAWINGS
The invention will be described more in detail below with reference to the accompanying drawings, in which:
FIG. 1 shows DSC thermograms of novel halogen-free boron based ionic hf-BILs liquids.
FIG. 2 shows densities of novel halogen-free boron based ionic liquids (hf-BILs) as a function of temperature.
FIG. 3 shows an Arrhenius plot of viscosity for selected hf-BILs as a function of temperature.
FIG. 4 shows the wear depths at 40 N load for 100Cr6 steel against AA2024 aluminum lubricated by hf-BILs in comparison with 15W-50 engine oil.
FIG. 5 shows the friction coefficients at 40 N load for 100Cr6 steel against AA2024 aluminum lubricated by hf-BILs in comparison with 15W-50 engine oil.
FIG. 6 shows the friction coefficient curves at 20 N load for 100Cr6 steel against AA2024 aluminium lubricated by hf-BILs in comparison with 15W-50 engine oil.
FIG. 7 shows the friction coefficient curves at 40 N load for 100Cr6 steel against AA2024 aluminum lubricated by hf-BILs in comparison with 15W-50 engine oil.
DETAILED DESCRIPTION OF THE INVENTION
Regarding n in R, R′=C n H 2n+1 of tetraalkylphosphonium cations, it is noted that borate with shorter (both linear and branched) alkyl chains are less miscible in oils (in particular, with mineral oils), while longer chain alkyl groups (both linear and branched) have higher miscibility with mineral oils. Therefore, an increase in the length of alkyl groups (n) is expected to result in a more homogeneous lubricant. However, the length of R and R′ should be optimized for each specific type of the oil and an optimum temperature interval for the lubricant, because too long alkyl chains will lead to a lower mobility of the additive in lubricant and, therefore, to compromised both anti-wear and friction reducing efficiency of the additive. Therefore, n is at least 1 and could be up to about 80 without negatively affecting the performance of the compound according to the invention.
In order to be well miscible with today's engine oils, such as POA 40 and POA 60 (Statoil) having carbon chain lengths of 40 and 60 carbon atoms, respectively, the value of n should be no less than 40 and 60, respectively. Thus, in one embodiment n≦60. The limit n≦80 is motivated by possible future products of motor oils with even longer alkyl chains, supposedly up to at least n=80.
A skilled person can in the light of the description make a routine optimization experiment and determine a suitable value of n and branched or/and non-branched character of the alkyl groups in tetraalkylphosphonium, imidazolium and pyrrolidinium cations.
It is conceived to use the lubricant components for reducing friction and reducing wear on a number of different materials both metals and non-metals. Examples of non-metals include but are not limited to ceramics with/without DLC (diamond-like-coatings) or/and graphene-based coatings. Examples of metals include but are not limited to alloys, steel, and aluminium with/without DLC (diamond-like-coatings) or/and graphene-based coatings.
A new family of hf-BILs was synthesized and purified following an improved protocol and a detailed study of their tribological and physicochemical properties including thermal behavior, density and viscosity, was carried out. The tribological properties were studied with 100Cr6 steel balls on an AA2024 aluminum disc in a rotating pin-on-disc test.
All compounds tested from this novel class of hf-BILs have outstanding antiwear as well as friction performance as compared with the fully formulated engine oil.
Synthesis schemes for the halogen free boron based ionic liquids according to the invention are shown below:
Synthesis
All novel halogen-free boron based ionic liquids (hf-BILs) were synthesized and purified using a modified literature methods.
Example 1
Tributyloctylphosphonium bis(mandelato)borate ([P4448][BMB])
Mandelic acid (3.043 g, 20 mmol) was added slowly to an aqueous solution of lithium carbonate (0.369 g, 5 mmol) and boric acid (0.618 g, 10 mmol) in 50 mL water. The solution was heated up to about 60° C. for two hours. The reaction was cooled to room temperature and tributyloctylphosphonium chloride (3.509 g, 10 mmol) was added. The reaction mixture was stirred for two hours at room temperature. The organic layer of reaction product formed was extracted with 80 mL of CH 2 Cl 2 . The CH 2 Cl 2 organic layer was washed three times with 60 mL water. The CH 2 Cl 2 was rotary evaporated at reduced pressure and product was dried in a vacuum oven at 60 for 2 days. A viscous colorless ionic liquid was obtained in 84% yield (5.30 g). m/z ESI-MS (−): 311.0 [BMB] − ; m/z ESI-MS (+): 315.3 [P4448] + .
Example 2
Tributyltetradecylphosphonium bis(mandelato)borate ([P44414][BMB])
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (3.043 g, 20 mmol) of mandelic acid and tributyltetradecylphosphonium chloride (4.349 g, 10 mmol). A viscous colorless ionic liquid was obtained in 81% yield (5.75 g). m/z ESI-MS (−): 310.9 [BMB] − ; m/z ESI-MS (+): 399.2 [P44414] + .
Example 3
Trihexyltetradecylphosphonium bis(mandelato)borate ([P66614][BMB])
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (3.043 g, 20 mmol) of mandelic acid and trihexyltetradecylphosphonium chloride (5.189 g, 10 mmol). A viscous colorless ionic liquid was obtained in 91% yield (7.25 g). m/z ESI-MS (−): 311.0 [BMB] − ; m/z ESI-MS (+): 483.3 [P66614] + .
Example 4
Tributyloctylphosphonium bis(salicylato)borate ([P4448][BScB])
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.762 g, 20 mmol) of salicylic acid and tributyloctylphosphonium chloride (3.509 g, 10 mmol). A viscous colorless ionic liquid was obtained in 88% yield (5.28 g). m/z ESI-MS (−): 283.1 [BScB] − ; m/z ESI-MS (+): 315.3 [P4448] + .
Example 5
Tributyltetradecylphosphonium bis(salicylato)borate ([P44414][BScB])
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.762 g, 20 mmol) of salicylic acid and tributyltetradecylphosphonium chloride (4.349 g, 10 mmol). A viscous colorless ionic liquid was obtained in 94% yield (6.44 g). m/z ESI-MS (−): 283.0 [BScB] − ; m/z ESI-MS (+): 399.4 [P44414] + .
Example 6
Trihexyltetradecylphosphonium bis(salicylato)borate ([P66614][BScB])
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.762 g, 20 mmol) of salicylic acid and trihexyltetradecylphosphonium chloride (5.189 g, 10 mmol). A viscous colorless ionic liquid was obtained in 95% yield (7.30 g). m/z ESI-MS (−): 283.0 [BScB] − ; m/z ESI-MS (+): 483.5 [P66614] + .
Example 7
Tributyltetradecylphosphonium bis(oxalato)borate ([P44414][BScB])
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (1.80 g, 20 mmol) of oxalic acid and tributyltetradecylphosphonium chloride (4.349 g, 10 mmol). A viscous colorless ionic liquid was obtained.
Example 8
Trihexyltetradecylphosphonium bis(oxalato)borate ([P66614][BOB])
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (1.80 g, 20 mmol) of oxalic acid and trihexyltetradecylphosphonium chloride (5.189 g, 10 mmol). A viscous colorless ionic liquid was obtained. m/z ESI-MS (−): [BOB] − ; m/z ESI-MS (+): 483.5 [P66614] + .
Example 9
Tributyltetradecylphosphonium bis(malonato)borate ([P44414][BMLB])
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.081 g, 20 mmol) of malonic acid and tributyltetradecylphosphonium chloride (4.349 g, 10 mmol). A viscous colorless ionic liquid was obtained.
Example 10
Trihexyltetradecylphosphonium bis(malonato)borate ([P66614][BMLB])
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.081 g, 20 mmol) of malonic acid and trihexyltetradecylphosphonium chloride (5.189 g, 10 mmol). A viscous colorless ionic liquid was obtained. m/z ESI-MS (−): [BMLB] − ; m/z ESI-MS (+): 483.5 [P66614] + .
Example 11
Tributyltetradecylphosphonium bis(succinato)borate ([P44414][BSuB])
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.362 g, 20 mmol) of succinic acid and tributyltetradecylphosphonium chloride (4.349 g, 10 mmol). A viscous colorless ionic liquid was obtained.
Example 12
Trihexyltetradecylphosphonium bis(succinato)borate ([P66614][B SuB])
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.362 g, 20 mmol) of succinic acid and trihexyltetradecylphosphonium chloride (5.189 g, 10 mmol). A viscous colorless ionic liquid was obtained.
Example 13
Tributyltetradecylphosphonium bis(glutarato)borate ([P44414][BMB])
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.642 g, 20 mmol) of glutaric acid and tributyltetradecylphosphonium chloride (4.349 g, 10 mmol). A viscous colorless ionic liquid was obtained.
Example 14
Trihexyltetradecylphosphonium bis(glutarato)borate ([P66614][BGklB])
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.642 g, 20 mmol) of glutaric acid and trihexyltetradecylphosphonium chloride (5.189 g, 10 mmol). A viscous colorless ionic liquid was obtained.
Example 15
Tributyltetradecylphosphonium bis(adipato)borate ([P44414][BAdB])
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.923 g, 20 mmol) of adipic acid and tributyltetradecylphosphonium chloride (4.349 g, 10 mmol). A viscous colorless ionic liquid was obtained.
Example 16
Trihexyltetradecylphosphonium bis(adipato)borate ([P66614][BAdB])
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.923 g, 20 mmol) of adipic acid and trihexyltetradecylphosphonium chloride (5.189 g, 10 mmol). A viscous colorless ionic liquid was obtained.
Example 17
Choline bis(salicylato)borate ([Choline][BScB])
Salicylic acid (5.524 g, 40 mmol) was added slowly to an aqueous solution of lithium carbonate (0.738 g, 10 mmol) and boric acid (1.236 g, 20 mmol) in 40 mL water. The solution was heated upto about 60° C. for two hours. The reaction was cooled to room temperature and choline chloride (2.792 g, 20 mmol) was added. The reaction mixture was stirred for two hours at room temperature. The organic layer of reaction product formed was extracted with 80 mL of CH 2 Cl 2 . The CH 2 Cl 2 organic layer was washed three times with 80 mL water. The CH 2 Cl 2 was rotary evaporated at reduced pressure and the product was dried in a vacuum oven at 60 for 2 days. A white solid ionic liquid was recrystallized from CH 2 Cl 2 (5.44 g, 70% yield). m/z ESI-MS (−): 283.0 [BScB] − ; m/z ESI-MS (+): 103.9 [Choline] + .
Example 18
N-ethyl-N-methylpyrrolidinium bis(salicylato)borate ([EMPy][BScB])
Salicylic acid (5.524 g, 40 mmol) was added slowly to an aqueous solution of lithium carbonate (0.738 g, 10 mmol) and boric acid (1.236 g, 20 mmol) in 40 mL water. The solution was heated upto about 60° C. for two hours. The reaction was cooled to room temperature and N-ethyl-N-methylpyrrolidinium iodide (4.822 g, 20 mmol) was added. The reaction mixture was stirred for two hours at room temperature. The organic layer of reaction product formed was extracted with 80 ml of CH 2 Cl 2 . The CH 2 Cl 2 organic layer was washed three times with 80 mL water. The CH 2 Cl 2 was rotary evaporated at reduced pressure and the product was dried in a vacuum oven at 60 for 2 days. A white solid ionic liquid was recrystallized from CH 2 Cl 2 (6.167 g, 78% yield). m/z ESI-MS (−): 283.0 [BScB] − ; m/z ESI-MS (+): 113.9 [EMPy] + .
Example 19
N-ethyl-N-methylpyrrolidinium bis(mandelato)borate [EMPy][BMB]
The procedure is similar to that used in the synthesis of [EMPy][BScB]. The reaction started with lithium carbonate (0.369 g, 5 mmol), boric acid (0.618 g, 10 mmol), mandelic acid (3.043 g, 20 mmol) and N-ethyl-N-methylpyrrolidinium iodide (2.41 g, 10 mmol). A viscous ionic liquid was obtained in 67% yield (2.85 g). MS (ESI) calcd for [C 6 H 16 N] + m/z 114.2. found m/z 114.1; calcd for [C 16 H 12 O 6 B] − m/z 311.0. found m/z 311.0.
Example 20
1-ethyl-2,3-dimethylimidazolium bis(mandelato)borate [EMIm][BMB]
Mandelic acid (3.043 g, 20 mmol) was added slowly to an aqueous solution of lithium carbonate (0.369 g, 5 mmol) and boric acid (0.618 g, 10 mmol) in 50 mL water. The solution was heated upto about 60° C. for two hours. The reaction was cooled to room temperature and 1-ethyl-2,3-dimethylimidazolium iodide (2.52 g, 10 mmol) was added. The reaction mixture was stirred for two hours at room temperature. The bottom layer of the reaction product formed was extracted with 80 mL of CH 2 Cl 2 . The CH 2 Cl 2 organic layer was washed three times with 100 mL water. The CH 2 Cl 2 was rotary evaporated at reduced pressure and the final product was dried in a vacuum oven at 60° C. for 2 days. A viscous ionic liquid was obtained in 78% yield (3.40 g).
MS (ESI) calcd for [C 7 H 13 N 2 ] + m/z 125.2. found m/z 125.2; calcd for [C 16 H 12 O 6 B] − m/z 311.0. found m/z 311.1.
Example 21
1-ethyl-2,3-dimethylimidazolium bis(salicylato)borate [EMIm][BScB]
The procedure is similar to that used in the synthesis of [EMIm][BMB]. The reaction started with lithium carbonate (0.369 g, 5 mmol), boric acid (0.618 g, 10 mmol), salicylic acid (2.762 g, 20 mmol) and 1-ethyl-2,3-dimethylimidazolium iodide (2.52 g, 10 mmol). A white solid product was obtained in 83% yield (3.38 g). MS (ESI) calcd for [C 7 H 13 N 2 ] + m/z 125.2. found m/z 125.1; calcd for [C 14 H 8 O 6 B] − m/z 283.0. found m/z 283.0.
Example 22
1-methylimidazole-trimethylamine-BH 2 bis(mandelato)borate [MImN111BH 2 ][BMB]
Mandelic acid (3.043 g, 20 mmol) was added slowly to an aqueous solution of lithium carbonate (0.369 g, 5 mmol) and boric acid (0.618 g, 10 mmol) in 50 mL water. The solution was heated upto about 60° C. for two hours. The reaction was cooled to room temperature and 1-methylimidazole trimethylamine BH 2 iodide (2.70 g, 10 mmol) was added. The reaction mixture was stirred for two hours at room temperature. The bottom layer of the reaction product formed was extracted with 80 mL of CH 2 Cl 2 . The CH 2 Cl 2 organic layer was washed three times with 100 mL water. The CH 2 Cl 2 was rotary evaporated at reduced pressure and the final product was dried in a vacuum oven at 60° C. for 2 days.
Example 23
1,2-dimethylimidazole-trimethylamine-BH 2 bis(mandelato)borate [MMImN111BH 2 ][BMB]
The procedure is similar to that used in the synthesis of [MimN111BH 2 ][BMB]. The reaction started with lithium carbonate (0.369 g, 5 mmol), boric acid (0.618 g, 10 mmol), mandelic acid (3.043 g, 20 mmol) and 1,2-dimethylimidazole trimethylamine BH 2 iodide (2.841 g, 10 mmol) was added. A liquid product was obtained.
Example 24
1-methylimidazole-trimethylamine-BH 2 bis(salicylato)borate [MImN111BH 2 ][BScB]
Salicylic acid (5.524 g, 40 mmol) was added slowly to an aqueous solution of lithium carbonate (0.738 g, 10 mmol) and boric acid (1.236 g, 20 mmol) in 40 mL water. The solution was heated upto about 60° C. for two hours. The reaction was cooled to room temperature and 1-methylimidazole trimethylamine BH 2 iodide (5.40 g, 20 mmol) was added. The reaction mixture was stirred for two hours at room temperature. The organic layer of reaction product formed was extracted with 80 ml of CH 2 Cl 2 . The CH 2 Cl 2 organic layer was washed three times with 80 mL water. The CH 2 Cl 2 was rotary evaporated at reduced pressure and the product was dried in a vacuum oven at 60 for 2 days. A liquid product was obtained.
Example 25
1,2-dimethylimidazole-trimethylamine-BH 2 bis(salicylato)borate [MMImN111BH 2 ][BScB]
The procedure is similar to that used in the synthesis of [MImN111BH 2 ][BScB]. The reaction started with lithium carbonate (0.369 g, 5 mmol), boric acid (0.618 g, 10 mmol), salicylic acid (2.762 g, 20 mmol) and 1,2-dimethylimidazole trimethylamine BH 2 iodide (2.841 g, 10 mmol) was added. A liquid product was obtained.
Instrumentation Used in the Invention
NMR experiments were collected on a Bruker Avance 400 (9.4 Tesla magnet) with a 5 mm broadband autotunable probe with Z-gradients at 30° C. NMR spectra were collected and processed using the spectrometer “Topspin” 2.1 software. 1 H and 13 C spectra were reference to internal TMS and CDCl 3 . External references were employed in the 31 P (85% H 3 PO 4 ) and 11 B (Et 2 O.BF 3 ).
The positive and negative ion electrospray mass spectra were obtained with a Micromass Platform 2 ESI-MS instrument.
A Q100 TA instrument was used for differential scanning calorimetric (DSC) measurements to study the thermal behavior of hf-BILs. An average weight of 5-10 mg of each sample was sealed in an aluminum pan and cooled to −120° C. then heated upto 50° C. at a scanning rate of 10.0° C./min.
Viscosity of these hf-BILs was measured with an AMVn Automated Microviscometer in a temperature range from 20 to 90° C. using a sealed sample tube.
The wear tests were conducted at room temperature (22° C.) on a Nanovea pin-on-disk tester according to ASTM G99 using 6 mm 100Cr6 balls on 45 mm diameter AA2024 aluminum disks. The composition, Vicker's hardness and average roughness, R a , of the steel balls and aluminum disks are shown in Table 1. The disks were lubricated with 0.1 mL of lubricant. Experiments were conducted at loads of 20 and 40 N for a distance of 1000 m, with a wear track diameter of 20 mm and a speed of 0.2 m/s. The friction coefficient was recorded throughout the experiment. On completion of the wear tests, the wear depth was measured using a Dektak 150 stylus profilometer.
TABLE 1 Composition, hardness and roughness of alloys used in this study Elemental Composition Alloy (wt %) AA2024 100Cr6 C — 0.98-1.10 Cu 3.8-4.9 — Si 0.5 max 0.15-0.3 Mn 0.3-0.9 0.25-0.45 Mg 1.2-1.8 — Cr 0.1 max 1.3-1.6 Zn 0.25 max Ti 0.15 max S — 0.025 max P — 0.025 max Others 0.15 max — Fe 0.5 max Balance Al Balance — Hardness (Vickers) 145 850 R a (μm) 0.09 0.05 max
Results and Discussion on the Invention
Thermal Behaviour of hf-BILs
FIG. 1 shows the differential scanning calorimetry (DSC) traces of hf-BILs under discussion. All these hf-BILs are liquids at room temperature and they exhibit glass transitions below room temperature (−44° C. to −73° C.). Glass transition temperatures (T g ) for these hf-BILs are also tabulated in Table 2. It is known that T g of orthoborate ionic liquids are higher than those for the corresponding salts of the fluorinated anions. T g of the orthoborate ionic liquids with the cation P66614 + and different anions decreases in the order BMB − >BScB − >BOB − >BMLB − . hf-BILs with BMB − and BScB − have considerably higher T g values compared with these of hf-BILs with BScB − and BMLW, most probably because of the phenyl rings present in the structure of the former anions (BMW and BScW).
For common orthoborate anions with different phosphonium cations, a decrease in T g is observed with an increase in size of alkyl chains in the cations. This trend is more easily seen in hf-BILs with the BScW anion and different phosphonium cations: T g fall in the order P4448 + (−49° C.)>P44414 + (−54° C.)>P66616 + (−56° C.) (see Table 2). Del Sesto et al. have observed a similar trend for ionic liquids of phosphonium cations with bistrifylamide (NTf 2 ) and dithiomaleonitrile (dtmn) anions. Lowest T g of hf-BILs (down to −73° C. for P66614-BMLB) are reached with P66616 + as the cation, probably because of a larger size, lower symmetry and a low packing efficiency of this cation.
Density Measurements of hf-BILs
FIG. 2 shows a linear variation of densities with temperature for hf-BILs. By comparing the effect of anions on the densities of hf-BILs, densities fall in the order BScB − >BMB − >BOB − >BMLB − . For the same anion, density of hf-BILs decreases with an increase in the size of the cation as P4448 + >P44414 + >P66616 + . The density values of P44414-BMB and P44414-BScB are very similar at all measured temperatures. Density of hf-BILs decreases with an increase in the length of alkyl chains in cations, because the van der Walls interactions are reduced and that leads to a less efficient packing of ions. The parameters characterizing density of these hf-BILs as a function of temperature are tabulated in Table 2. For increasing temperatures from +20 to +90° C., density of hf-BILs decreases linearly. This behaviour is usual for ionic liquids.
TABLE 2 Physical Properties of halogen-free boron based ionic liquids (hf-BILs) Density equation d = b − aT/g cm −3 T g /° C. from (where T is ° C.) Ea (η)/ DSC hf-BILs a B R 2 kcal mol −1 measurement P4448-BMB 7 × 10 −4 1.0784 0.9991 12.2 −46 P44414-BMB 7 × 10 −4 1.0541 0.9998 12.7 −44 P66614-BMB 6 × 10 −4 1.0208 0.9995 11.6 −55 P4448-BScB 7 × 10 −4 1.0919 0.9999 11.9 −49 P44414-BScB 6 × 10 −4 1.0532 0.9998 10.8 −54 P66614-BScB 7 × 10 −4 1.0333 1 10.6 −56 P66614-BOB 6 × 10 −4 0.9571 0.9998 11.6 −71 P66614-BMLB 6 × 10 −4 0.9865 0.9996 10.0 −73
Dynamic Viscosity of Hf-BILs
FIG. 3 shows temperature dependences of viscosities of hf-BILs. These dependences can be fit to the Arrhenius equation for viscosity, η=η o exp(E a (η)/k B T), in the whole temperature range studied. Here, η o is a constant and E a (η) is the activation energy for viscous flows. Activation energies, E a (η), for different hf-BILs are tabulated in Table 2.
Some of novel hf-BILs have shown very high viscosity in the temperature range between 20-30° C., which was not measurable by the viscometer used in this study. However, viscosity of hf-BILs decreases markedly with an increase in temperature (from ca 1000 cP at ca 20° C. down to ca 20 cP at ca 90° C., see FIG. 3 ). Viscosity of ionic liquids depends on electrostatic forces and van der Walls interactions, hydrogen bonding, molecular weight of the ions, geometry of cations and anions (a conformational degree of freedom, their symmetry and flexibility of alkyl chains), charge delocalization, nature of substituents and coordination ability. For a given cation, P66616 + , viscosities fall in the order BMB − (E a =11.6 kcal mol −1 )>BOB − (E a =11.6 kcal mol −1 )>BScB − (E a =10.6 kcal mol −1 )>BMLB − (E a =10.0 kcal mol −1 ) (see Table 2).
Tribological Performance of hf-BILs
FIG. 4 compares the antiwear performance for hf-BILs with this for the 15W-50 engine oil at loads of 20 and 40 N for a sliding distance of 1000 m. The wear depths for the 15W-50 engine oil were 1.369 μm and 8.686 μm at 20 N and 40 N loads, respectively. hf-BILs have considerably reduced wear of aluminum used in this study, in particular, at a high load (40 N). For example, aluminum lubricated with P66614-BMB the wear depths were 0.842 μm and 1.984 μm at 20 N and 40 N loads, respectively.
Mean friction coefficients for the selected hf-BILs in comparison with 15W-50 engine oil are shown in FIG. 5 . The friction coefficients for the 15W-50 engine oil were 0.093 and 0.102 at 20 N and 40 N, respectively. All the tested hf-BILs have lower mean friction coefficients compared with 15W-50 engine oil. For example, the friction coefficients for P66614-BMB were 0.066 and 0.067 at 20 N and 40 N loads, respectively.
FIGS. 6 and 7 show time-traces of the friction coefficient for the selected hf-BILs and the 15W-50 engine oil at 20 N ( FIG. 6 ) and 40 N ( FIG. 7 ) during 1000 m sliding distance. The friction coefficients are stable at 20 N both for 15W-50 engine oil and hf-BILs. There is no an increase in the friction coefficients until the end of the test for all lubricants examined here. The friction coefficients for hf-BILs were lower than those for 15W-50 engine oil at all times of the test (see FIG. 3 ).
At the load of 40 N the friction coefficient for the 15W-50 engine oil varied considerably over a sliding distance. At the beginning of the test, the friction coefficient was stable but a sudden increase occurred at a sliding distance of ca 200 m and remained that high for a 400 m sliding distance. In the beginning of the test a thin tribofilm separated the surfaces and prevented them from a direct metal-to-metal contact. A sudden increase in the friction coefficient is the evidence of that the tribofilm formed by standard additives present in 15W-50 engine oil is not stable on aluminum surfaces.
To the contrary, novel hf-BILs according to the invention exhibit a different trend compared to than in the 15W-50 engine oil. In the case of P66614-BMB and P66614-BMLB, there was no increase in the friction coefficient over the whole period of the tribological test. The friction coefficients increased (for P66614-BScB and P66614-BOB) in the very beginning of the test, but then they stabilized after a sliding distance of 50 m. Thus, stable tribofilms (at least until 1000 m sliding distances) are formed at aluminum surfaces lubricated with novel hf-BILs already after a short sliding distance.
Stability Studies
The tetraalkylphosphonium-orthoborate according to the invention based on phosphonium cations containing only P—C bonds are considerably more stable to hydrolysis compared for instance to compounds comprising P—N bonds. We have proven experimentally the hydrolytic stability of our novel hf-BILs. A small droplet of [P 6,6,6,14 ] [BScB] was put in distilled water and left inside water for 10 days to confirm the hydrolytic stability of these hf-BILs. There was no change in appearance. The sample was analysed by ESI-MS; peaks at m/z 483.5 and m/z 283.0 for [C 32 H 68 P] + and [C 14 H 8 O 6 B] − , respectively, and the absence of other peaks in ESI-MS spectra confirmed the hydrolytic stability of these hf-BILs. | Anti-wear and friction-reducing lubricants and additives to lubricants for both ferrous and non-ferrous materials with/without DLC (diamond-like-coatings) or graphene-based coatings, which are halogen free boron based ionic liquids comprising a combination of an anion chosen from a mandelato borate anion, a salicylato borate anion, an oxalato borate anion, a malonato borate anion, a succinato borate anion, a glutarato borate anion and an adipato borate anion, with at least one cation selected from a tetraalkylphosphonium cation, a choline cation, an imidazolium cation and a pyrrolidinium cation, wherein said at least one cation has at least one alkyl group substituent with the general formula C n H 2n+1 , wherein 1≦n≦80. Advantages of the invention include that it provides halogen free ionic liquids for lubrication and that sensitivity for hydrolysis is reduced. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of pending U.S. patent application Ser. No. 14/469,266, filed Aug. 26, 2014, and entitled “Prescription Control System”, which claims the benefit of U.S. Provisional Patent Application No. 61/869,956 filed Aug. 26, 2013, the contents of which are fully incorporated by reference herein.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to a prescription control system for regulating the dispensing of medications; more particularly, the present invention is directed to a prescription control system for regulating the dispensing of addictive pharmaceutical agents such as narcotics, wherein the system includes a pill dispenser with a simplified delivery device and a number of safety systems, including audio and visual recording and tamper warning capabilities.
[0003] The highly addictive properties of many medications can pose a large threat to patients prescribed these medications by medical personnel, such as doctors or nurse practitioners. While these medications are considered controlled substances, the only layer of control is between the manufacturer and the pharmacy. Control is lost once the pharmacy distributes the narcotics to the patient.
[0004] In an attempt to create additional control, prescription narcotics have warnings that doctors and pharmacists are required by law to explain to the patient. Unfortunately, there is no way to ensure that the patient will follow these warnings. This inability to regulate the patient's use of prescription narcotics makes it easy for noncomplying patients to enter a cycle of drug abuse, such as that outlined in FIG. 1 .
[0005] Everyone is subject to the danger of becoming addicted. Addiction is not selective or isolated to any social or economic class and does not age discriminate. Anybody may become an addict, even if they have no initial intentions of becoming addicted. Patients from all walks of life are handed a 28 to 30 day supply of medication, given the warnings, and instructed to use the medication only as prescribed. The problem is that the addictive properties of these medications can make it difficult for the patient to heed the warnings and abide by the prescription.
[0006] If addiction takes its hold on a patient, the results can be devastating. Often, the first step is that the patient will progressively run out of their medication within shorter and shorter periods of time; a 30 day prescription may be consumed in 20 days while the next 30 day supply may be consumed in an even shorter amount of time, such as 10 to 15 days. As patients seek to replenish their supply, they may begin to “shop” for medications by making up stories about how their medication was lost, damaged, or stolen. They may ask doctors for early refills or in some cases seek to buy the drug from illegal street vendors at exorbitant prices.
[0007] Patients can become so addicted that they will beg, borrow, and steal to get more of the medication. When all else fails, they may feel forced by the nature of their addiction to turn to non-pharmaceutical drugs such as heroin or cocaine. This often leads to legal problems where the patients may end up in drug court, with the ultimate result being that the government becomes responsible for providing and paying for rehabilitation. In worst cases, a patient may die due to an overdose.
[0008] Accordingly, there exists a need for a device which dispenses controlled substances, such as narcotics, only at the rate designated by the prescribing doctor. This device should be portable so as to provide proper regulation of the patient's drug regimen without requiring the patient to be tied to a non-portable, home-based medication dispenser. The present invention fills these and other needs.
SUMMARY OF THE INVENTION
[0009] The present invention is directed to a medication dispensing device for dispensing a dosage of a medication to a patient. The dosage is dispensed to the patient upon receipt of a valid request, the valid request including an authorized patient identification input and a dosage availability determined in accordance with a medical professional's prescription. In one aspect, the medication dispensing device comprises a case defining a medication holding area and a dosage holding area, the dose holding area including an entry end and a dispensing end. A first gate is located at the entry end between the medication holding area and the dosage holding area, and is operable to selectively open to allow the dosage to pass from the medication holding area to the dosage holding area. A second gate is located at the dispensing end and is operable to selectively open to allow the dosage to pass from the dosage holding area to a retrieval area accessible to the patient. A central processing unit (CPU) is disposed within the case and includes a memory, wherein the dosage availability is stored in memory. A patient authentication device is in communication with the CPU, and is configured to receive the authorized patient identification input. A battery is configured for providing electrical energy to the CPU. Upon receipt of the valid request, the CPU operates to: i) open the first gate to pass the dosage to the dosage holding area; ii) close the first gate after the dosage has passed to the dosage holding area; iii) open the second gate after the first gate has closed to dispense the dosage to the patient; and iv) close the second gate after the dosage has been dispensed to the patient.
[0010] In another aspect, the first gate and the second gate are each operably coupled to first and second actuators, respectively, wherein each of first and second actuators are powered by the battery to selectively open its respective gate upon receiving the respective command from the CPU. The medication dispensing device may further comprises a photogate associated with the dosage holding area, wherein the photogate is operable to initiate a control signal to the CPU when the dosage interrupts the photogate so that the CPU closes the first gate. Also, a camera and microphone may be provided for recording video data and audio data in the memory upon receipt of an unauthorized patient identification input.
[0011] In another aspect, the medication dispensing device may further comprise a tray for holding the medication, wherein the tray is configured to be positioned within the medication holding area. The tray may include a dispensing slot configured to coincide with the first gate, and the dispensing slot may be proportioned so that only a single dosage may pass through the dispensing slot at a time. The case may include a tray shutter operable to selectively open to allow loading of the tray within the medication holding area, and a tray shutter locking pin to secure the tray shutter in a closed position. The tray shutter locking pin is retractable to allow the tray shutter to open for loading of the tray. The case may further define a dosage retrieval area, wherein the dosage passes into the dosage retrieval area after passing through the second gate. Further, the case may include a retrieval shutter operable to selectively open to allow the patient to remove the dosage from the dosage retrieval area. A retrieval shutter locking pin may secure the retrieval shutter in a closed position, wherein the retrieval shutter locking pin is retractable to allow the retrieval shutter to open. The medication dispensing device may further comprises a vibrating motor associated with the medication holding area, wherein the vibrating motor is powered by the battery upon receipt of the valid request to aid transport of the dosage to and through the first gate.
[0012] In another aspect, the case may include a first panel and a second panel having first and second sidewalls, respectively. Each of the first and second sidewalls may include at least one pair of corresponding case contacts that form a completed circuit when the first and second panels are disposed together. The CPU operates to secure at least one of the first and second gates in the closed position upon severing of the completed circuit.
[0013] In yet another aspect, the device may further include a camera and microphone, wherein the camera and microphone operate to record video data and audio data in the memory upon severing of the completed circuit. Further, the device may include a wireless transceiver that operates to transmit the video and audio data to a remote monitoring server. In addition, a global positioning system (GPS) node may be provided to transmit a location of the device to the remote monitoring server upon severing of the completed circuit. The device may also include a camera, microphone and touchscreen display, wherein the CPU is operable to initiate a videoconferencing application program to remotely engage with a medical professional via a videoconference session.
[0014] In another aspect, a medication dispensing device is provided that includes a case including a medication delivery system for selectively holding the medication and delivering the dosage to the patient. A CPU is disposed within the case and including a memory, wherein the dose availability is stored in the memory. A patient authentication device is in communication with the CPU and configured to receive the authorized patient identification input. A camera is configured to record video data in the memory, and a microphone configured to record audio data in the memory. A battery is configured for providing electrical energy to the CPU. Upon receipt of the valid request, the CPU operates the medication delivery system to deliver the dosage to the patient. Upon receipt of an invalid request, the camera and microphone operate to record video data and audio data in the memory, wherein the invalid request includes an unauthorized patient identification input at the patient authentication device. Further, the case may include a first panel and a second panel, wherein the first panel includes a first sidewall, and the second panel includes a second sidewall. Each of the first and second sidewalls include at least one pair of corresponding case contacts that form a completed circuit when the first and second panels are disposed together, wherein the camera and the microphone operate to record video data and audio data in the memory upon severing of the completed circuit.
[0015] In yet another aspect, a medication dispensing device is provided that includes a case including a medication delivery system configured for selectively holding the medication and delivering the dosage to the patient. The case further includes a first panel and a second panel, wherein the first panel includes a first sidewall, and the second panel includes a second sidewall. Each of the first and second sidewalls includes at least one pair of corresponding case contacts that form a completed circuit when the first and second panels are disposed together. A CPU is disposed within the case and includes a memory, wherein the dose availability is stored in the memory. A camera is configured to record video data in the memory, and a microphone is configured to record audio data in the memory. A battery is configured for providing electrical energy to the CPU. Upon receipt of the valid request, the CPU operates the medication delivery system to deliver the dosage to the patient, and the camera and microphone operate to record video data and audio data in the memory upon severing of the completed circuit.
[0016] In a further aspect of the present invention, a medication dispensing device comprises a cartridge unit and a control unit. The cartridge housing has a bottom surface and an upwardly extending sidewall defining a cartridge receiving area with the sidewall further defining a dispensing channel formed therethrough to allow passage of the dosage from the cartridge receiving area to the patient. A cartridge is configured to reside within the cartridge receiving area and hold one or more dosages. A driven member is positioned within the cartridge receiving area and is configured to engage the cartridge with the driven member being selectively actuatable to drive the cartridge so as to cause dispensing of a next sequential dosage through the dispensing channel. The control unit comprises a main housing configured for removable coupling to the cartridge housing and having a top surface and a downwardly extending sidewall defining a controller receiving area. The downwardly extending sidewall is configured to coincide with the upwardly extending sidewall of the cartridge housing to prevent access to the cartridge receiving area and the controller receiving area. A driver member is positioned with the controller receiver area and is configured to engage the driven member such that actuation of the driver member upon receipt of the valid request operates to actuate the driven member. A motor driven locking mechanism is moveable between locked and unlocked positions, wherein when in the locked position the cartridge unit is secured to the control unit and wherein when in the unlocked position the cartridge unit is separable from the control unit thereby providing access to the cartridge. A mobile computing device includes a central processing unit (CPU) and a memory, wherein the dosage availability is stored in the memory and the mobile computing device is configured to receive the authorized patient identification input. A battery is configured for providing electrical energy to the driver member and the motor driven locking mechanism.
[0017] In still a further aspect, a medication dispensing device comprises a cartridge unit and a control unit. The cartridge unit comprises a cartridge housing having a bottom surface and an upwardly extending sidewall defining a cartridge receiving area. The sidewall further defines a dispensing channel formed therethrough to allow passage of the dosage from the cartridge receiving area to the patient. A cartridge is configured to reside within the cartridge receiving area and hold one or more dosages. The cartridge includes a plurality of walls in spaced parallel relation with one another and extending generally perpendicular to the dispensing channel. A back wall extends across a rear edge of the plurality of wells to thereby define a plurality of dosage wells wherein each well is configured to contain a stack of dosages. A respective dispensing wheel is positioned at a forward edge of the plurality of wells wherein each dispensing wheel includes a recess configured to receive a single dosage at a time from its respective stack. A driven member is positioned within the cartridge receiving area and configured to engage the cartridge and wherein the driven member is coupled to the dispensing wheels. Upon receipt of a valid request the driver member is energized to drive rotation of the driven member and dispensing wheels so as to advance each respective recess until the next sequential dosage becomes aligned with the dispensing channel thereby dispensing the dosage. The control unit comprises a main housing configured for removable coupling to the cartridge housing and having a top surface and a downwardly extending sidewall defining a controller receiving area. The downwardly extending sidewall is configured to coincide with the upwardly extending sidewall of the cartridge housing. When coupled to the sidewalls prevent access to the cartridge receiving area and the controller receiving area. A driver member is positioned within the controller receiver area and is configured to engage the driven member such that actuation of the driver member upon receipt of the valid request operates to actuate the driven member. A mobile computing device includes a central processing unit (CPU) and a memory, wherein the dosage availability is stored in the memory. The mobile computing device is configured to receive the authorized patient identification input and a battery is configured to provide electrical energy to the driver member and the motor driven locking mechanism.
[0018] In yet another aspect, a prescription control system is provided. The system includes a medication filling device configured to sort and count one or more medications; a tray configured to engage the medication filling device, wherein a selected medication is sorted, counted and loaded onto the tray; and a medication dispensing device for dispensing a dosage of the selected medication to a patient. The dosage is dispensed to the patient upon receipt of a valid request. The medication dispensing device comprises a case defining a medication holding area and a dosage holding area, wherein the dose holding area includes an entry end and a dispensing end. The case includes a tray shutter operable to selectively open to allow loading of the tray within the medication holding area. The device further includes a first gate located at the entry end between the medication holding area and the dosage holding area. The first gate is operable to selectively open to allow the dosage to pass from the medication holding area to the dosage holding area. The device includes a second gate located at the dispensing end that is operable to selectively open to allow the dosage to pass from the dosage holding area to a retrieval area accessible to the patient. The device includes a CPU disposed within the case and including a memory, wherein the dosage availability is stored in memory. The device includes a patient authentication device in communication with the CPU that is configured to receive the authorized patient identification input, and a battery configured for providing electrical energy to the CPU. Upon receipt of the valid request, the CPU operates to: i) open the first gate to pass the dosage to the dosage holding area; ii) close the first gate after the dosage has passed to the dosage holding area; iii) open the second gate after the first gate has closed to dispense the dosage to the patient; and iv) close the second gate after the dosage has been dispensed to the patient.
[0019] Additional objects, advantages and novel features of the present invention will be set forth in part in the description which follows, and will in part become apparent to those in the practice of the invention, when considered with the attached figures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] The accompanying drawings form a part of the this specification and are to be read in conjunction therewith, wherein like reference numerals are employed to indicate like parts in the various views, and wherein:
[0021] FIG. 1 is a flow diagram illustrating the cycle of abuse suffered by patients that become addicted to one or more medications;
[0022] FIG. 2 is a system schematic of an embodiment of a prescription control system in accordance with an aspect of the present invention;
[0023] FIG. 3A is a plan view of an embodiment of a medication dispensing device used within the prescription control system shown in FIG. 2 ;
[0024] FIG. 3B is an internal plan view of the components comprising the medication dispensing device shown in FIG. 3A ;
[0025] FIG. 3C is a side view of the medication dispensing device used within the prescription control system shown in FIG. 2 ;
[0026] FIG. 4 is a block diagram showing communication pathways of the components comprising the medication dispensing device shown in FIGS. 3A-3C ;
[0027] FIG. 5 is an embodiment of a prescription drug tray configured to be used in conjunction with the medication dispensing device shown in FIGS. 3A-3C ;
[0028] FIG. 6 shows a logic flow diagram for initialization of the medication dispensing device shown in FIGS. 3A-3C ;
[0029] FIG. 7 shows a logic flow diagram for dispensing a medication from the medication dispensing device shown in FIGS. 3A-3C ;
[0030] FIG. 8 shows a logic flow diagram for a catastrophic sequence encountered by the medication dispensing device shown in FIGS. 3A-3C ;
[0031] FIG. 9 is a perspective view of an alternative embodiment of a medication dispensing device in accordance with the present invention;
[0032] FIG. 10 is an end perspective view of the medication dispensing device shown in FIG. 9 showing the dispensing door in a closed position;
[0033] FIG. 11 is an end perspective view of the medication dispensing device shown in FIG. 9 showing the dispensing door in an open position;
[0034] FIG. 12 is an exploded view of the medication dispensing device shown in FIG. 9 ;
[0035] FIG. 13 is a side perspective view of the housing members of the medication dispensing device shown in FIG. 9 in a decoupled position;
[0036] FIG. 14A is a side perspective view of the main housing of the medication dispensing device shown in FIG. 9 showing the locking tab in the extended position;
[0037] FIG. 14B is a side perspective view of the main housing of the medication dispensing device shown in FIG. 9 showing the locking tab in the retracted position;
[0038] FIG. 15 is a side perspective view of the cartridge housing of the medication dispensing device shown in FIG. 9 ;
[0039] FIG. 16 is a side perspective view of the cartridge housing of the medication dispensing device shown in FIG. 9 with the cartridge cover removed;
[0040] FIG. 17 is a detailed view of the dispensing channel of the cartridge housing of the medication dispensing device shown in FIG. 9 ;
[0041] FIG. 18 is a side perspective view of the cartridge housing of the medication dispensing device shown in FIG. 9 with a replaceable cartridge in an unloaded position;
[0042] FIG. 19 is a side perspective view of the cartridge housing of the medication dispensing device shown in FIG. 9 with a replaceable cartridge in a loaded position; and
[0043] FIG. 20 is a perspective view of an alternative embodiment of a cartridge for use within a medication dispensing device in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0044] Referring now to the drawings in detail, and specifically to FIG. 2 , a schematic of a prescription control system in accordance with an aspect of the present invention is generally designated by reference numeral 10 . Following surgery or after being involved in an accident or some other traumatic event, for instance, a patient may receive a prescription 12 from his or her treating physician/trained medical professional (“physician” or “doctor”). This prescription may be for a medication known to lead to addiction, such as a narcotic. Prescription 12 may be a hardcopy prescription slip or may be an electronic prescription. Patient data (such as, but not limited to, name, birth date, purported symptoms, etc.) and prescription data (such as, but not limited to, medication name(s), dosage data, etc.) may be entered onto a physician's computing system 14 , which then communicates 15 this data to a designated pharmacy computing system 16 for processing and fulfillment. While the present invention will be described with regard to electronic communications, such as those exchanged through a wireless network or over the Internet, it should be understood by those skilled in the art that all or some of such communications may include exchange of hardcopy materials, such as a traditional written prescription, and such hardcopy communications are to be regarded as within the scope of the present invention.
[0045] After prescription 12 is received by pharmacy computing system 16 , pharmacy computing system 16 uploads 17 information related to the prescription, such as the prescription data and patient data, received from physician's computing system 14 or from a traditional written prescription 12 to a hand-held medication dispensing device 18 . This information can be uploaded by populating an onboard central processing unit (CPU) 20 having on-chip internal memory storage, as seen in FIGS. 3B and 4 . Alternatively, CPU 20 may operate to access a separate external memory storage module housed within medication dispensing device 18 . In another aspect, the information related to the prescription may be uploaded 21 to medication dispensing device 18 directly form physician's computing system 14 or may be manually entered into medication dispensing device 18 by the pharmacist who received and is charged with filling prescription 12 ordered by the prescribing physician. As described, uploading of the information or data related to the prescription into the memory of CPU 20 may be conducted through wireless connectivity or may be conducted through a wired connection, such as through a USB data port 22 . Medication dispensing device 18 is then loaded with the prescribed type and number of medication as per the prescription's orders.
[0046] The prescribed medication may be either manually loaded into medication dispensing device 18 by a pharmacist or it may be loaded 23 via a medication filling device 24 in accordance with a further aspect of the present invention. Medication filing device 24 may also independently receive the electronically transmitted prescription 12 either directly from physician's computing system 14 via communication 25 , from pharmacy computing system 16 filling the prescription ordered by the prescribing physician via communication 26 , or it may be manually entered into medication filling device 24 device by the pharmacist who received and is charged with filling the prescription. Medication filling device 24 can then assist the pharmacist in filling the prescription, such as by mechanically sorting and counting the prescribed medication. The sorted and counted medication can then be directly loaded into medication dispensing device 18 or may be loaded onto a tray 27 for verification by the pharmacist before tray 27 is loaded into medication dispensing device 18 . A more detailed description of a tray 27 in accordance with this aspect of the present invention will be provided below with regard to FIG. 5 . Medication filling device 24 may also be used to program medication dispensing device 18 with the patient data and prescription data through a hardware/software interface via a hard wire connection or wirelessly.
[0047] As will be discussed in more detail below, medication dispensing device 18 will only dispense a dosage of medication upon receipt of a valid request. A valid request includes input of an authorized patient identification input or access code (discussed below) and requires a dosage availability in accordance with the directions provided by prescription 12 that is stored in the memory of medication dispensing device 18 . By way of example, if a dosage may be taken 4 times daily, medication dispensing device 18 will define a dosage availability as a dosage retrieval once every 6 hours (plus or minus a margin of time, such as, for example, 15 to 30 minutes) plus any emergency doses allocated by the prescription, i.e. a limited number of doses in addition to those regularly scheduled as per prescription 12 . Emergency doses may be requested at any time until all such emergency doses have been exhausted by the patient, at which point no additional emergency doses will be available and the patient will only be able to receive regularly scheduled doses until a new prescription is obtained and stored with the memory of medication dispensing device 18 . A third party vendor, which may include a remote monitoring server 28 , may be responsible for servicing and monitoring medication dispensing device 18 and may receive 29 a , 29 b prescription data from physician's computing system 14 and/or pharmacist's computing system 16 and monitor patient compliance and medication dispensing device 18 integrity (described below) to ensure that the patient is adhering to prescription 12 . Should indications warrant (such as a physical breach of the medication dispensing device 18 ), remote monitoring server 28 may communicate 30 such information to additional parties 31 , such as law enforcement entities, for appropriate intervention/action.
[0048] Turning now to FIGS. 3A , 3 B, 3 C and 4 , medication dispensing device 18 generally includes a case 32 having a front panel 34 and a back panel 35 . Medication dispensing device 18 is powered by a rechargeable battery 36 . Battery 36 may be recharged through a USB charge port 38 . After a predetermined time period of non-activity, CPU 20 will place the battery and other components within device 18 in a low energy state. If the battery level drops below a first programmed level, an alarm will sound on the device using a speaker 48 and/or an alert will be shown on a display 58 . If the battery level drops to a second programmed level device 18 will report 37 the event or alarm (hereinafter “event”) to remote monitoring server 28 and power down. CPU 20 will automatically reboot to the last programmed state when the battery level is increased by charging above the first programmed level, and communicate 37 this event to remote monitoring server 28 to inform vendor that device 18 is back online. While offline, reserve power from battery 36 will allow for a global positioning system (GPS) ping from node 40 until battery 36 is completely discharged. Medication dispensing device 18 can only be manually powered down via an override request issued by remote monitoring server 28 when it is intended that medication dispensing device 18 be placed in storage. The override request allows the vendor to access a power down protocol stored in the memory of CPU 20 so as to deactivate medication dispensing device 18 .
[0049] Front and back panels 34 , 35 include corresponding intermediate sides which join to form completed side walls 41 of case 32 . In accordance with an aspect of the invention, case 32 is proportioned so as to be a portable, hand-held unit. By way of example, case 32 may be configured to be no more than about 3 inches (7.5 cm) wide, about 5 inches (12.5 cm) long and about 1 inch (2.5 cm) deep. Intermediate sides 41 of both front and back panels 34 , 35 may include at least one pair of corresponding case contacts 42 which form a completed circuit upon formation of the completed side walls 41 . As will be discussed in more detail below, the completed circuit(s) created by case contacts 42 may be monitored by CPU 20 such that a warning or other security feature may be initiated should the circuit(s) become severed, such as during an attempt to pry open case 32 , which would be considered a catastrophic event. While shown and described as case contacts on respective side walls of front and back panels 34 , 35 , it should be understood by those skilled in the art that any suitable circuit configuration may be used so long as the circuit is interrupted when front panel 34 and back panel 35 become partially or completely separated from one another so as to generate the warning or other security feature. Such circuit configurations should be interpreted as within the scope of the present invention. To that end, medication dispensing device 18 may further include one or more of video camera 44 , microphone 46 and speaker 48 . Speaker 48 may be activated using an amplifier 49 to issue an audible warning. Additionally and/or alternatively, video camera 44 and/or microphone 46 may be activated so as to record video data and/or audio data, respectively, upon occurrence of a catastrophic event, such as a break in the circuit that is formed by case contacts 42 . The objective of recording the video and audio data is to help determine the facts surrounding the occurrence of the catastrophic event. This video and audio data can then be transmitted 37 to remote monitoring server 28 by way of a wireless receiver/transceiver (R/T) 50 for review and evaluation by the owner of device 18 or additional parties 31 . Furthermore, GPS node 40 may provide information regarding the location of device 18 should a warning/security breach take place when case contacts 42 are compromised. GPS node 40 may be either an active node continually transmitting 37 its location at predetermined time intervals or may be a passive node which will transmit 37 its location after being “pinged” automatically by remote monitoring server 28 or manually by additional party 31 . The video, audio and/or GPS data may then be forward to additional party 31 , such as a law enforcement entity, (see FIG. 2 ) if police action is indicated by such data.
[0050] A dosage 52 of medication 54 is dispensed by medication dispensing device 18 to a patient only upon the receipt of a valid dose request, wherein the valid dose request must comply with the prescription/dosage data in accordance with prescription 12 . A dose request may be initiated by activation of a patient authentication device 56 . Patient authentication device 56 may be a biometric sensor such as, but not limited to, one or more of a fingerprint scanner, facial recognition device, retinal scanner, voice recognition or similar system.
[0051] Medication dispensing device 18 may also include a touchscreen display 58 . Touchscreen display 58 may only be activated upon proper authentication via patient authentication device 56 , or may become activated upon a failed authentication wherein touchscreen display 58 is used to receive an optional access code override (such as via a touchscreen keypad and associated passcode as is known in the art). The access code override may be any type of access code, such as an alpha-numeric access code. If the authentication attempt is invalid (i.e., the entered biometric or access code does not match an authorized stored biometric or access code stored in memory), touchscreen display 58 will display an error and request that the user re-authenticate using patient authenticate device 56 or input of the optional code override. After a set number of authentication attempts and/or code attempts, the system will timeout for a preset period of time and report the event to remote monitoring server 28 via WiFi, SMS, or similar wireless communication using R/T 50 . If failed attempts continue, CPU 20 will interpret these attempts as a catastrophic event such that camera 44 and microphone 46 may be activated to transmit video and audio data to remote monitoring server 28 and GPS node 40 may be “pinged” as described above.
[0052] If “emergency doses” have been prescribed (i.e., doses in addition to those regularly scheduled as per prescription 12 ), a patient may selectively access an emergency dose contained within medication dispensing device 18 at any time until all emergency doses have been consumed. Using an emergency dose will record an event in a data file stored in the memory of CPU 20 , and if desired upload the event to remote monitoring server 28 , pharmacist computing system 16 and/or physician computing system 14 . Otherwise, dosing times will be restricted to those programmed into the memory of CPU 20 as described above. An upcoming dosing interval (e.g., every 6 hours plus or minus 15 to 30 minutes) will trigger an alert through speaker 48 , with programmed repeated alerts given during the dosing interval. The patient can request a dose at any time during this interval. If the interval passes without a dose request, this will be recorded on the data file in the memory of CPU 20 .
[0053] Touchscreen display 58 may also allow for additional functionality such as displaying information regarding the medication dispensing device (e.g., serial number, service number, etc.), prescribed medication (e.g., medication name, side effects, compatibilities, incompatibilities, etc.), prescription data (e.g., number and timing of dosages, etc.), dosage data (e.g., time of last dosage, time of next available dosage, number of emergency doses remaining, etc.), prescription compliance and the like. In accordance with an embodiment of the present invention, CPU 20 and its associated memory may also include a videoconferencing program application, such as SKYPE or FACETIME, which may be initiated by the patient wherein the touchscreen display 58 , video camera 44 , microphone 46 and speaker 48 enable remote videoconferencing between the patient and the physician and/or the pharmacist and/or third party vendor personnel associated with remote monitoring server 28 should the patient have any questions or concerns regarding the medication, its dosage or medication dispensing device 18 . In accordance with a further embodiment of the present invention, the code override may be remotely utilized by third party vendor associated with remote monitoring server 28 such as for system maintenance/trouble shooting or by an additional party 31 (e.g., law enforcement) such as to gain access to the prescription/dosage data stored within the memory of CPU 20 .
[0054] In order to dispense dosage 52 upon receipt of a valid request, case 32 including a medication delivery system for holding the medication and delivering the dose to the patient, wherein the medication delivery system includes a medication holding area 60 and a dosage holding area 62 . The system further includes a first gate 64 is located at an entry end dosage holding area 62 of between medication holding area 60 and dosage holding area 62 and is operable (such as by way of a first actuator 66 ) to selectively open and thereby allow an individual dosage 52 of medication 54 housed in medication holding area 60 to enter dosage holding area 62 . The system further includes a second gate 68 is located at a dispending end at the opposing end of dosage holding area 62 and prevents release of dosage 52 until second gate 68 is selectively opened (such as by way of a second actuator 70 ). To facilitate movement of the medication/individual dosage through medication dispensing device 18 , a vibrating motor 72 is associated with the medication holding area 60 and is energized when dosage 52 is being dispensed. The vibration of motor 72 serves to jostle medication 54 until individual dosage 52 is immediately adjacent the opening created by opened first gate 64 and in the proper orientation so as to enter dosage holding area 62 . In accordance with an aspect of the present invention, first and second actuators 66 , 70 are servomotors 73 where, at most, only one servomotor 73 is operable at a time so that first or second gates 64 , 68 are never both in an open position at the same time.
[0055] In accordance with a further aspect of the present invention, a photogate 74 is associated with dosage holding area 62 wherein photogate 74 regulates activation of actuators 66 , 70 . For instance, first actuator 66 may be powered so as to open first gate 64 wherein dosage 52 exits medication holding area 60 and enters dosage holding area 62 . Dosage 52 interrupts photogate 74 such that first actuator 66 is returned to its original state and first gate 64 is closed. Second actuator 70 can then be powered to open second gate 68 and thereby allow dosage 52 to exit the dosage holding area 65 . Once photogate 74 is no longer impeded by dosage 52 , second actuator 70 can then return to its original state thereby closing second gate 68 . In this manner, release of medication may be controlled so as to limit distribution of medication 54 to a single dosage 52 per valid request.
[0056] Case 32 may be configured so as to be substantially waterproof. To help ensure waterproofing of the interior components of device 18 , medication dispensing device 18 may further define a dosage retrieval area 76 located after second gate 68 . Case 32 includes a retrieval shutter 78 operable to selectively open once dosage 52 enters the dosage retrieval area 76 and second gate 68 is closed by second actuator 70 . Retrieval shutter 78 is sealed within case 32 by a watertight gasket along the inner and/or outer edges of retrieval shutter 78 . Retrieval shutter 78 is configured to slidably engage case 32 wherein retrieval shutter 78 slides open to allow passage of dosage 52 . To secure retrieval shutter 78 in a closed position when a dosage is not being removed, case 32 carries a retrieval shutter locking pin 80 that engages retrieval shutter 78 to prevent unwanted or unauthorized sliding of the shutter. Retrieval shutter locking pin 80 may be retracted upon command from CPU 20 such that retrieval shutter 78 can open and dosage 52 be removed. When retrieval shutter 78 is opened, a time stamp will be recorded in the data file and associated with this event. If retrieval shutter 78 has not been closed satisfactorily in certain period of time, the device will continuously sound a warning through speaker 48 and/or touchscreen display 58 . After a second period of time, an alarm may be sent to remote monitoring server 28 notifying the third party vendor of the retrieval shutter's malfunction so that proper corrective action may be readily employed.
[0057] As best seen in FIG. 5 , medication 54 may be loaded into medication dispensing device 18 via a tray 27 . As described above, tray 27 may be manually loaded by the pharmacist or may be loaded via medication filling device 24 . In either case, once tray 27 has been filled with the proper type and number of medication 54 , tray 27 is inserted into medication holding area 60 . To facilitate insertion of tray 27 , case 32 is configured to include a tray shutter 82 configured to allow passage of tray 27 therethrough. Similar to retrieval shutter 78 described above, tray shutter 82 is slidably sealed within case 32 by a watertight gasket along the inner and/or outer edges of tray shutter 82 wherein tray shutter 82 slides open to allow passage of tray 27 . To secure tray shutter 82 in a closed position when tray 27 is not being inserted or removed, case 32 carries a tray shutter locking pin 84 that engages tray shutter 82 to prevent unwanted or unauthorized sliding of tray shutter 82 . Pin 84 may be retracted upon command from CPU 20 such that tray shutter 82 can open and tray 27 can be inserted or removed.
[0058] Tray 27 includes a bottom 86 with upwardly extending side walls 88 , 90 , rear wall 92 and front wall 94 defining a tray interior 96 . Each of side walls 88 , 90 form an acute angle with rear wall 92 such that rear wall 92 has a greater length than front wall 94 . Additionally, each of side walls 88 , 90 also increase in width as they extend from rear wall 92 toward front wall 94 such that rear wall 92 has a smaller width than front wall 94 . Bottom 86 may also include a central valley 98 such that bottom halves 86 a and 86 b are sloped as they extend from central valley 98 to side walls 88 , 90 , respectively.
[0059] Tray 27 is proportioned so as to substantially occupy medication holding area 60 defined by case 32 . That is, side walls 88 , 90 of tray 27 are configured to lie against medication holding area side walls 60 a , 60 b , respectively, such that little to no gap is formed between tray 27 and medication holding area side walls 60 a , 60 b . Tray side walls 88 , 90 are of such length that rear wall 92 lies against tray shutter 82 while front wall 94 abuts first gate 64 when tray 27 is loaded into medication dispensing device 18 . Front wall 94 is configured to define an opening 100 proportioned to allow individual dosage 52 (see FIG. 3B ) to pass from tray interior 96 through first gate 64 into dosage holding area 62 . The internal surface of case front panel 34 is configured to seat against the top edges of walls 88 , 90 , 92 , 94 so as to prevent ejection of medication 54 from tray 27 should medication dispensing device 18 be inverted after tray 27 is loaded into the device. Further, the interior surface of the bottom panel of case 32 includes a ramp portion or other retaining feature so as to hold the top edge of rear wall 92 against the inner surface of front panel 34 . As a result, tray 27 is pitched such that the portion of tray bottom 86 closest to rear wall 92 is higher than the portion closest to front wall 94 . This pitch, combined with the slope created by bottom halves 86 a , 86 b in conjunction with valley 98 , operates to direct medication 54 toward tray front wall 94 , opening 100 and first gate 64 .
[0060] Multiple versions of tray 27 may be fabricated wherein each tray 27 includes a tray opening 100 having a different size. In this manner, a pharmacist can selectively choose a tray 27 for loading wherein tray opening 100 is selected to be slightly larger than medication 54 prescribed. As a result, tray opening 100 effectively throttles the dispensing of individual dosages 52 such that only one pill is distributed into dosage holding area 62 per request.
[0061] FIGS. 6-8 show logic flow diagrams for various actions carried out by medication dispensing device 18 . The power-up and initialization protocol is shown in FIG. 6 . Initially, at step 102 , CPU 20 queries the security measures (i.e., case contacts 42 , actuators 66 , 70 ) to verify that all measures are intact and operating. If the measures are not intact, a warning is issued (such as an auditory warning via speaker 48 ) at step 104 . Following the warning, CPU 20 determines whether the warning is a catastrophic warning at step 106 requiring initiation of the defense routine and device lockdown (see FIG. 8 ) at step 108 . Alternatively, at step 110 , if the security measures are intact or if the warning is not a catastrophic warning, CPU 20 queries receiver/transceiver (R/T) 50 to determine if there is external wireless connectivity. If there is wireless connectivity, R/T 50 conducts a data exchange with physician computing system 14 , the pharmacy computing system 16 and/or the data server of remote monitoring server 28 at step 112 .
[0062] Following the data exchange, or should no wireless connectivity be detected, CPU 20 then interrogates the memory of CPU 20 to determine if there is a valid prescription file stored in memory at step 114 . At step 116 , if there is no valid prescription file, medication dispensing device 18 enters hibernation mode until another power-up sequence is initiated. If a valid prescription 12 is on file, medication dispensing device 18 enters stand-by mode awaiting a dose request from the patient at step 118 . The device exits stand-by mode upon a dose request, such as through activation of patient authorization device 56 (i.e., the biometric sensor) at step 120 . If the biometric scan is successful, touchscreen display 58 is activated and the patient can request a dosage at step 122 . If the biometric scan is unsuccessful at step 124 , a warning is issued and the patient is prompted to attempt a new scan at step 126 . If there are a preselected number of unsuccessful scans (e.g., 3 unsuccessful scans) CPU 20 reinitiates the power-up protocol and queries the device's security measures as discussed above at step 128 .
[0063] Turning now to FIG. 7 , displayed is a logic flow diagram to determine if a dosage may be dispensed upon a patient request (i.e. whether the request is a valid request). Prior to dispensing a dosage, CPU 20 queries the security measures to verify that they are intact at step 130 (as discussed above). If the security measures are not intact, a warning is issued at step 132 and CPU 20 determines whether the warning constitutes a catastrophic warning at step 134 necessitating initiation of device's 18 defense routine and device lockout (see FIG. 8 ) at step 136 . If the security measures are intact or if the warning is not a catastrophic warning, CPU 20 interrogates the data file stored in its memory to determine whether the request is within an authorized prescription window at step 138 . If the request is not within an authorized prescription window, CPU 20 interrogates the data file to determine whether any emergency doses are available at step 140 . If no emergency doses are available, CPU 20 reinitiates the dispense routine.
[0064] If the request is within an authorized prescription window, of if an emergency dosage is available (step 142 ), CPU 20 initiates engagement of first actuator 66 , motor 72 and photogate 74 at step 144 so as to direct an individual dosage 52 from medication holding area 60 /tray 27 into dosage holding area 62 as described above. Upon passage of dosage 52 into dosage holding area 62 , photogate 74 is blocked/interrupted at step 146 wherein photogate 74 sends a signal to CPU 20 of its state change. CPU 20 then disengages first actuator 66 so as to close first gate 64 , deactivates motor 72 and photogate 74 at step 148 . Once first gate 64 is closed, CPU 20 sends a command to engage second actuator 70 and logs the occurrence of the dosage dispensing in the data file at step 150 . If case 32 includes a retrieval shutter 78 , CPU 20 issues a command to retrieval shutter locking pin 80 to retract and thereby allow retrieval shutter 78 to open and dispense dosage 52 to the patient at step 152 . At step 154 , CPU 20 then disengages second actuator 70 thereby dosing second gate 68 and issues a command to close retrieval shutter 78 and extend retrieval shutter locking pin 80 .
[0065] FIG. 8 shows a logic flow diagram for a catastrophic warning. If a warning is determined to constitute a catastrophic warning (see above), CPU 20 generates a data log of the occurrence and activates camera 44 and microphone 46 to record video and audio data at step 156 . CPU 20 also locks all gates, shutters, servomotors and the touchscreen display. CPU 20 then determines whether there is external connectivity via R/T 50 at step 158 . At step 160 , if there is no connectivity and the warning has not been fixed, CPU 20 logs the time and tags all data (i.e., camera and microphone recordings) for upload once external connectivity is established at step 162 . If there is no connectivity and the warning has been fixed, CPU 20 still logs the time and tags all data for upload once external connectivity is established at step 164 , but also attempts to place all systems in normal operating condition. If all systems are operable at step 166 , the device is returned to normal operation at step 168 . However, is all systems are not operable, CPU 20 determines whether there is external connectivity so as to exchange the catastrophic warning data collected.
[0066] On the other hand, if there is external connectivity, the data (i.e., camera and microphone recordings) are exchanged with an external server at step 170 , such as remote monitoring server 28 . CPU 20 then determines whether the warning has been fixed at step 172 . If the warning has not been fixed, CPU 20 logs the event and camera 44 and microphone 46 continue to record video and audio data. This data is then exchanged with remote monitoring server 28 or tagged for later upload should external connectivity have been lost at step 174 . However, if the warning has been fixed, CPU 20 attempts to place all systems in normal operating condition. If all systems are operable, the medication dispensing device 18 is returned to normal operation. If all systems are not operable, CPU 20 determines whether there is external connectivity so as to continue to exchange the catastrophic warning data being collected, such as by camera 44 , microphone 46 and/or GPS node 40 .
[0067] Turning now to FIGS. 9-19 , an additional embodiment of a medication dispensing device in accordance with the present invention is generally indicated by reference numeral 218 . Medication dispensing device 218 generally includes a cartridge housing 220 having an upwardly extending sidewall 222 removably secured to a downwardly extending sidewall 224 of a main housing 226 . In certain embodiments, sidewalls 222 / 224 may include one or more pairs of opposing case contacts so as to verify device integrity as described above with regard to device 18 . Should anybody attempt to tamper with device 218 , the case contacts will become disrupted such that a trigger signal may be initiated as discussed above, and as further discussed below. An optional rubber guard 225 may encircle part or all of sidewalls 222 / 224 when cartridge housing 220 is coupled with main housing 226 . In accordance with an aspect of the present invention, a portion of sidewalls 222 / 224 may be configured to include an extended lobe 222 a / 224 a whose external edge 228 defines the terminus of a dispensing channel 230 . Rubber guard 225 does not overlap lobe portion 222 a / 224 a such that a door 232 may selectively open and close channel 230 .
[0068] As seen most clearly in FIGS. 16 and 17 , lobe 222 a (and 224 a , not shown) defines an extended channel 230 through which a dosage 52 must pass when being dispensed. Channel 230 may be proportioned so as to allow only a single dosage to pass through the channel at a time, and such proportions may be varied as needed depending upon the size and shape of the prescribed medication. In accordance with an aspect of the present invention, channel 230 may be configured to have a non-linear profile such that dosage 52 must traverse a tortuous path before exiting device 218 . Non-linear channel 230 may assist in preventing unauthorized dispensing of a dosage as any tool inserted within non-linear channel 218 in an attempt to dislodge an authorized dosage will become obstructed by one or more walls of channel 218 .
[0069] Returning now to FIGS. 9-12 , medication dispensing device 218 may also include a mobile computing device, such as, for example, a smartphone 234 . Smartphone 234 may be secured to main housing 226 by a front cover 236 . In accordance with an aspect of the embodiment of device 218 , smartphone 234 may be utilized so as to harness its inherent memory and computing power, and may replace one or more of the functionalities and modalities described above with regard to device 18 , namely CPU 20 , GPS module 40 , camera 44 , microphone 46 , speaker 48 , amplifier 49 , patient authentication device 56 and touchscreen 58 . Thus, it should be understood by those skilled in the art that medication dispensing device 218 may include individual components such as those described above with regard to device 18 , but instead utilizes smartphone 234 to provide similar features and functionalities.
[0070] Turning now to FIG. 13 , in accordance with an aspect of the present invention, cartridge housing 220 is configured for removable attachment to main housing 226 , such as through one or more corresponding slots and tabs. Cartridge housing 220 may include one or more slots 238 (only one shown) which are configured to mate with corresponding tabs 240 , such as 240 a , 240 b as shown, so as to secure the two housings 220 / 226 together. As shown most clearly in FIGS. 14A and 14B , one of tabs 240 , such as tab 240 b , may be coupled to an actuator member, such as motor 242 via a threaded rotating shaft 243 . Tab 240 b may be driven upon powering of motor 242 via battery 244 . In this manner, tab 240 b may be slidably driven upon shaft 243 between an extended position (as shown in FIG. 14A ) whereby tab 240 b resides in its respective slot 238 to secure housings 220 / 226 together, and a retracted position (as shown in FIG. 14B ) whereby tab 240 b is withdrawn from its slot thereby permitting removal of cartridge housing 220 from main housing 226 . In accordance with an aspect of the present invention, motor 242 is only powered upon receipt of a proper authentication input by a device administrator, such as a pharmacist, for example. An authentic input by an administrator may also operate to override any warning issued by the disruption of the case contacts, if provided.
[0071] As further shown in FIGS. 12 , 14 A and 14 B, main housing 226 may further include a driver member 246 and associated actuator (drive motor) 248 . Driver member 246 is coupled to a driven member 250 , such as a pulley, in cartridge housing 220 as will be described in more detail below. By way of example, and by no means limiting specifically thereto, driver member 246 may include a gear 252 extending outwardly from the plane formed by the terminal edge of downwardly extending sidewall 224 . To prevent dust or debris from entering main housing 226 , a main housing cover 227 may be included. Rotation of driver member 246 and gear 252 may be translated through mating 45 degree miter gears, where a first miter gear 254 a is coupled to drive motor 248 and a second miter gear 254 b is coupled to driver member 246 .
[0072] With reference to FIGS. 15-17 , gear 252 may be configured to engage pulley shaft 256 on driven member (pulley) 250 residing within cartridge housing 220 . Thus, as gear 252 is rotated upon powering of drive motor 248 , pulley shaft 256 is caused to rotate such that driven member 250 advances belt 258 within cartridge receiving area 260 defined by cartridge wall 261 . Drive motor 248 may only be powered once a valid request for a dosage has been inputted into smartphone 234 , similar to that process discussed above with regard to device 18 . A passive member (pulley) 262 may be employed to assist advancement of belt 258 as will be discussed in greater detail below. To prevent contamination of cartridge receiving area 260 and any loaded dosages 52 contained therein, cartridge housing 220 may include a cover plate 264 which is selectively removable, such as through a thumb screw 266 . An additional pulley cover plate 268 may also be used to prevent contamination (see FIG. 18-19 ).
[0073] As shown in FIGS. 16-19 , a belt 258 has a plurality of outwardly extending fingers 272 which define a plurality of dosages slots 274 therebetween. Dosage slots 274 are proportioned to receive a single respective dosage 52 therein. Inner wall 276 of belt 258 is sized to snuggly engage pulley 250 / 262 so as to enable rotation of belt 258 upon powering of drive motor 248 as discussed above. Pulleys 250 / 262 and/or inner wall 276 of belt 258 may also be configured to include cogs 278 and/or slots (not shown) to assist rotation of the belt, prevent slipping of the belt and improve indexing of the belt with respect to dispensing slot 230 . That is, drive motor 248 may be indexed to power rotation of driver member 246 so as to advance belt 258 only that distance required to align a next sequential dosage 52 with dispensing slot 230 . Proper indexing ensures that only a single dosage is dispensed upon receipt of a valid request as discussed above with regard to embodiment 18 .
[0074] In accordance with an aspect of the embodiment of medication dispensing device 218 , belt 258 may be configured to remain within cartridge receiving area 260 while dosages 52 are individually added to respective dosage slots 274 when device 218 is being loaded. In a further aspect, such as that shown in FIGS. 18 and 19 , medication dispensing device 218 may include a cartridge 270 comprising belt 258 ′ and cartridge cover 280 . Belt 258 ′ is similar to belt 258 but is configured to include a floor 282 integrally formed with belt inner wall 276 ′ and outwardly extending fingers 272 ′. Cover 280 includes a top panel 284 and outer sidewall 286 . Cover 280 is proportioned so as to snuggly fit upon belt 258 ′ such that dosages 52 cannot fall out of dosage slots 274 ′ when the cover is in place. In this manner, cartridge 270 may be loaded within cartridge receiving area 260 such that belt 258 ′ fits snuggly upon pulleys 250 / 262 as described above. Cover 280 may then be removed from cartridge 270 via one or more cartridge tabs 288 . Dosages 52 will then be retained within their respective dosage slots 274 ′ via fingers 272 ′ of the belt and cartridge cover 264 and cartridge wall 261 of the cartridge housing 220 .
[0075] Turning now to FIG. 20 , a further embodiment of a medication dispensing device 218 may replace cartridge housing 220 with cartridge housing 320 . Cartridge housing 320 includes an upwardly extending sidewall 322 configured to mate with downwardly extending sidewall 224 of main housing 226 as described above. As shown in FIG. 20 , cartridge housing 320 may be configured not to include an extended lobe as described above. Main housing 226 would likewise be configured so as not to include an extended lobe 224 a . However, for improved security, an extended lobe portion, and non-linear dispensing channel, may be included if desired.
[0076] Cartridge housing 320 includes a cartridge receiving area 360 which includes a plurality of walls 362 arranged in spaced parallel relation with one another. A back wall 364 extends across the rear end of walls 362 so as to define a number of dispensing channels 366 . By way of example, cartridge 320 is shown to include five dispensing channels 366 , although it should be understood by those skilled in the art that any number of channels may be included. The opposing, forward edge of walls 362 terminate at a plurality of dispensing wheels array, wherein each dispensing channel 366 terminates at a dedicated dispensing wheel 368 . Each dispensing wheel 368 includes a recess 370 which is proportioned to receive a single dosage 52 from a stack of dosages loaded within the dispensing channels. Recesses 370 may be rotationally offset from one another a common number of degrees, such that the sum of the total number of degrees equals 360. By way of example, cartridge 320 having five dispensing channels would have five associated dispensing wheels. As a result, each recess 370 would have its center offset 72 degrees apart from the next adjacent recess (72 degrees multiplied by 5 equals 360 degrees).
[0077] Driven member 372 , such as a toothed gear, is coupled to dispensing wheels 368 via a common shaft (not shown) such that powering of drive motor 248 operates to drive driven member 372 to rotate dispensing wheels 368 the common number of degrees (i.e. 72 degrees as shown in FIG. 20 ). In this manner, recess 370 of one dispensing wheel is rotated so as to correlate with the dispensing slot 230 ′ and thereby dispense a single dosage. The recess of three other dispensing wheels may then advance 72 degrees such that the dosage residing within each respective recess is trapped between its respective dispensing wheel 368 and cartridge housing 320 or cover plate 264 (not shown). The remaining dispensing wheel, which was earlier emptied by dispensing its dosage, may advance 72 degrees so as to coincide with its stack of dosages whereby a single dosage 52 is loaded into the empty recess.
[0078] To assist loading of dosages 52 into their respective recesses 370 , each dispensing channel 366 may include a biasing member 374 . One end of biasing member 374 may rest against or be secure to back wall 364 while the opposing end of biasing member 374 engages the stack of dosages within its respective channel 366 . Optionally, a biasing plate (not shown) may be placed between biasing member 374 and dosage 52 . It is further envisioned that cartridge 360 may be a removable/replaceable cartridge similar to cartridge 270 such that an empty cartridge may be removed from cartridge receiving area 360 while a loaded cartridge may be inserted into the receiving area such that its dispensing channels properly align with dispensing wheels 368 .
[0079] In accordance with the above, the present invention provides numerous advantages and aspects that are not provided for in the existing art. For example, medication dispensing device 18 operates to dispense controlled substances, such as narcotics, only at the rate designated by the prescribing doctor using, among other components, first and second gates that define a dosage holding area and selectively and controllably dispensing such medication. Further, medication dispensing device 18 is portable so as to provide proper regulation of the patient's drug regimen without requiring the patient to be tied to a non-portable, home-based medication dispenser. Also, medication dispensing device 18 includes security features that operate to record sound data, video data, and/or GPS data, when a breach of device 18 occurs, and transmits such data to a remote monitoring system so that appropriate action may be taken by the owner of device 18 or a third party vendor. Other advantages are also provided.
[0080] The foregoing description of the preferred embodiment of the invention has been presented for the purpose of illustration and description. It is not intended to be exhaustive nor is it intended to limit the invention to the precise form disclosed. It will be apparent to those skilled in the art that the disclosed embodiments may be modified in light of the above teachings. The embodiments described are chosen to provide an illustration of principles of the invention and its practical application to enable thereby one of ordinary skill in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. Therefore, the foregoing description is to be considered exemplary, rather than limiting, and the true scope of the invention is that described in the following claims. | A medication dispensing device comprises a cartridge unit and a control unit. The cartridge unit comprises a cartridge housing defining a dispensing channel to allow passage of the dosage from the cartridge to the patient. A cartridge holds dosages, with a driven member engaging the cartridge. The driven member drives the cartridge to dispense a dosage. The control unit comprises a main housing for coupling to the cartridge housing. A driver member engages the driven member to actuate the driven member. A motor driven locking mechanism is moveable between locked and unlocked positions. When in the locked position the cartridge unit is secured to the control unit. When in the unlocked position the cartridge unit is separable from the control unit thereby providing access to the cartridge. A mobile computing device stores dosage availability and receives an authorized patient identification input before dispensing a dosage. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims benefit of U.S. Provisional Patent Application Ser. No. 61/448,102 filed Mar. 1, 2011, which is herein incorporated by reference.
FIELD
[0002] Embodiments described herein relate to semiconductor manufacturing processes and apparatus. More specifically, methods and apparatus for forming and treating material layers on semiconductor substrates are disclosed.
BACKGROUND
[0003] The CMOS field-effect transistor is the functional core of most semiconductor devices. Over the past 50 years, Moore's Law has driven reduction in the size of MOSFETs and closer packing of MOSFETs on smaller chips. As size has been reduced, manufacturing challenges have mounted.
[0004] Typically, a MOSFET includes a gate structure disposed over a channel region. The gate structure controls flow of electricity through the channel region by changing the electronic properties of the channel region when a voltage is applied to the gate structure. The gate structure generally includes a gate electrode and a gate dielectric between the gate electrode and the channel region. When a voltage is applied to the gate electrode, an electric field is established in the gate dielectric and the channel region that changes the flow of charge carriers through the channel region.
[0005] The gate dielectric is typically formed from silicon nitride, silicon oxynitride, metal oxide, metal nitride, or metal silicate. The gate electrode is commonly silicon. Various processes, including plasma CVD, thermal treatment, DPN, RTP, remote plasma processes, and oxidation processes are commonly performed on a substrate to build a MOSFET gate structure. In one process, a layer of silicon oxide is formed on a substrate in a PECVD chamber. The substrate is moved to a DPN chamber for nitridation. The substrate is moved to an RTP chamber for re-oxidation. Then the substrate is moved to a second PECVD chamber for silicon deposition. The chambers are generally coupled to a transfer chamber that moves the substrates from process to process.
[0006] Production platforms such as that described above, and the processes they perform, are expensive and have limited throughput. Pathways for processing substrates must be changed among the various chambers to change processing order, with impacts on throughput. Apparatus and methods of processing substrates using multi-functional chambers would streamline production, increase throughput, and reduce the need for substrate handling.
[0007] Accordingly, there is a continuing need for efficient and cost-effecting methods and apparatus for forming gate structures on substrates.
SUMMARY
[0008] A chamber for processing semiconductor substrates is described in one embodiment. The chamber includes a substrate support with an in-situ plasma source facing the substrate support and a radiant heat source spaced apart from the substrate support. The substrate support may be between the in-situ plasma source and the radiant heat source. The radiant heat source may be a bank of thermal lamps. The in-situ plasma source may be an inductive or capacitive plasma source, or a microwave or millimeter wave plasma source.
[0009] The chamber may include a remote plasma source connected to the chamber and disposed through a wall facing the substrate support or adjacent to the substrate support. The remote plasma source may be connected to a gas distributor disposed through the in-situ plasma source. A window may be disposed between the radiant heat source and the substrate support, and the substrate support may rotate.
[0010] In another embodiment, a chamber is described having a high ion density plasma source and a low ion density plasma source, both positioned to expose a substrate disposed on a substrate support to a plasma. A radiant heat source may be included in the chamber, and may be located with the substrate support between the plasma sources and the radiant heat source.
[0011] In another embodiment, a method of processing a substrate in a processing chamber is provided. The method includes forming an oxide layer on the substrate by exposing the substrate to a plasma generated in the chamber, performing a plasma nitridation process on the substrate in the chamber, thermally treating the substrate using a radiant heat source disposed in the chamber while exposing the substrate to oxygen radicals formed outside the chamber, and forming an electrode on the substrate by exposing the substrate to a plasma generated in the chamber. The above steps may be performed without removing the substrate from the chamber.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] So that the manner in which the above-recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
[0013] FIG. 1 is a cross-sectional view of a processing chamber according to one embodiment.
[0014] FIG. 2 is a flow diagram summarizing a method according to another embodiment.
[0015] To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures. It is contemplated that elements disclosed in one embodiment may be beneficially utilized on other embodiments without specific recitation.
DETAILED DESCRIPTION
[0016] A multi-functional chamber may be configured to perform a variety of material and thermal processes on a substrate without removing the substrate from the chamber. FIG. 1 is a cross-sectional view of such a chamber 100 according to one embodiment. The chamber of FIG. 1 is capable of performing various plasma and thermal deposition and treatment processes on a substrate simultaneously, concurrently, or sequentially. The substrate may remain in the chamber while a series of processes is performed on the substrate, or the substrate may be removed at times and returned later to the chamber for subsequent processing.
[0017] The chamber 100 of FIG. 1 has an enclosure 102 with a first portion 104 , a second portion 106 , and a third portion 108 . The enclosure 102 may be anodized aluminum or quartz, or may be anodized aluminum with a quartz chamber liner, such materials being resistant to most processes performed in manufacturing field-effect transistors. The first, second, and third portions 104 , 106 , and 108 , may be formed integrally together or removably attached using fasteners (not shown).
[0018] A substrate support 110 is disposed within the enclosure 102 , and extends through the third portion 108 to a control assembly 112 . The control assembly 112 may have a motor rotationally coupled to the substrate support 110 , a thermal control module 114 for providing a thermal control fluid through a conduit 116 in the substrate support, and an electrical unit 118 for providing electrical bias to the substrate support 110 or for electrostatically immobilizing a substrate on the substrate support 110 .
[0019] A plasma source 120 is disposed in the first portion 104 of the enclosure 102 facing the substrate support 110 . The plasma source 120 is an inductive plasma source comprising a plurality of conductive loops 122 energized by one or more RF power sources 124 . A process gas source 160 is fluidly coupled to the chamber 100 by a process gas conduit 126 disposed through the plasma source 120 , with a gas distributor 128 positioned in a central portion of the plasma source 120 facing the substrate support 110 . Process gases to be activated by the plasma source 120 may be provided to the chamber 100 through the gas distributor 128 . An inductive plasma source useful in the chamber 102 is described in commonly assigned U.S. patent application Ser. No. 12/780,531, entitled “Inductive Plasma Source With Metallic Shower Head Using B-Field Concentrator”, filed May 14, 2010, and incorporated herein by reference.
[0020] A heat source 130 is disposed in the enclosure 102 , spaced apart from a surface 132 of the substrate support 110 . The heat source 130 may be a radiant heat source, for example a plurality of heat lamps, which may be arranged in a bank, for example in a honeycomb pattern. A quartz window 134 is disposed between the heat source 130 and the substrate support 110 to control the radiation from the heat source 130 , for example by allowing for filters to be applied to the quartz window to filter desired wavelengths and allow other wavelengths to propagate. The quartz window 134 may protect the heat source 130 from the process environment of the chamber 100 . The substrate support 110 is shown positioned between the heat source 130 and the plasma source 120 for convenience, but such positioning is not required. For example, an annular heat source may be positioned around a periphery of the second part 106 of the enclosure 102 between the substrate support 110 and the plasma source 120 , with a quartz window or shield separating the heat source from the process environment. In the embodiment of FIG. 1 , the substrate support 110 may comprise a material that is substantially transparent to the radiation from the heat source 130 , enabling thermal processing of a substrate disposed on the surface 132 of the substrate support 110 .
[0021] A source of radicals 136 may be coupled to the chamber 100 through the process gas conduit 126 and gas distributor 128 , or through alternative access points. The source of radicals 136 may be a remote plasma source, which may be energized by RF or microwave power.
[0022] Gases are exhausted from the chamber by coupling a pumping port 150 with a vacuum source 152 . The pumping port 150 may be at any convenient location of the chamber. In the embodiment of FIG. 1 , the pumping port 150 is a pumping plenum disposed in the second portion 106 of the enclosure 102 near the surface 132 of the substrate support 110 . A substantially continuous opening 162 leads to a channel 154 that circumnavigates the chamber 100 and is connected to a vacuum conduit 156 leading to the vacuum source 152 . The pumping port may also be a round portal formed in the enclosure 102 and coupled to the vacuum source 152 by a conduit.
[0023] The plasma source 120 of FIG. 1 , as shown and described, is an inductive plasma source. In alternate embodiments, the plasma source 120 may be a capacitive plasma source such as a planar gas distributor disposed facing the substrate support 110 and generally parallel thereto. The planar gas distributor may have gas flow openings disposed through the surface of the gas distributor that faces the substrate support 110 . The gas flow openings will generally communicate with one or more gas plenums formed in the gas distributor to ensure gas flows evenly through all the openings. Thermal control channels may be interspersed with the gas flow plenums to afford heating or cooling of the gas distributor and/or gases flowing through the gas distributor. Electrical power such as RF power is coupled to the planar gas distributor, the substrate support, or both to establish an electric field between the gas distributor and the substrate support.
[0024] In another embodiment, the plasma source 120 of FIG. 1 may be a microwave or millimeter wave source. A coaxial source of long-wave radiation may be disposed in a configuration facing the substrate support 110 , with a reflector between the coaxial source and the first portion 104 of the enclosure 102 to direct the emitted radiation toward the substrate support 110 . The coaxial source may be one or more coaxial cables arranged in an antenna structure that may be a spiral shape, a boustrophedonic shape, or any desired distributed shape. A magnetron power source is typically coupled to the coaxial antenna structure to establish the radiation field.
[0025] In the embodiment of FIG. 1 , the substrate support 110 as shown and described is a pedestal-style substrate support. In an alternate embodiment, the substrate may be supported by an support ring extending inward from the second portion 106 of the enclosure between the heat source 130 and the plasma source 120 . Such an arrangement may provide more direct access to the substrate for the heat source 130 . In embodiments wherein the heat source 130 is a lamp array, a plurality of lift pins may be interspersed with the lamps and actuated by a lift pin assembly to engage the substrate and lift it above the support ring for transporation into and out of the chamber 100 .
[0026] FIG. 2 is a flow diagram summarizing a method 200 according to another embodiment. At 202 , a substrate is disposed on a substrate support in a multi-functional chamber, such as the chamber 100 of FIG. 1 . At 204 , the substrate is exposed to a plasma formed in the multi-functional chamber, and a layer is deposited on the substrate. A plasma source, which may be inductive or capacitive, disposed in the multi-functional chamber is energized with electric power, for example RF power at one or more frequencies between about 300 kHz and about 1,000 MHz, for example about 13.56 MHz. A deposition precursor gas is provided to a reaction space between the plasma source and the substrate support and activated by the plasma source. The activated precursor forms a layer on the substrate. In one embodiment, the deposition precursor is a silicon source such as silane, which forms a layer of silicon on the substrate. In another embodiment, the deposition precursor is a nitrogen source, such as nitrogen gas or ammonia, which may add nitrogen to the surface of the substrate, for example in a DPN process. In another embodiment, the deposition precursor may be a metal source or reducing gas for performing an ALD process. In general, the plasma formed in the chamber is an ion-rich plasma or a plasma having high ion density.
[0027] At 206 , the substrate is exposed to a plasma formed outside the chamber, for example in a microwave or RF chamber remote from the chamber containing the substrate. The plasma is flowed into the chamber containing the substrate, and the substrate is exposed to the plasma. The plasma may be a remote plasma, but is generally a radical-rich plasma or a plasma having high radical density and/or low ion-density. Such a plasma may be provided to perform an oxidation process to repair an oxide layer that has been exposed to an ion-reactive process previously, such as the operation 204 . Such a plasma may also be an nitrogen and fluorine containing plasma provided to perform a cleaning operation on the substrate. In some embodiments, a remote plasma may be provided to the chamber and re-activated by forming an electric field in the chamber, as in the operation 204 described above.
[0028] At 208 , a radiant heat source disposed in the multi-functional chamber is activated to perform a thermal process on the substrate. The thermal process may be performed in the presence of a reactive gas, which may be activated by a plasma source disposed in the chamber, remote from the chamber, or both. In one example, a reoxidation process may be performed by activating the radiant heat source and heating the substrate to a temperature of at least about 600° C. while providing a gas comprising oxygen radicals. Such a reoxidation process may follow a process in which the substrate is exposed to a plasma formed in the chamber, such as the operation 204 described above. In one embodiment, a DPN operation and a subsequent reoxidation operation are performed on a substrate in a single multi-functional chamber such as the chamber 100 of FIG. 1 . In another embodiment, the thermal process may be a dopant activation process performed following a plasma doping operation.
[0029] At 210 , a second layer is deposited on the substrate by forming a plasma in the multi-functional chamber. The second layer may be any layer typically formed by a plasma deposition process, include a second silicon layer, a metal oxide layer, a doped silicon layer, and the like.
[0030] While the foregoing is directed to embodiments of the invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof. | Methods and apparatus for processing semiconductor substrates are described. A processing chamber includes a substrate support with an in-situ plasma source, which may be an inductive, capacitive, microwave, or millimeter wave source, facing the substrate support and a radiant heat source, which may be a bank of thermal lamps, spaced apart from the substrate support. The support may be between the in-situ plasma source and the radiant heat source, and may rotate. A method or processing a substrate includes forming an oxide layer by exposing the substrate to a plasma generated in a process chamber, performing a plasma nitridation process on the substrate in the chamber, thermally treating the substrate using a radiant heat source disposed in the chamber while exposing the substrate to oxygen radicals formed outside the chamber, and forming an electrode by exposing the substrate to a plasma generated in the chamber. | 2 |
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