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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a gas chromatograph used for measuring component concentrations in various samples.
2. Description of the Related Art
A gas chromatograph is provided with a column for separating sample components, a carrier gas supply unit for supplying carrier gas to the column and a detector for detecting eluted components from the column, and also has an injector for injecting a sample into the carrier gas, which is placed on the upstream side of the column.
A flow controller unit for controlling a flow rate, which includes a valve and a flow-rate sensor, is installed in the carrier gas supply unit so that a carrier gas, supplied from a carrier gas inlet, is supplied to a column from the valve through the flow-rate sensor.
With respect to the carrier gas supply unit, a structure in which a carrier gas passage is formed inside a metal substrate has been proposed (see Japanese Patent Application Laid-Open No. 11-218528). In this metal substrate, only one carrier gas passage is formed.
In the case of using a packed column in which a filler has been filled up as the column, since a bleeding component from the packed column is large, upon a temperature-rise analysis (that is, a method in which the temperature of the packed column raises during analysis), a base line on the chromatogram fluctuates largely, affecting adversely on a quantitative analysis. For this reason, generally, two of the same packed columns are installed, and these are connected to respective detectors. Then, the fluctuations in the base line are cancelled by obtaining a difference between detection outputs of these detectors.
The carrier gas has been supplied to each of the packed columns from each of the corresponding carrier gas supply units.
However, generally, a gas chromatograph has a column oven having a temperature ranging from room temperature to about 400° C. and a sample vaporization chamber having a temperature of about 250° C., together with heat-generating parts, such as a detector. Hence, there is a temperature difference of 2 to 3° C. between the carrier gas passages of the two carrier gas supply units.
It has generally been known that, even if the volume flow rate of gas is constant, there is a change of 0.6% in the mass flow rate when the surrounding temperature changes by 1° C. Moreover, the temperature coefficient of the flow-rate sensor is about 0.4%/° C. For this reason, a difference in a level of 2 to 3% occurs between the carrier-gas flow rates of the two carrier gas passages due to the above-mentioned temperature difference of 2 to 3° C. Consequently, base-line fluctuations occur in the chromatogram, resulting in adverse effect on the quantitative analysis.
There are differences among the flow rates of carrier gases, supplied from carrier gas passages made of a plurality of flow-passage assemblies to supply gases to a plurality of packed columns due to the above-mentioned temperature difference in the passage assemblies, resulting in a base-line shift of chromatogram that affects adversely on the quantitative analysis.
There have been demands for a constant carrier-gas flow rate not only in an attempt to cancel base-line fluctuations by obtaining a difference between a pair of detectors, but also in an attempt to use a plurality of gas chromatographs under the same conditions.
Moreover, there have been the same demands in capillary columns as in packed columns.
SUMMARY OF THE INVENTION
The objective of the present invention is to make carrier gas flow rates constant in a plurality of gas chromatographs.
A gas chromatograph set of the present invention comprises a plurality of gas chromatographs and a flow passage assembly. Each of the gas chromatographs includes a column for separating sample-components, a carrier gas supply unit for supplying a carrier gas to the column, and a detector for detecting eluted components from the column. Each carrier gas supply unit comprises a carrier gas passage and a flow controller unit for controlling a flow-rate that is connected to the carrier gas passage. The flow passage assembly comprises a metal plate inside where the carrier gas passages of the gas chromatographs are formed.
In the present invention, since a plurality of carrier gas passages are formed inside the commonly-used metal plate, it is possible to eliminate a temperature difference among the carrier gas passages, and consequently to eliminate a difference in the carrier gas flow rates among the gas chromatographs.
Since the flow passage assembly is shared, it becomes possible to cut costs.
With respect to the kinds of gas chromatograph to which the present invention is suitably applied, those which use a packed column in which the filler is filled up are proposed.
Moreover, with respect to the usage method of a gas chromatograph to which the present invention is suitably applied, a system in which two sets of gas chromatographs are installed to make a pair, with a sample is injected into one of the gas chromatographs so that a difference of detection signals between the two detectors can be obtained, is proposed. With this system, since a difference between detection signals from the detectors of the two gas chromatographs is obtained, it becomes possible to obtain a stable base line, and consequently to carry out an accurate quantitative analysis.
The foregoing and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTIONS OF THE DRAWINGS
FIG. 1 is a flow passage drawing that schematically shows one embodiment;
FIG. 2 is a plan view that shows a carrier gas supply unit in the embodiment;
FIG. 3 is a plan view that shows a positional relationship between elements such as valves and flow passages inside a substrate in the carrier gas supply unit; and
FIG. 4 , consisting of FIGS. 4(A) to 4(C) , is a plan view that shows a metal plate that forms a flow passage assembly in the carrier gas supply unit.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 schematically shows one embodiment. Two sets of gas chromatographs are provided. In one of the gas chromatographs, a carrier gas supply unit, which supplies a carrier gas to a column 10 - 1 through an injection port 8 - 1 , is provided with a valve 2 - 1 that is connected to a carrier gas inlet, a flow-rate sensor 4 - 1 placed on the downstream side of the valve 2 - 1 and a pressure sensor 6 - 1 . The valve 2 - 1 is feed-back controlled based upon a detection signal from the flow-rate sensor 4 - 1 so as to fix the flow rate to a predetermined value.
The other gas chromatograph also has the same structure, and a carrier gas supply unit, which supplies a carrier gas to a column 10 - 2 through an injection port 8 - 2 , is provided with a valve 2 - 2 that is connected to a carrier gas inlet, a flow-rate sensor 4 - 2 placed on the downstream side of the valve 2 - 2 and a pressure sensor 6 - 2 . The valve 2 - 2 is also feed-back controlled based upon a detection signal from the flow-rate sensor 4 - 2 so as to fix the flow rate to a predetermined value.
Carrier gas passages of the two carrier gas supply units constitute a flow passage assembly 14 in which the respective carrier gas passages are formed inside of a common single substrate made of metal having superior heat conductivity. The valves 2 - 1 and 2 - 2 , the flow-rate sensors 4 - 1 and 4 - 2 and the pressure sensors 6 - 1 and 6 - 2 are attached to the metal substrate of the flow passage assembly 14 , and are respectively connected to the respective carrier gas passages.
Detectors 12 - 1 and 12 - 2 , which respectively detect eluted components, are connected to the columns 10 - 1 and 10 - 2 on the downstream side.
A flow controller unit is constituted by valves 2 - 1 and 2 - 2 and flow-rate sensors 4 - 1 and 4 - 2 .
In this gas chromatograph set, the two gas chromatographs may be used as independent gas chromatographs, respectively. Moreover, in the case of one of them being used as a reference system in an attempt to suppress fluctuations in the base line, a sample is injected into only one of the injection ports 8 - 1 and 8 - 2 so that a difference in the detection signals from the two detectors can be obtained.
FIGS. 2 to 4 specifically show a carrier gas supply unit in this embodiment.
FIG. 2 is a plan view in which carrier gas inlet connectors 16 - 1 and 16 - 2 , valves 2 - 1 and 2 - 2 , flow-rate sensors 4 - 1 and 4 - 2 and pressure sensors 6 - 1 and 6 - 2 are placed and secured onto a metal substrate of the flow passage assembly 14 . Reference numerals, 18 - 1 a and 18 - 2 a, respectively represent carrier gas outlets of the respective carrier gas supply units. Two holes 38 , formed on both sides of each of alignments of the carrier gas outlets 18 - 1 a and 18 - 2 a, are used for securing a block (not shown) that introduces a carrier gas toward the downstream side.
As indicated by broken lines in FIG. 3 , the carrier gas passages are formed inside the metal substrate of the flow passage assembly 14 , and are connected to carrier gas inlet connectors 16 - 1 and 16 - 2 , valves 2 - 1 and 2 - 2 , flow-rate sensors 4 - 1 and 4 - 2 and pressure sensors 6 - 1 and 6 - 2 that are secured to the substrate, through inlet/outlet holes formed on the substrate surface. One of the carrier gas passages is connected to the carrier gas outlet 18 - 1 from the carrier gas inlet connector 16 - 1 through the flow-rate sensor 4 - 1 via the valve 2 - 1 , and the pressure sensor 6 - 1 is connected to the carrier gas passage in the middle of the passage. In the same manner, the other carrier gas passage is connected to the carrier gas outlet 18 - 2 from the carrier gas inlet connector 16 - 2 passing through the flow-rate sensor 4 - 2 via the valve 2 - 2 , and the pressure sensor 6 - 2 is connected to the carrier gas passage in the middle of the passage.
Referring to FIG. 4 , the flow passage assembly 14 is explained.
The flow passage assembly is constituted by three metal plates, that is, an upper plate 14 a, a middle plate 14 b and a lower plate 14 c, and is arranged so that the upper plate 14 a is placed on the upper side and the lower plate 14 c is placed on the lower side, with the middle plate 14 b being placed in between; thus, these plates are integrally joined to one another.
The two carrier gas passages are formed in the middle plate 14 b as grooves that penetrate the plate in the thickness direction. One of the carrier gas passages is provided with three flow passage grooves 22 - 1 , 28 - 1 and 36 - 1 . One end of the flow passage groove 22 - 1 forms an inlet hole 20 - 1 b . The other end 24 - 1 b of the flow passage groove 22 - 1 is adjacent to one end 26 - 1 b of the flow passage groove 28 - 1 , and the valve 2 - 1 is connected between the two ends 24 - 1 b and 26 - 1 b . The other end 30 - 1 b of the flow passage groove 28 - 1 and an end 34 - 1 b of a flow passage branched from the middle of the flow passage groove 28 - 1 are adjacent to one end 32 - 1 b of the flow passage groove 36 - 1 so that the flow-rate sensor 4 - 1 is connected among the three ends 30 - 1 b , 32 - 1 b and 34 - 1 b . The other end of the flow passage groove 36 - 1 serves as a carrier gas outlet 18 - 1 b . The pressure sensor 6 - 1 is connected to a groove end 29 - 1 b of a branched flow passage groove from the flow passage groove 28 - 1 .
In the same manner, the other carrier gas passage is provided with three flow passage grooves 22 - 2 , 28 - 2 and 36 - 2 . One end of the flow passage groove 22 - 2 forms an inlet hole 20 - 2 b. The other end 24 - 2 b of the flow passage groove 22 - 2 is adjacent to one end 26 - 2 b of the flow passage groove 28 - 2 , and the valve 2 - 2 is connected to the two ends 24 - 2 b and 26 - 2 b in between. The other end 30 - 2 b of the flow passage groove 28 - 2 and an end 34 - 2 b of a flow passage branched from the middle of the flow passage groove 28 - 2 are adjacent to one end 32 - 2 b of the flow passage groove 36 - 2 so that the flow-rate sensor 4 - 2 is connected among the three ends 30 - 2 b, 32 - 2 b and 34 - 2 b. The other end of the flow passage groove 36 - 2 serves as a carrier gas outlet 18 - 2 b. The pressure sensor 6 - 2 is connected to a groove end 29 - 2 b of a branched flow passage groove from the flow passage groove 28 - 2 .
The upper plate 14 a to be superposed on the upper face of the middle plate 14 b is provided with through holes 20 - 1 a, 20 - 2 a, 24 - 1 a, 24 - 2 a, 30 - 1 a, 30 - 2 a, 32 - 1 a, 32 - 2 a, 18 - 1 a, 18 - 2 a, 29 - 1 a, 29 - 2 a, 34 - 1 a and 34 - 2 a formed therein at positions that respectively correspond to the respective ends of the flow passage grooves in the middle plate 14 b, that is, 20 - 1 b, 20 - 2 b, 24 - 1 b, 24 - 2 b, 30 - 1 b, 30 - 2 b, 32 - 1 b, 32 - 2 b, 18 - 1 b, 18 - 2 b, 29 - 1 b, 29 - 2 b, 34 - 1 b and 34 - 2 b, when the upper plate 14 a is positioned on the middle plate 14 b so as to be superposed thereon.
The lower plate 14 c to be superposed on the lower face of the middle plate 14 b is provided with no through holes at positions corresponding to the flow passage grooves of the middle plate 14 b in a manner so as to close the lower face side of the flow passage grooves of the middle plate 14 b.
The upper plate 14 a , middle plate 14 b and lower plate 14 c are respectively provided with through holes 38 a , 38 b and 38 c for attaching the inlet connectors 16 - 1 and 16 - 2 , the valves 2 - 1 and 2 - 2 , the flow-rate sensors 4 - 1 and 4 - 2 , the pressure sensors 6 - 1 and 6 - 2 , and a block used for directing carrier gases toward the downstream side (not shown in the Figure), and these through holes 38 a , 38 b and 38 c are formed at positions that are made corresponding with one another when the upper plate 14 a , the middle plate 14 b and the lower plate 14 c are positioned and respectively superposed.
The upper plate 14 a, the middle plate 14 b and the lower plate 14 c, shown in FIG. 4 , are positioned and superposed on one another, and joined to each other to form an integral substrate serving as the flow passage assembly 14 with flow passages formed therein, and the inlet connectors 16 - 1 and 16 - 2 , the valves 2 - 1 and 2 - 2 , the flow-rate sensors 4 - 1 and 4 - 2 , and the pressure sensors 6 - 1 and 6 - 2 are then attached onto the upper plate 14 a; thus, the carrier gas supply unit is formed.
In accordance with this carrier gas supply unit of the present embodiment, in the first carrier gas passage, carrier gas, directed through the carrier gas inlet 16 - 1 , is directed to the valve 2 - 1 through the flow passage 22 - 1 inside the substrate of the flow passage assembly 14 , and from the valve 2 - 1 , the gas is again directed to the flow-rate sensor 4 - 1 through the flow passage 28 - 1 inside the substrate. The carrier gas that has passed through the flow-rate sensor 4 - 1 is again directed to the carrier gas outlet 18 - 1 through the flow passage 36 - 1 inside the substrate, and supplied to the injection port 8 - 1 therefrom. Moreover, the gas is also directed to the pressure sensor 6 - 1 from the middle point of the flow passage 28 - 1 so as to detect the pressure.
The second carrier gas passage also has the same structure, and carrier gas directed through the carrier gas inlet 16 - 2 is directed to the valve 2 - 2 through the flow passage 22 - 2 inside the substrate, and from the valve 2 - 2 , the gas is again directed to the flow-rate sensor 4 - 2 through the flow passage 28 - 2 inside the substrate. The carrier gas that has passed through the flow-rate sensor 4 - 2 is again directed to the carrier gas outlet 18 - 2 through the flow passage 36 - 2 inside the substrate, and supplied to the injection port 8 - 2 therefrom. Moreover, the gas is also directed to the pressure sensor 6 - 2 from the middle point of the flow passage 28 - 2 so as to detect the pressure.
In the respective carrier gas passages, the flow rates are measured by the respective flow-rate sensors 4 - 1 and 4 - 2 so that the valves 2 - 1 and 2 - 2 are feed-back controlled so as to set predetermined flow rates.
Since the first and second carrier gas passages are formed inside the common metal substrate of the flow passage assembly 14 , the two carrier gas passages are always maintained at the same temperature. Consequently, a sample is injected into the injection port of one of the gas chromatographs with the other chromatograph having no sample injected therein, and an analysis is carried out in this state so as to obtain a difference between the detectors of the two gas chromatographs; thus, it becomes possible to suppress fluctuations in the base line.
A method of manufacturing the flow passage assembly 14 will be described.
The metal plates 14 a, 14 b and 14 c are made of metal having high thermal conductivity, and preferable material examples include stainless steel and iron, with a preferable thickness in a range of 0.2 to 1 mm.
Onto the metal plates 14 a, 14 b and 14 c, the passage grooves and the through holes are formed through etching or stamping processes. The metal plates 14 a, 14 b and 14 c are joined to one another through pressure welding. Specifically, the pressure welding refers to a process in which metal plates are pressed so as to be integrally welded by applying a pressure of about 10 MPa in a high-temperature atmosphere of no less than 800° C.
Although the embodiments have exemplified a structure in which carrier gas flow passages of two gas chromatographs are formed by a common flow passage assembly, carrier gas flow passages of three or more gas chromatographs may be formed by a common flow passage assembly.
The gas chromatograph of the present invention can be utilized to quantity-measure component concentrations in a sample in various fields, such as chemical, biochemical, environmental and medical fields.
Although the present invention has been described and illustrated in detail, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, the spirit and scope of the present invention being limited only by the terms of the appended claims. | A gas chromatograph set of the present invention comprises a plurality of gas chromatographs and a flow passage assembly. Each of the gas chromatographs includes a column for separating sample-components, a carrier gas supply unit for supplying a carrier gas to the column and a detector for detecting eluted components from the column. The carrier gas supply unit comprises a carrier gas passage, and a flow controller unit for controlling a flow-rate that is connected to the carrier gas passage. The flow passage assembly comprises a metal plate inside which the carrier gas passages of the gas chromatographs are formed. | 6 |
CROSS-REFERENCES TO RELATED APPLICATIONS
This nonprovisional application claims priority under 35 U.S.C. § 119(a) on Patent Application No. 2001-329938 filed in Japan on Oct. 26, 2001, the entirety of which is herein incorporated by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a V-type internal combustion engine capable of draining liquid, e.g., such as rainwater pooled within a space formed in a V-shaped bank of the internal combustion engine, and more particularly to a V-type internal combustion engine having a crankshaft oriented in a substantially horizontal direction.
2. Description of the Background Art
In a V-type internal combustion engine having a crankshaft oriented in a substantially horizontal direction, e.g., for example as seen in JP-U-62-69029, the entirety of which is hereby incorporated by reference, a coolant pump is disposed on one end surface of the internal combustion engine at a position adjacent to the V-shaped bank of cylinders. Rainwater falling from above pools within the space formed in the V-bank and is difficult to removed or drained therefrom.
In the case of an internal combustion engine to be mounted on a motorcycle, when the engine is exposed to the elements and rain falls thereon, a drive unit of a dynamic valve system and a generator are disposed at the V-bank on both sides of the internal combustion engine. Accordingly, liquid such as rainwater cannot be drained and may tend to pool and eventually cause damage to the surrounding components.
SUMMARY OF THE INVENTION
The present invention overcomes the shortcomings associated with the background art and achieves other advantages not realized by the background art.
An object of the present invention is to provide a v-type internal combustion engine in which the disadvantages of the background art are overcome and/or reduced.
One or more of these and other objects are accomplished by a V-block internal combustion engine comprising a crankshaft orientated in a substantially horizontal direction; a V-block cylinder block opening upwardly with respect to the horizontal direction of the crankshaft; a V-shaped valley being formed within an upper portion of the V-block cylinder block; a cover for covering an end surface of the internal combustion engine with respect to a direction of the crankshaft; a drainage channel for draining liquid pooling in the V-shaped valley; wherein the V-shaped valley is formed in the cover.
One or more of these and other objects are further accomplished by an internal combustion engine comprising at least four cylinders and four pistons of the engine operatively engaged in a four cycle arrangement; a crankcase; a crankshaft orientated in a substantially horizontal direction; a V-block, cylinder block opening upwardly with respect to the horizontal direction of the crankshaft and being connected to an upper end surface of the crankcase; a V-shaped valley being formed within an upper portion of the V-block cylinder block; a cover for covering an end surface of the internal combustion engine with respect to a direction of the crankshaft; a drainage channel for draining liquid pooling in the V-shaped valley; wherein the V-shaped valley is formed in the cover; an oil pan connected on a lower end surface of the crankcase; a pair of left and right cylinder heads; a front cover being connected to a front face of the crankcase and V-block cylinder block; and a rear cover being connected to a rear face of the crankcase and the V-block, cylinder block.
One or more of these and other objects are further accomplished by a method of preventing a collection of water in the V-shaped valley of either of the aforementioned internal combustion engines, the method comprising the steps of draining liquid accumulating within the V-shaped valley being formed within the upper portion of the V-block cylinder block; and guiding the liquid through the drainage channel to a position external to the internal combustion engine.
Since liquid such as rainwater fallen from above to the aforementioned V-type internal combustion engine is drained out of the internal combustion engine through the V-shaped valley, the V-type internal combustion engine is prevented from rusting and/or contamination from foreign liquids and matter. Therefore, corrosion or dirt is prevented from occurring at the V-shaped bank valley of the aforementioned V-type internal combustion engine. Even when corrosion or dirt occurs in the aforementioned drainage channel, it cannot be viewed from the outside, and a desirable overall appearance is maintained.
According to additional aspects of the claimed invention discussed in greater detail hereinafter, the aforementioned drainage channel is isolated from the internal space of the internal combustion engine inwardly with the front cover. Liquid pooled in the aforementioned V-shaped bank valley and drained therefrom will never mix with engine oil or the like. Since the aforementioned drain port faces sideways and obliquely downward of the internal combustion engine, drained liquid will never flow downward along the side surface of the internal combustion engine. In addition, the drainage channel does not impair the appearance because it is provided at an indistinctive position. When the crankshaft is mounted in the direction of travel of a compact vehicle such as a motorcycle, the arrangement is even more effective because the aforementioned drain port cannot be viewed from the front.
When the aforementioned drainage channel does not require a specific member for forming the drainage channel, the number of the components can be reduced and thus the costs can be reduced. In addition, since the communication passage introducing liquid downward from the upper portion of the internal combustion engine is laid along the outlet passage of the water pump, the outlet passage of the water pump feeding coolant from the lower portion of the internal combustion engine toward the respective cylinder on the upper portion of the internal combustion engine does not interfere with the aforementioned communication passage.
Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood from the detailed description given hereinafter and the accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention, and wherein:
FIG. 1 is a front view of a V-type, four cylinder, four cycle internal combustion engine according to an embodiment of the present invention;
FIG. 2 is a vertical, cross sectional view taken along the line II—II in FIG. 1;
FIG. 3 is a frontal, cross sectional view taken along the line III—III in FIG. 2;
FIG. 4 is a plan, cross sectional view taken along the line IV—IV in FIG. 1;
FIG. 5 is a front view of a front cover according to an embodiment of the present invention; and
FIG. 6 is a rear view of a coolant pump cover according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will hereinafter be described with reference to the accompanying drawings. FIG. 1 is a front view of a V-type, four cylinder, four cycle internal combustion engine according to an embodiment of the present invention. FIG. 2 is a vertical, cross sectional view taken along the line II—II in FIG. 1 . FIG. 3 is a frontal, cross sectional view taken along the line III—III in FIG. 2 . FIG. 4 is a plan, cross sectional view taken along the line IV—IV in FIG. 1 . FIG. 5 is a front view of a front cover according to an embodiment of the present invention. FIG. 6 is a rear view of a coolant pump cover according to an embodiment of the present invention. In the following discussion of the accompanying drawings, the terms “on, up and down, left and right, and front and rear” refer to directions of orientation with respect to and as viewed on the basis of the motorcycle to which an engine 1 is mounted in a preferred embodiment.
A V-type, four cylinder, four stroke (cycle) internal combustion engine 1 is mounted on a motorcycle in a preferred application of the present invention. The engine 1 includes a crankshaft 11 oriented in a fore-and-aft direction of the vehicle, e.g., a so-called vertical orientation. As shown in FIG. 2, a constant-mesh gear transmission 2 is built in a rear half of an interior of the V-type four cylinder, four stroke (cycle) internal combustion engine 1 .
As shown in FIG. 1 and FIG. 2, the main body of the aforementioned V-type, four cylinder, four cycle internal combustion engine 1 includes a crankcase 4 , an oil pan 3 connected on the lower end surface of the crankcase 4 , a cylinder block 5 connected to the upper end surface of the crankcase 4 and including a pair of left and right cylinder banks arranged in V-shape and constructed of four cylinders (not shown). The cylinders are arranged alternately on the left and the right with respect to the direction of the axis of rotation of the aforementioned crankshaft 11 . The engine 1 also includes a pair of left and right cylinder heads 6 connected respectively to the left and right cylinder banks, a pair of left and right head covers 7 connected to both of the cylinder heads 6 , a front cover 8 connected to the front face of the aforementioned crankcase 4 and the cylinder block 5 , and a rear cover 9 connected to the rear face of the crankcase 4 and the cylinder block 5 . The front cover 8 corresponds to a first cover as discussed in the remainder of this description.
As shown in FIG. 2, a front bearing holding portion 12 , an intermediate bearing holding portion 13 , and a rear bearing holding portion 14 are formed by the combination of the crankcase 4 and the cylinder block 5 integrally therewith. The crankshaft 11 is rotatably supported by the bearings held by the front bearing holding portion 12 , the intermediate bearing holding portion 13 , and the rear bearing holding portion 14 respectively. Pistons (not shown) are slidably fitted to the aforementioned cylinders and the pistons are reciprocated by intermittent combustion of an air-fuel mixture supplied into the combustion chambers of the cylinders. The reciprocating motion of the pistons rotates the crankshaft 11 counterclockwise (clockwise when viewing the V-type, four cylinder, four stroke internal combustion engine 1 from the front) via a connecting rod 15 .
The main shaft 16 is rotatably supported by the crankcase 4 at a position lower than the crankshaft 11 . An output portion of the multi plate friction speed change clutch 17 is fitted on the front end portion of the main shaft 16 projected forward from the crankcase 4 , a driven gear 19 is fitted on the input portion of the multi plate friction speed change clutch 17 , and a drive gear 18 is formed integrally with the crankshaft 11 and engages the driven gear 19 . Accordingly, a rotational torque of the crankshaft 11 is transmitted to the main shaft 16 via the multi plate friction speed change clutch 17 when the multi-plate friction speed change clutch 17 is connected.
A counter shaft 20 is rotatably supported by the crankcase 4 on the right side of the main shaft 16 , a speed change gear group 21 on the main shaft side and the speed change gear group on the counter side (not shown) are provided on the main shaft 16 and the counter shaft 20 respectively. An output gear 22 on the counter shaft 20 engages the input gear 24 on the output shaft 23 , so that one of the gears in the speed change gear group 21 on the main shaft side and one of the gears in the speed change gear group on the counter side are selectively engaged by the axial movement of any one of three shift forks (not shown) provided on the shift drive shaft (not shown) Power is transmitted from the main shaft 16 via the counter shaft 20 to the output shaft 23 at a prescribed change gear ratio. A drive shaft (not shown) oriented in the fore-and-aft direction is connected to the output shaft 23 , and the drive shaft is connected to the rear axle of the motorcycle (not shown) via a pair of bevel gears (not shown). The rear wheel is driven by the rotation of the output shaft 23 and thus the motorcycle can travel.
Further, an AC generator drive gear 25 is integrally fitted on the rear end portion of the crankshaft 11 projected rearward from the crankcase 4 and the cylinder block 5 . The AC generator drive gear 25 is connected to the input shaft of the AC generator 26 via a transmission mechanism (not shown), so that the crankshaft 11 and the AC generator 26 rotate simultaneously. The AC generator 26 is disposed at a valley, space or recess formed on the rear portion of the V-bank of the V-type, four cylinder, four stroke (cycle) internal combustion engine 1 .
A drive sprocket 27 of the dynamic valve system (not shown) is disposed at the front portion of the crankshaft 11 projected forwardly from the front bearing holding portion 12 and at a position rearward of the drive gear 18 . As shown in FIG. 1, a cam shaft 10 is rotatably supported at a mating surface between the cylinder head 6 and the head cover 7 . An endless chain is routed between the driven sprocket that is built in the cam shaft 10 and the drive sprocket 27 , so that the cam shaft 10 is rotated at half the rotational speed of the crank shaft 11 in accordance with the rotation of the crankshaft 11 .
In addition, as shown in FIG. 2 and FIG. 3, the cylinder block 5 is formed with a cam chain chamber 28 in which the aforementioned endless chain can be forwarded. As shown in FIG. 3, the bottom wall 29 of the V-bank is formed in such a manner that the portion near the widthwise center of the cylinder block 5 is the lowest. As shown in FIG. 2, the front part of the bottom wall 29 of the V-bank is slightly inclined downward (when the mating surface between the crankcase 4 and the cylinder block 5 is oriented horizontally) in comparison with the rear portion of the bottom wall 29 of the V-bank and with respect to a direction of the crankshaft 11 . Therefore, rainwater falling on the V-bank of the cylinder block 5 flows forward from the rear portion of the bottom wall 29 of the V-bank.
As shown in FIG. 2, a wall 31 of the cam chain chamber extending vertically downward and forming the front wall of the cam chain chamber 28 is formed integrally with the rear end of the contact portion 30 that comes into contact with the upper portion of the front cover 8 . The lower portion of the wall 31 of the cam chain chamber is formed with a communication hole 32 in contact with the upper surface of the bottom wall 29 of the V-bank, and a vertically elongated cylindrical portion 33 in front view in contact with the upper portion of the communication hole 32 is formed so as to project forwardly from the wall 31 of the cam chain chamber.
As shown in FIG. 5, the front cover 8 is formed of a set back recess 34 . The set back recess 34 is recessed rearward, on the upper left portion thereof from the border line extending obliquely from the position below the cylindrical portion 38 (which will be described hereinafter) toward the obliquely upper right when viewed from the front (obliquely upper left when viewed on the basis of the vehicle body). The set back recess 34 then extends vertically downward from a position slightly offset leftward and downward from the position below the aforementioned cylindrical portion 33 . The recess 34 then inclines toward the obliquely lower left from a position immediately above the multi plate friction speed change clutch 17 . A pump hole 35 is formed on the set back recess 34 at a lower position on the front face thereof, and coolant outlet ports 36 are formed on the set back recess 34 at the upper left and right positions thereof. Further, a shallow groove 37 is formed on the front face of the set back recess 34 so as to extend from the pump hole 35 toward the coolant outlet ports 36 .
A cylindrical portion 38 having the same cross section as the vertically elongated cylindrical portion 33 projecting forward from the wall 31 of the cam chain chamber of the cylinder block 5 is provided on the upper inner surface (rear surface) of the front cover 8 so as to project toward the rear. A lead-in path 39 is defined by the cylindrical portions 33 , 38 , and a communication hole 40 communicating with the bottom of the cylindrical portion 38 and the outer portion of the front cover 8 is provided on the front cover 8 .
A coolant pump cover 41 , which corresponds to the second cover referred to hereinafter in the remainder of this description, for covering the set back recess 34 on the front cover 8 so as to be flush with the front surface of the front cover 8 is provided as shown in FIG. 6 . The coolant pump cover 41 is formed with a spiral recess 43 and the coolant passage 44 of the coolant pump 42 at the position corresponding to the groove 37 of the front cover 8 . The casing of the coolant pump 42 is formed by bolts to be passed through the bolt holes 45 on the coolant pump cover 41 and screwed into the bolt holes 46 on the front cover 8 . A pump rotor (not shown) is inserted into and rotatably supported by the spiral recess 43 on the aforementioned coolant pump cover 41 from the front toward the rear, and the pump rotor is connected to the crankshaft 11 via a transmission mechanism such as a belt or the like, not shown.
As shown in FIG. 4, the coolant pump cover 41 is formed with a thermostat chamber 47 at the position forward of the spiral recess 43 . The thermostat chamber 47 is connected with the inlet pipe joint 48 and a bypass pipe joint 49 . The thermostat chamber 47 accommodates a thermostat (not shown) and the inlet pipe joint 48 is connected to the radiator (not shown) via a hose (not shown). The bypass pipe joint 49 is connected to the coolant exit (not shown) of the V-type, four cylinder, four stroke (cycle) internal combustion engine 1 via a hose (not shown). The aforementioned coolant outlet port 36 is connected to the coolant passage 50 (See FIG. 3) of the V-type, four cylinder, four stroke (cycle) internal combustion engine 1 .
As shown in FIG. 4, the coolant pump cover 41 is formed in such a manner that the side edge 53 of the front plate portion 52 of the coolant pump cover 41 can be brought into intimate contact with the side wall 51 of the set back recess 34 of the front cover 8 . A communication passage 56 is defined by the wall 54 and the side wall 51 of the set back recess of the front cover 8 and the front plate portion 52 and the side wall 55 of the coolant pump cover 41 .
Since the embodiment shown in the figure is constructed as described above, the following operation is performed. When the V-type internal combustion engine 1 starts and the crankshaft 11 rotates, the pump rotor of the coolant pump 42 is rotated. Since the coolant is cold during startup, the thermostat (not shown) closes the water passage leading to the inlet pipe joint 48 and opens the water passage leading to the bypass pipe joint 49 .
Therefore, coolant is drawn from the coolant passage 50 into the V-type internal combustion engine 1 via the hose and the bypass pipe joint 49 into the coolant passage 44 of the coolant pump 42 . After being pressurized, coolant flows through the coolant passage 44 and the coolant outlet port 36 into the coolant passage 50 . Accordingly, localized overheating is avoided in the V-type 4 cylinder 4 stroke cycle internal combustion engine 1 by the circulation of coolant. When coolant is heated to a value exceeding a prescribed temperature, a thermostat (not shown) is actuated, and the water passage led to the bypass pipe joint 49 is closed, and the water passage led to the inlet pipe joint 48 is opened.
Therefore, coolant heated in the engine 1 is fed to the radiator (not shown) and cooled therein. Coolant is then cooled and drawn into the spiral recess 43 of the coolant pump 42 via the hose (not shown) and the inlet pipe joint 48 and pressurized therein. Coolant then flows back to the coolant passage 50 in the engine 1 via the coolant passage 44 and the coolant outlet port 36 , so that the engine 1 can be kept at proper temperatures.
When the motorcycle (not shown) travels in rain or other foul weather, and rainwater falls on the V-type, four cylinder internal combustion engine 1 , rainwater pools on the bottom wall 29 of the V-bank of the engine 1 . The rainwater flows forward along the bottom wall 29 of the V-bank inclined downward toward the front, and passes through the communication hole 32 on the wall 31 of the cam chain chamber. The water then flows into the lead-in path 39 defined by the cylindrical portion 33 and the cylindrical portion 38 .
The lower edge 53 of the front plate portion 52 of the coolant pump cover 41 is in contact with the side wall 51 of the set back recess 34 of the front cover 8 in a watertight manner (a packing or the like may be interposed as necessary). The communication passage 56 is defined by the side wall 51 of the set back recess 34 and the wall 54 of the set back recess on the front cover 8 and the front plate portion 52 and the side wall 55 of the coolant pump cover 41 . The communication passage 56 is inclined toward the lower left in front view (lower right when viewed on the basis of the vehicle body) along the side wall 51 of the set back recess 34 of the front cover 8 . Accordingly, rainwater introduced into the lead-in path 39 flows through the communication hole 40 into the communication passage 55 and then flows obliquely downward in the communication passage 55 . Water is then drained from the opening 57 between the lower end portion of the side wall 51 of the set back recess 34 on the front cover 8 and the peripheral wall 54 of the coolant pump 42 toward the outside of the vehicle.
Generally, when the motorcycle is traveling, rainwater drained from the opening 57 flows rearward of the vehicle body, e.g., as a mist due to wind blown while the vehicle is moving. Therefore, the water rarely adheres on the crankcase 4 , the cylinder block 5 , the cylinder head 6 and the body of the V-type engine 1 . Accordingly, contamination of the crankcase 4 , cylinder block 5 , the cylinder head 6 , and the like due to rain may be avoided. Since the bottom wall 29 of the V-bank inclines downward toward the front, rainwater falling on the bottom wall 29 of the V-bank does not pool on the bottom wall 29 of the V-bank, but is instead drained to the outside of the engine, even when the vehicle is stopped. In addition, since the communication passage 56 is formed along the coolant passage 44 of the coolant pump 42 , the coolant passage 44 does not interfere with the communication passage 56 .
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 as would be obvious to one skilled in the art are intended to be included within the scope of the following claims. | In a V-type internal combustion engine having a crankshaft oriented in a substantially horizontal direction, drainage channels for draining liquid such as rainwater pooling within a recess formed within the V-shaped of the engine are formed in covers for covering the end surface of the internal combustion engine in an axial direction of the crankshaft. Accordingly, liquid such as rainwater pooling on the V-shaped bank of the V-type internal combustion engine is advantageously drained from the engine with the present apparatus and methods. | 5 |
BACKGROUND OF THE INVENTION
Imidazolylcyanoguanidines in which the imidazole and cyanoguanidine are joined through a linear connecting group are known as H-2 receptor inhibitors. See U.S. Pat. No. 3,950,333 to Durant et al. In addition, compounds have been prepared similar to those of Durant et al in which the imidazole moiety has been replaced by an alkylaminoalkylfuran moiety. See U.S. Pat. No. 4,128,658 to Price et al. The instant compounds differ in utilizing the aminoalkyl benzofuran moiety.
SUMMARY OF THE INVENTION
This invention is concerned with aminoalkyl benzofuran compounds wherein the aminoalkyl benzofuran is connected to a guanidine or guanidine-like moiety through a linear connecting group. Thus, it is an object of this invention to describe such compounds. A further object of this invention is to descrbe processes for the preparation of such compounds. A still further object is to describe the use of such compounds as gastric acid secretion inhibitors in mammals. Further objects will become apparent from a reading of the following description.
DESCRIPTION OF THE INVENTION
The compounds of this invention are best realized in the following structural formula: ##STR1## wherein R 1 and R 2 are independently loweralkyl of from 1-3 carbons and R 1 and R 2 may be joined to form together with the nitrogen atom to which they are attached, a 5- or 6-membered heterocyclic ring, which may optionally contain another hetero atom selected from oxygen or N-R 4 wherein R 4 is hydrogen or loweralkyl;
X is sulfur or a methylene group;
n is 2,3 or 4;
R 3 is hydrogen loweralkyl, cycloloweralkyl, cycloloweralkylloweralkyl, loweralkenyl, loweralkynyl, phenylloweralkyl, hydroxyloweralkyl, loweralkoxyloweralkyl and di(loweralkyl)aminoloweralkyl; and
Y is sulfur, ═CHNO 2 or ═NR 4 where
R 4 is nitro, cyano or loweralkylsulfonyl.
In the instant invention, the term "loweralkyl" unless otherwise defined is intended to include those alkyl groups, of either a straight or branched configuration, which contain from 1-5 carbon atoms. Exemplary of such alkyl groups are methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, pentyl and the like.
The term "loweralkoxy" is intended to include those alkoxy groups of either straight or branched configuration, which contain from 1-5 carbon atoms. Exemplary of such alkoxy groups are methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentoxy and the like.
The term "loweralkenyl" is intended to include those alkenyl groups, of either a straight or branched configuration, which contain from 2-5 carbon atoms. Exemplary of such alkenyl groups are vinyl, allyl, butenyl, 1-methyl-2-butenyl, pentenyl, and the like.
The term "loweralkynyl" is intended to include those alkynyl groups of either straight or branched configuration which contain from 2-5 carbon atoms. Exemplary of such alkynyl groups are ethynyl, propargyl, butynyl, pentynyl and the like. The heterocycle formed when R 1 and R 2 are joined may be piperidine, or pyrrolidine and the like.
The term "cycloloweralkyl" is intended to include those cycloalkyl groups which contain from 3-6 carbon atoms. Exemplary of such groups are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The heterocycle formed by joining R 1 and R 2 may be piperidine, pyrrolidine, morpholine, piperazine, N-methyl piperazine and the like.
The preferred compounds of the instant invention are realized in the above structural formula when: R 1 and R 2 are the same and are loweralkyl of from 1-3 carbon atoms;
X is sulfur;
n is 2;
R 3 is hydrogen, loweralkyl or loweralkynyl and
Y is ═CHNO 2 , or ═N--CN;
Further preferred compounds are realized when;
R 1 and R 2 are methyl;
X is sulfur;
n is 2;
R 3 is hydrogen, methyl, ethyl, or propargyl; and
Y is ═CH--NO 2 or ═N--CN.
The most preferred compounds are those wherein:
R 1 and R 2 are methyl;
X is sulfur;
n is 2;
R 3 is hydrogen or methyl; and
Y is ═CH--NO 2 or ═N--CN.
The compounds according to the invention readily form physiologically acceptable salts. Such salts include salts with inorganic and organic acids such as hydrochlorides, hydrobromides and sulphates. Particularly useful salts of organic acids are formed with aliphatic mono- or di-carboxylic acids. Examples of such salts are acetates, maleates and fumarates. The compounds may also form hydrates.
The compounds according to the invention can be administered orally, topically or parenterally or by suppository, of which the preferred route is the oral route. They may be used in the form of the base or as a physiologically acceptable salt. They will be in general be associated with a pharmaceutically acceptable carrier or diluent, to provide a pharmaceutical composition.
The compounds according to the invention can be administered in combination with other active ingredients, e.g. conventional antihistamines if required. For oral administration the pharmaceutical composition can most conveniently be in the form of capsules or tablets, which may be slow release tablets. The composition may also take the form of a dragee or may be in syrup form. Suitable topical preparation include ointments, lotions, creams, powders and sprays.
A convenient daily dose by the oral route would be of the order of 100 mg. to 1.2 g. per day, in the form of dosage units containing from 20 to 200 mg. per dosage unit. A convenient regimen in the case of a slow release tablet would be twice or three times a day.
Parenteral administration may be by injection at intervals or as a continuous infusion. Injection solutions may contain from 10 to 100 mg./ml. of active ingredient.
For topical application a spray, ointment, cream or lotion may be used. These compositions may contain an effective amount of the active ingredient, for example of the order of 11/2 to 2% by weight of the total composition.
The compounds of the present invention may be made by reacting a primary amine of the formula: ##STR2## in which R 1 , R 2 , n, and X have the meanings given herein with a compound capable of introducing directly or indirectly the group: ##STR3## in which R 3 and Y have the meanings given herein. Compounds which are capable of directly introducing the group: ##STR4## are, isothiocyanates R 3 NCS, or compounds of the formula: ##STR5## wherein P is a leaving group. The reaction with the isothiocyanate may be carried out by allowing the amine and isothiocyanate to stand in a solvent such as acetonitrile. The reaction between the amine (II) and: ##STR6## may be carried out in a solvent e.g. ethanol or acetonitrile at ambient or elevated temperatures in the presence of silver nitrate as required. The amine (II) and the compound. ##STR7## may be stirred in solvents such as ethanol and acetonitrile at ambient or elevated temperatures. Where R 3 represents hydrogen, alkali metal cyanates and thiocyanates are used. Examples of leaving groups are halogen, methylthio or alkoxy, preferably methylthio. The introduction of the group: ##STR8## may also be effected indirectly by first reacting the amine (II) with a compound of the formula: ##STR9## in which P is a leaving group as defined above. This reaction may be effected in a solvent, e.g. ether or acetonitrile at a temperature from ambient to reflux. Treatment of the resulting compound of formula (III): ##STR10## where Y represents ═NR 4 or ═CH--NO 2 with a primary amine R 3 NH 2 at a temperature from ambient to reflux gives the desired end product.
The preferred compounds of this invention wherein Y is a nitromethylene group (═CHNO 2 ) or a cyanoimino group (═N--CN) are prepared according to the following reaction scheme: ##STR11## wherein R 1 , R 2 , R 3 , n and X are as defined above.
In the first step of the reaction for the preparation of the nitromethylene compound (I-A), the amine starting material (II) is treated with 1,1-bis-methylthio-2-nitroethene in a suitable solvent, preferably acetonitrile or a lower alcohol, such as ethanol. The reaction may be carried out at about 20° C. to the reflux temperature of the reaction mixture. The reaction is substantially complete in about 8 hours to several days. It is preferred to stir the reaction mixture overnight at about 55°-60° C.
In the first step of the reaction for the preparation of cyanoimino compound (I-B) the amine starting material (II) is reacted with dimethyl cyanodithioimidocarbonate in a suitable solvent, preferably acetonitrile or a lower alcohol, such as ethanol. The reaction may be carried out at about 20° C. to the reflux temperature of the reaction mixture. The reaction is substantially complete in about 1 hour to several days. It is preferred to stir the reaction mixture overnight at about room temperature.
The next step of this reaction sequence is the same for Compounds IVA and IVB and involves the displacement of the methylthio group of Compound IVA and IVB by a loweralkylamino group. A loweralkyl amine is employed and the reaction is carried out by dissolving the amine in a solvent, such as a lower alcohol, preferably ethanol. The reaction is carried out at from 0° C. to the reflux temperature of the reaction mixture. However, where volatile amines are employed the reaction mixture must either be maintained at from 0° C. to room temperature or, if heating is required, the reaction must be placed in a sealed reaction vessel. It is preferred to use atmospheric pressure for the reaction, and to keep the temperature at about room temperature or less. The reaction is complete in about 1 hour to several days, with most reactions requiring stirring overnight. The products (I-A and I-B) are isolated using techniques known to those skilled in this art.
The starting materials (II) wherein X is sulfur are prepared according to the following reaction scheme: ##STR12##
In the above reaction scheme, methylbenzofuran-2-carboxylic acid is esterified using ethanol in the presence of acid to prepare the ethyl ester derivative thereof. The preferred acid is a mineral acid such as sulfuric. The reaction is carried out generally at reflux for from 12 to 36 hours, using ethanol as the solvent.
The methyl group is brominated with a brominating agent, preferably a free radical brominating agent such as N-bromosuccinimide in the presence of a free radical initiator such as α,α'-azobisisobutyronitrile used in catalytic amounts. The reaction is carried out at from 35° C. to the reflux temperature of the reaction mixture and is generally complete in from 2 to 8 hours. An inert solvent, immune to bromination, such as carbon tetrachloride, is employed.
The brominated compound is then treated with an amine to produce the aminomethyl side chain. The reaction is carried out in an inert solvent such as ether, tetrahydrofuran, and the like. The amine reagent is employed in excess, or a separate non-reactive base such as a tertiary amine, is employed to neutralize the liberated hydrogen bromide. The reaction is carried out at from 0° to 30° C. and is generally complete in from 0.5 to 3 hours.
The 2-position ester is then reduced to the hydroxymethyl group using a reducing agent, such as lithium aluminum hydride, lithium borohydride and the like. The reaction is carried out in a solvent immune to reduction such as ether, tetrahydrofuran, and the like. The reaction is carried out at about 5° to 37° C. and generally is complete in from 1 to 3 hours.
The 2-hydroxymethyl benzofuran is then treated with an amino alkyl mercaptan. The reaction is carried out in the presence of acid, generally mineral acid such as concentrated hydrochloric acid at from 5° to 30° C., and is complete in from 20 to 64 hours. The product is isolated using techniques known to those skilled in the art.
The compounds (II) wherein X is a methylene group are prepared according to the following reaction scheme wherein Z is the substituent on the benzo portion of the molecule which may be undergoing reactions simultaneously with the instant synthetic scheme: ##STR13## wherein m is 4,5 or 6.
In the foregoing reaction scheme an appropriately substituted benzofuran is lithiated and then treated with a compound Br(CH 2 ) m Br where m is as defined above. The reaction is carried out in an inert solvent such as ether, tetrahydrofuran and the like. The benzofuran is added to a solution of lithium diisopropylamide in the solvent in order to prepare the 2-lithium benzofuran intermediate which is then reacted with the dibromo compound. A reaction promoter such as hexamethylphosphoramide is usually present. The reaction is generally carried out at from -20° to 20° C., preferably at about 0° C. and is complete in about 3 to 10 hours.
The bromo compound is then converted to the phthalimide with an alkali metal salt of phthalimide in a solvent such as dimethylformamide at from 20° to 60° C. preferably at room temperature, and is complete in about 12 to 30 hours.
The phthalimido derivative is then cleaved with hydrazine to prepare the amino group. The reaction is carried out at from 25° to 100° C. preferably from about 50° to 75° C., and is complete in about 2 to 24 hours. A solvent such a loweralkanol, preferably ethanol, is employed, and the product is isolated using techniques known to those skilled in the art.
An alternate procedure for the preparation of the alkylaminomethyl substituent on the benzofuran is outlined in the following reaction scheme where Z' is the 2-position substituent which may also be undergoing synthetic reactions simultaneously with the instant synthetic scheme: ##STR14## wherein R 1 and R 2 are as previously defined and R 5 is loweralkyl.
In the instant reaction the starting group is the carboxylic acid which may esterified and then converted to the amide, or the amide may be prepared directly if the substituents on the remainder of the molecule would allow.
The ester is prepared with ethanol in the presence of an acid as described in the esterification previously described.
The amide is prepared with an appropriately substituted amine and a catalytic amount of a base such as an alkali metal alkoxide. The reaction is carried out in a solvent such as a lower alkanol at from 25° to 80° C. If temperatures higher than the boiling point of the reaction mixture are called for, a pressurized vessel may be employed. The reaction is generally complete in from 12 to 36 hours.
The amide is then reduced to prepare the substituted amino methyl group. The reducing agent may be lithium aluminum hydride, borane, and the like and is carried out in a solvent such as ether, tetrahydrofuran, and the like and is generally complete in from 2 to 6 hours. The products are isolated using techniques known to those skilled in the art.
EXAMPLE 1
N-Cyano-N'-[2-(6-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-N"-methylguanidine
A. Ethyl 6-Methylbenzofuran-2-carboxylate
A solution of 6-methylbenzofuran-2-carboxylic acid (111.0 g., 0.636 mole) and concentrated sulfuric acid (4 ml.) in ethanol (1 l.) is boiled under reflux for 16 hours. About 2/3 of the solvent is removed by distillation at reduced pressure. The residue is poured into 1 l. of ice water. The oily ester is taken up in ether, washed with saturated sodium bicarbonate solution and water and dried over sodium sulfate. Distillation at reduced pressure affords 90.5 g. (70%) of ethyl 6-methylbenzofuran-2-carboxylate, b.p. 174°-176° C. (17 mm.). The product crystallizes in the receiver, m.p. 35°-42° C.
B. Ethyl 6-(bromomethyl)benzofuran-2-carboxylate
N-Bromosuccinimide (37.4 g., 0.21 mole) is added to a solution of ethyl-6-methylbenzofuran-2-carboxylate (40.8 g., 0.2 mole) and α,α'-azobisisobutyronitrile (500 mg.) in carbon tetrachloride (300 ml.). The suspension is boiled under reflux for 3 hours. It is then cooled and the succinimide removed by filtration. The carbon tetrachloride solution is washed with water and dried over sodium sulfate. The solution is then evaporated at reduced pressure. The solid residue is recrystallized from hexane to yield 47.4 g. (69%) of crystalline ethyl 6-(bromomethyl)benzofuran-2-carboxylate, m.p. 95°-102° C. NMR (CDCl 3 ): δ1.40 (3H,t,CH 3 ), 4.40(2H,q,CH 2 O), 4.58 (2H, s,CH 2 Br).
C. Ethyl 6-(dimethylaminomethyl)benzofuran-2-carboxylate
A solution of ethyl 6-(bromomethyl)benzofuran-2-carboxylate (47.0 g., 0.166 mole) in ether (75 ml.) is added during 30 minutes to a stirred solution of dimethylamine (18.9 g., 0.42 mole) in ether (100 ml.). The temperature is kept at 0°-5° C. during the addition by means of an ice bath. The mixture is then stirred for 30 minutes without being cooled. The precipitated dimethylamine hydrobromide is removed by filtration. The ether solution is extracted with 400 ml. of 5% hydrochloric acid. The aqueous solution is made basic by the addition of 40% sodium hydroxide solution. The liberated amine is taken up in ether and dried over sodium sulfate. Evaporation of the solvent leaves as an oily residue 36.2 g. (88%) of ethyl 6-(dimethylaminomethyl)benzofuran-2-carboxylate. NMR (CDCl 3 ): δ1.40 (3H, t,CH 3 CH 2 ),2.26(6H,s,CH 3 N),3.53(2H,s,CH 2 N), 4.43(2H, q, CH 2 O).
D. 6-(Dimethylaminomethyl)-2-benzofuranmethanol
Ethyl 6-(dimethylaminomethyl)benzofuran-2-carboxylate (36.1 g., 0.146 mole) in ether (150 ml.) is added dropwise during 1 hour to a stirred suspension of lithium aluminum hydride (5.5 g., 0.146 mole) in ether (150 ml.). The mixture is then cooled in an ice bath and treated successively with 5.7 ml. of water, 5.7 ml. of 15% sodium hydroxide solution and 17 ml. of water. The precipitated white solid is removed by filtration. The ether solution is evaporated to give 29.6 g. of a crystalline residue of 6-(dimethylaminomethyl)-2-benzofuranmethanol, m.p. 78.5°-80° C.
E. 2-(2-Aminoethylthiomethyl)-6-(dimethylaminomethyl)-benzofuran
6-(Dimethylaminomethyl)-2-benzofuranmethanol (28.3 g., 0.138 mole) is added to an ice-cold solution of cysteamine hydrochloride (17.2 g., 0.151 mole) in concentrated hydrochloric acid (70 ml.). The resulting solution is allowed to stand at room temperature for 45 hours. It is then cooled in an ice bath and made strongly basic by the addition of 10 N sodium hydroxide solution. The product is extracted with five portions of methylene chloride. The extracts are combined, washed with water and dried over Na 2 SO 4 . Evaporation of the solvent leaves 29.8 g. (82%) of 2-(2-aminoethylthiomethyl)-6-(dimethylaminomethyl)-benzofuran as an orange viscous oil. NMR (CDCl 3 ): δ1.70 (2H, br s, NH 2 ), 2.22 (6H, s, CH 3 N), 2.65-2.9 (4H, m, SCH 2 CH 2 N), 3.44 (2H, s, PhCH 2 N), 3.75 (2H, s, PhCH 2 S), 6.45 (1H, s, furan H).
F. N-Cyano-N'-[ 2-(6-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-S-methylisothiourea
A solution of 2-(2-aminoethylthiomethyl)-6-(dimethylaminomethyl)benzofuran (12.0 g, 0.0454 mole) and dimethyl cyanodithioimidocarbonate (7.0 g., 0.048 mole) in acetonitrile (48 ml.) is allowed to stand 2 hours at room temperature. The solvent is evaporated at reduced pressure and the viscous oily residue is chromatographed on a column of 250 g. of silica gel. Elution with 8% methanol in chloroform removes the product. There is obtained 14.6 g. (89%) of N-cyano-N'-[2-(6-dimethylaminomethyl-2-(benzofuranylmethylthio)ethyl]-S-methylisothiourea as a yellow oil which gradually crystallizes, m.p. 98°-100° C.
G. N-Cyano-N'-[2-(6-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-N"-methylguanidine
A solution of N-cyano-N'-[2-(6-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-S-methylisothiourea (8.8 g., 0.024 mole) and methylamine (31 g.) in ethanol (90 ml.) is allowed to stand at room temperature for 3 hours. The solvent is evaporated at reduced pressure. The residual oil gradually crystallizes, m.p. 62°-65° C. Two crystallizations of this product from acetonitrile-ether gives 7.0 g, (84%) of N-cyano-N'-[2-(6-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-N"-methylguanidine as white needles, m.p. 115.5°-117.5° C.
EXAMPLE 2
N-Cyano-N'-[2-(7-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-N"-methylguanidine
This compound is prepared by the series of reactions described in Example I except that in Step A 7-methylbenzofuran-2-carboxylic acid is substituted for the 6-methylbenzofuran-2-carboxylic acid used in Example 1. The compounds thus obtained are:
Step A--Ethyl 7-methylbenzofuran-2-carboxylate, b.p. 164° C./18 mm. Hg.
Step B--Ethyl 7-bromomethyl)benzofuran-2-carboxylate, m.p. 81°-83° C.
Step C--Ethyl 7-(dimethylaminomethyl)benzofuran-2-carboxylate
Step D--7-(Dimethylaminomethyl)-2-benzofuranmethanol
Step E--2-(2-Aminoethylthiomethyl)-7-(dimethylaminomethyl)benzofuran
Step F--N-Cyano-N'-[2-(7-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-S-methylisothiourea
Step G--N-Cyano-N'-[2-(7-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-N"-methylguanidine, m.p. 103.5°-105.5° C.
EXAMPLE 3
N-Cyano-N'-[2-(5-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-N"-methylguanidine
This compound is prepared by the series of reactions described in Example 1 except that in Step A 5-methylbenzofuran-2-carboxylic acid is substituted for the 6-methylbenzofuran-2-carboxylic acid used in Example 1. The compounds thus obtained are:
Step A--Ethyl 5-methylbenzofuran-2-carboxylate
Step B--Ethyl 5-(bromomethyl)benzofuran-2-carboxylate
Step C--Ethyl 5-(dimethylaminomethyl)benzofuran-2-carboxylate
Step D--5-(Dimethylaminomethyl)-2-benzofuranmethanol
Step E--2-(2-Aminoethylthiomethyl)-5l -(dimethylaminomethyl)benzofuran
Step F--N-Cyano-N'-[2-(5-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-S-methylisothiourea
Step G--N-Cyano-N'-[2-(5-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-N"-methylguanidine
EXAMPLE 4
N-Cyano-N'-[2-(4-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-N"-methylguanidine
This compound is prepared by the series of reactions described in Example 1 except that in Step A 4-methylbenzofuran-2-carboxylic acid is substituted for the 6-methylbenzofuran-2-carboxylic acid used in Example 1. The compounds thus obtained are:
Step A--Ethyl 4-methylbenzofuran-2-carboxylate
Step B--Ethyl 4-(bromomethyl) benzofuran-2-carboxylate
Step C--Ethyl 4-(dimethylaminomethyl)benzofuran-2-carboxylate
Step D--4-(Dimethylaminomethyl)-2-benzofuranmethanol
Step E--2-(2-Aminoethylthiomethyl)-4-(dimethylaminomethyl)benzofuran
Step F--N-Cyano-N'-[2-(4-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-S-methylisothiourea
Step G--N-Cyano-N'-[2-(4-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-N"-methylguanidinee
EXAMPLE 5
N-Cyano-N'-[4-(6-dimethylaminomethyl-2-benzofuranyl)-butyl]-N"-methylguanidine
A. 2-(4-Bromobutyl)benzofuran-6-carboxylic acid
n-Butyllithium solution (2.29 M in hexane, 44 ml., 0.1 mole) is added to a solution of diisopropylamine (10.1 g., 0.1 mole) in tetrahydrofuran (150 ml.) and hexamethylphosphoramide (15 ml.). The resulting solution is treated with benzofuran-6-carboxylic acid (8.1 g., 0.05 mole) and then with 1,4-dibromobutane (10.8 g., 0.05 mole) at 0° C. The mixture is stirred at 0° C. for 6 hours. It is then quenched with water, acidified with hydrochloric acid and extracted with ethyl acetate. Evaporation of the solvent gives 2-(4-bromobutyl)benzofuran-6-carboxylic acid.
B. Ethyl 2-(4-bromobutyl)benzofuran-6-carboxylate
A solution of 2-(4-bromobutyl)benzofuran-6-carboxylic acid (29.7 g., 0.1 mole) and sulfuric acid (0.5 ml.) in ethanol (200 ml.) is boiled under reflux. The solution is concentrated to 7/8 volume at reduced pressure. The residue is poured into water. The oily ester is extracted with ether. Evaporation of the solvent provides ethyl 2-(4-bromobutyl)benzofuran-6-carboxylate.
C. Ethyl 2-(4-phthalimidobutyl)benzofuran-6-carboxylate
A solution of ethyl 2-(4-bromobutyl)benzofuran-6-carboxylate (3.25 g., 0.01 mole) and potassium phthalimide (2.04 g., 0.011 mole) in dimethylformamide (25 ml.) is stirred at 25°-27° C. for 18 hours. The solution is poured into water. The precipitated ethyl 2-(4-phthalimidobutyl)benzofuran-6-carboxylate is collected by filtration.
D. Ethyl 2-(4-aminobutyl)benzofuran-6-carboxylate
A solution of ethyl 2-(4-phthalimidobutyl)-benzofuran-6-carboxylate (3.9 g., 0.01 mole) and hydrazine hydrate (0.55 g., 0.011 mole) in ethanol (20 ml.) is heated at 60° C. for 8 hours. The solvent is evaporated at reduced pressure. The solid residue is treated with water and 5 N sodium hydroxide solution and then is extracted with chloroform. The evaporation of the solvent from the organic extract provides ethyl 2-(4-aminobutyl)benzofuran-6-carboxylate.
E. N,N-Dimethyl-2-(4-aminobutyl)benzofuran-6-carboxamide
A solution of ethyl 2-(4-aminobutyl)benzofuran-6-carboxylate (13.0 g., 0.05 mole), dimethylamine (35 g.), and a catalytic amount of sodium ethoxide (approximately 100 mg.) in ethanol (100 ml.) is heated in a sealed pressure bottle at 65° C. for 18 hours. Evaporation of the solvent provides N,N-dimethyl-2-(4-aminobutyl)benzofuran-6-carboxamide.
F. 2-(4-Aminobutyl)-6-(dimethylaminomethyl)benzofuran
N,N-dimethyl-2-(4-aminobutyl)benzofuran-6-carboxamide (13.0 g., 0.05 mole) in tetrahydrofuran (60 ml.) is added dropwise with stirring to lithium aluminum hydride (3.0 g., 0.08 mole) in tetrahydrofuran (60 ml.) at 25°-30° C. The mixture is stirred for 2 hours at 25°-30° C. and then is treated successively with 3 g. of water, 3 g. of 15% sodium hydroxide solution and 9 g. of water. The solid precipitate is removed by filtration. The tetrahydrofuran solution is evaporated at reduced pressure to provide 2-(4-aminobutyl)-6-dimethylaminomethyl)benzofuran.
G. N-Cyano-N'-[4-(6-dimethylaminomethyl-2-benzofuranyl)-butyl]-S-methylisothiourea
This compound is obtained by the reaction of 2-(4-aminobutyl)-6-(dimethylaminomethyl)benzofuran with dimethyl cyanodithioimidocarbonate following the procedure described in Example 1, Step F.
H. N-Cyano-N'-[4-(6-dimethylaminomethyl-2-benzofuranyl)butyl]-N"-methylquanidine
This compound is obtained by the reaction of N-cyano-N'-[4-(6-dimethylaminomethyl-2-benzofuranyl)butyl]-S-methylisothiourea with methylamine following the procedure described in Example 1, Step G.
EXAMPLE 6
N-Cyano-N'-[2-(6-diethylaminomethyl)-2-benzofuranylmethylthio)ethyl]-N"-methylguanidine
This compound is prepared by the series of reactions described in Example 2 except that in Step C diethylamine is substituted for the dimethylamine used in Example 2, Step C. The subsequent compounds thus obtained are:
Step C--Ethyl 6-(diethylaminomethyl)benzofuran-2-carboxylate
Step D--6-(Diethylaminomethyl)-2-benzofuranmethanol
step E--2-(2-Aminoethylthiomethyl)-6-(diethylaminomethyl)benzofuran
Step F--N-Cyano-N'-[2-(6-diethylaminomethyl-2-benzofuranylmethylthio)ethyl]-S-methylisothiourea
Step G--N-Cyano-N'-[2-(6-diethylaminomethyl)-2-benzofuranylmethylthio)ethyl]-N"-methylguanidine
EXAMPLE 7
N-Cyano-N'-[2-(6-(1-piperidinyl)methyl-2-benzofuranylmethylthio)ethyl]-N"-methylguanidine
This compound is prepared by the series of reactions described in Example 1 except that in Step C an equivalent quantity of piperidine is substituted for the dimethylamine in Example 1, Step C. The subsequent compounds thus obtained are:
Step C--Ethyl 6-[(1-piperidinyl)methyl]benzofuran-2-carboxylate
Step D--6-[(1-Piperidinyl)methyl]-2-benzofuranmethanol
Step E--2-(2-Aminoethylthiomethyl)-6-[(1-piperidinyl)-methyl]benzofuran
Step F--N-Cyano-N'-[2-(6-(1-piperidinyl)methyl-2-benzofuranylmethylthio)ethyl]-S-methylisothiourea
Step G--N-Cyano-N'-[2-(6-(1-piperidinyl)methyl-2-benzofuranylmethylthio)ethyl]-N"-methylguanidine
EXAMPLE 8
N-[2-(6-Dimethylaminomethyl-2-benzofuranylmethylthio)-ethyl]-N'-methyl-2-nitro-1,1-ethenediamine
A. N-[2-(6-Dimethylaminomethyl-2-benzofuranylmethylthio)-ethyl]-1-methylthio-2-nitroetheneamine
A solution of 2-(2-aminoethylthiomethyl)-6-(dimethylaminomethyl)benzofuran (Example 1, Step E) (8.0 g., 0.0303 mole) and 1,1-bismethylthio-2-nitroethene (5.25 g., 0.0318 mole) in acetonitrile (80 ml.) is heated at 55° C. for 16 hours. The solvent is evaporated at reduced pressure. The residue is chromatographed on a column containing 175 g. of silica gel made up in chloroform. The product is eluted with 5% methanol in chloroform and is obtained as a light orange viscous oil weighing 6.1 g. (53%).
B. N-[2-(6-Dimethylaminomethyl-2-benzofuranylmethylthio)-ethyl]-N'-methyl-2-nitro-1,1-ethenediamine
A solution of N-[2-(6-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-1-methylthio-2-nitroetheneamine (6.0 g., 0.0157 mole) and methylamine (20 g.) in ethanol (60 ml.) is allowed to stand 2 hours at 27° C. The solvent was evaporated at reduced pressure. The solid residue is recrystallized from acetonitrile-ether to yield 3.1 g. (54%) of N-[2-(6-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-N'-methyl-2-nitro-1,1-ethenediamine, m.p. 113°-114° C.
The products in the following table are prepared by the method of Step B of this Example except that methylamine is replaced by the appropriate amine R 3 NH 2 in the threefold or greater molar excess:
______________________________________ ##STR15##R.sub.3 M.P. °C.______________________________________CH.sub.2 CCH 155-156CH.sub.2 CHCH.sub.2 105-107 ##STR16## 148-149 ##STR17## 114-116CH.sub.2 CH.sub.2 OH 125-128CH.sub.2 CH.sub.2OCH.sub.3 115-116CH.sub.2 CH.sub.2N(CH.sub.3).sub.2 89-90 ##STR18## ##STR19## 109-112______________________________________
EXAMPLE 9
N-Cyano-N'-[2-(6-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]guanidine
A solution of N-cyano-N'-[2-(6-dimethylaminomethyl)-2-benzofuranylmethylthio)ethyl]-S-methylisothiourea (Example 1, Step F) (6.27 g., 0.0173 mole) and ammonia (12 g.) in ethanol (65 ml.) is heated in a sealed vessel for 36 hours at 55°-60° C. Volatile materials are then removed by distillation at reduced pressure. The residual oil consisting of the nearly pure product is purified by column chromatography on 85 g. of silica gel with elution by a 10% solution of methanol in chloroform affording N-cyano-N'-[2-(6-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]guanidine.
EXAMPLE 10
N-Cyano-N'-[2-(6-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-N"-(2-propynyl)guanidine
A solutiion of N-cyano-N'-[2-(6-dimethylaminomethyl)-2-benzofuranylmethylthio)ethyl]-S-methylisothiourea (Example 1, Step F) (6.55 g., 0.018 mole) and propargylamine (4.0 g., 0.073 mole) in acetonitrile (100 ml.) is heated in a sealed pressure vessel at 110°-120° C. for 36 hours. The reaction solution is then evaporated at reduced pressure. N-cyano-N'-[2-(6-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-N"-(2-propynyl)guanidine is obtained when the residual oil is chromatographed on silica gel with elution by an 8% solution of methanol in chloroform.
EXAMPLE 11
N-Benzyl-N'-cyano-N"-[2-(6-dimethylaminomethyl-2-benzofuranylthio)ethyl[guanidine
This compound is prepared by the procedure described in Example 10 except that an equivalent quantity of benzylamine is substituted for the proparglyamine used in Example 10.
EXAMPLE 12
N-[2-(6-Dimethylaminomethyl-2-benzofuranylmethylthio)-ethyl]-N'-(2-propenyl)thiourea
A solution of 2-(2-aminoethylthiomethyl)-6-(dimethylaminomethyl)benzofuran (Example 1, Step E) (2.6 g., 0.01 mole) and allyl isothiocyanate (1.1 g., 0.011 mole) in acetonitrile (15 ml.) is kept at 25°-27° C. for 16 hours. The solvent is evaporated and the residual oil chromatographed (silica gel/5% methanol in chloroform) to yield N-[2-(6-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-N'-(2-propenyl)thiourea.
EXAMPLE 13
N-[2-(6-Dimethylaminomethyl-2-benzofuranylmethylthio)-ethyl]-N'-nitroguanidine
A solution of 2-(2-aminoethylthiomethyl)-6-(dimethylaminomethyl)benzofuran (Example 1, Step E) (2.6 g., 0.01 mole) and S-methyl-N-nitroisothiourea (1.4 g., 0.01 mole) in acetonitrile (15 ml.) is kept at 25°-27° C. for 4 hours. The solvent is evaporated and the residue chromatographed on silica gel (5% methanol in chloroform elution) to yield N-[2-(6-dimethylaminomethyl-2-benzofuranylmethylthio)ethyl]-N'-nitroguanidine.
EXAMPLE 14
N-[2-(6-Dimethylaminomethyl-2-benzofuranylmethylthio)-ethyl]-N'-methanesulfonyl-N"-methylguanidine
A solution of 2-(2-aminoethylthiomethyl)-6-(dimethylaminomethyl)benzofuran (Example 1, Step E) (2.6 g., 0.01 mole) and methanesulfonyliminodithiocarbonic acid dimethyl ester (2.0 g., 0.01 mole) in methanol (15 ml.) is kept at 25°-27° C. for 4 hours. A solution of 10 g. of methylamine in 35 ml. of methanol is added and the resulting solution is kept at 25°-27° C. for 16 hours. The solvent is evaporated to leave N-[2-(6-dimethylaminomethyl-2-benzofuranylmethylthio)-ethyl]-N'-methanesulfonyl-N"-methylguanidine as a residual oil which is purified by column chromatography (silica gel/5% methanol in chloroform).
EXAMPLE 15
N-Cyano-N'-[3-(6-dimethylaminomethyl-2-benzofuranylmethylthio)propyl]-N"-methylguanidine
This compound is prepared by the series of reactions described in Example 1 except that in Step E an equivalent amount of 3-amino-1-propanethiol hydrochloride is substituted for the cysteamine hydrochloride employed in Example 1, Step E. The subsequent compounds thus obtained are:
Step E-2-(3-Aminopropylthiomethyl)-6-(dimethylaminomethyl)benzofuran
Step F--N-Cyano-N'-[3-(6-dimethylaminomethyl-2-benzofuranylmethylthio)propyl]-S-methylisothiourea
Step G--N-Cyano-N'-[3-(6-dimethylaminomethyl-2-benzofuranylmethylthio)propyl]-N"-methylguanidine | There are disclosed novel compounds described as aminoalkyl benzofuran derivatives in which the aminoalkyl benzofuran is connected to a guanidine moiety or functional equivalent thereof through a linear connecting group. Processes for the preparation of such compounds are also disclosed. The compounds are useful for the suppression of gastric acid secretions in mammals and compositions for such uses are also disclosed. | 2 |
INCORPORATION BY REFERENCE
The present application claims priority under 35 U.S.C. §119 to Japanese Patent Application Nos. 2003-393793 filed Nov. 25, 2003; 2003-424404 filed Dec. 22, 2003; 2003-424404 filed Dec. 22, 2003; 2003-424405 filed Dec. 22, 2003; 2004-058681 filed Mar. 3, 2004; 2004-058684 filed Mar. 3, 2004; 2004-058685 filed Mar. 3, 2004; 2004-172510 filed Jun. 10, 2004; 2004-178075 filed Jun. 16, 2004; 2004-178074 filed Jun. 16, 2004 and 2004-175038 filed Jun. 14, 2004. The content of the applications are incorporated herein by reference in their entireties.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a surface-coated cermet cutting tool (hereinafter referred to as a coated cermet tool) of which a hard coating layer exhibits excellent chipping resistance, in particular, during high-speed intermittent cutting of steel, cast iron, etc.
2. Description of the Related Art
Conventionally, a coated cermet tool is known, which is generally formed by coating, on a surface of a substrate (hereinafter, generally referred to as a tool substrate) made of tungsten carbide (hereinafter, referred to as WC)-based cemented carbide or titanium carbonitride (hereinafter, referred to as TiCN)-based cermet, a hard-coating layer composed of the following upper and lower layers (a) and (b):
(a) as the lower layer, a titanium compound layer having at least one or two of titanium carbide (hereinafter, referred to as TiC) layer, a titanium nitride (hereinafter, referred to as TiN) layer, a titanium carbonitride (hereinafter, referred to as TiCN) layer, a titanium carboxide (hereinafter, referred to as TiCO) layer, and a titanium oxycarbonitride (hereinafter, referred to as TiCNO) layer, all of which are formed by chemical vapor deposition, the titanium compound layer having a total average layer thickness of 3 to 20 μm, and
(b) as the upper layer, a deposited α-type aluminum oxide (hereinafter referred to as Al 2 O 3 ) layer having an α-type crystal structure deposited by chemical vapor deposition and an average layer thickness of 1 to 15 μm. The coated cermet tool is widely used for, for example, continuous or intermittent cutting of steel or cast iron.
Generally, it is also well known that a titanium compound layer or deposited α-type Al 2 O 3 layer constituting the hard-coating layer of a coated cermet tool has a granular crystal structure, and further a TiCN layer constituting the titanium compound layer has a lengthwise growth crystal structure formed by carrying out chemical vapor deposition in a moderate temperature range of 700 to 950° C. using as a reaction gas a mixed gas which includes organic carbonitride, for example, CH 3 CN in a conventional chemical vapor deposition reactor for increasing the strength of the layer, as disclosed in Japanese Unexamined Patent Application Publications Nos. 6-31503 and 6-8010.
In recent years, the performance of cutting tools has been markedly enhanced, and demands for labor saving and energy saving in cutting work and cost reduction have been increased. Accordingly, the cutting work is more often carried out at a higher speed range. The conventional coated cermet tools generally present no problem when they are used in the continuous cutting or intermittent cutting of steel, cast iron or the like under normal conditions. And, when the conventional cutting tools are used in a high-speed intermittent cutting under the severest cutting condition, i.e., in the high-speed intermittent cutting where mechanical and thermal impacts are repeatedly applied to the cutting edge at very short pitches, a titanium compound layer which is typically the lower layer of a hard-coating layer has high strength and exhibits excellent impact resistance. However, the deposited α-type Al 2 O 3 layer that constitutes the upper layer of a hard-coating layer, despite its hardness in high temperature and excellent heat resistance, is very brittle against the mechanical and thermal impacts. As a result, chipping (fine crack) easily occurs in the hard-coating layer, consequently shortening the usable life of cermet cutting tools.
SUMMARY OF THE INVENTION
The present invention is made to solve the above problems, and it is therefore an object of the present invention to provide a surface-coated cermet cutting tool with a hard-coating layer having excellent chipping resistance.
Considering the above problems, the inventors have conducted studies for improving the chipping resistance of a deposited α-type Al 2 O 3 layer that constitutes the upper layer of the hard-coating layer of the coated cermet tools, and have obtained the following results (a) to (c) described below.
(a) On a surface of a tool substrate, the titanium compound layer as a lower layer is formed under normal conditions using a conventional chemical vapor deposition reactor. An Al—Zr oxide layer [hereinafter, referred to as an (Al, Zr) 2 O 3 layer having a κ-type or θ-type crystal structure and satisfying the composition formula: (Al 1-X Zr X ) 2 O 3 (where value X is 0.003 to 0.05 in an atomic ratio when measured by an electron probe micro-analyzer (EPMA)] is deposited under the same normal conditions.
Next, the surface of the (Al, Zr) 2 O 3 layer is processed using the chemical vapor deposition reactor under the following conditions:
Composition of a reaction gas: in volume %, TiCl 4 : 0.2 to 3%, CO 2 : 0.2 to 10%, Ar: 5 to 50%, and H 2 : balance,
Temperature of reaction atmosphere: 900 to 1020° C.,
Pressure of reaction atmosphere: 7 to 30 kPa, and
Time: 25 to 100 min.
Then, a titanium oxide layer satisfying the composition formula: TiO Y , (wherein value Y is 1.2 to 1.9 in an atomic ratio to Ti when measured by Auger Electron Spectroscopy) and having an average layer thickness 0.05 to 1.5 μm are formed on the surface of the (Al, Zr) 2 O 3 layer.
In this state, by carrying out a heat-transforming treatment in an atmosphere of Ar gas, preferably, under the following conditions: a pressure of 7 to 50 kPa, a temperature of 1000 to 1200° C., and a holding duration of 10 to 120 minutes, to transform the (Al, Zr) 2 O 3 layer having the κ-type or θ-type crystal structure into the (Al, Zr) 2 O 3 layer having an α-type crystal structure. Then, by the operation of the titanium oxide layer formed on the surface of the (Al, Zr) 2 O 3 layer before the transformation the κ-type or θ-type crystal structure is wholly and simultaneously transformed into the α-type crystal structure and the progress of the heat transformation is markedly promoted. Thus, cracks generated at the time of the transformation become extremely fine and the titanium oxide particulates are uniformly and dispersedly distributed. Further, the high temperature strength of the (Al, Zr) 2 O 3 layer itself is markedly enhanced by the effect of Zr as a constituent element of the (Al, Zr) 2 O 3 layer. As a result, the heat-transformed α-type (Al, Zr) 2 O 3 layer has a uniformed structure in which cracks generated by the transformation process has fine characteristics over the entire length, in addition to high strength, very strong resistance against mechanical and thermal impacts and excellent chipping resistance. Accordingly, in the coated cermet tool having a hard-coating layer composed of the heat-transformed α-type (Al, Zr) 2 O 3 layer as the upper layer and the titanium compound layer (this titanium compound layer does not exhibit any change during heat-transforming treatment under the above-mentioned conditions) as the lower layer, the heat-transformed α-type (Al, Zr) 2 O 3 layer exhibits excellent chipping resistance, even in a high-speed intermittent cutting accompanied with severe mechanical and thermal impacts, while it has the same high temperature hardness and heat resistance as the excellent high temperature hardness and heat resistance inherent to an α-type Al 2 O 3 layer. Thus, with the presence of the titanium compound layer having high strength, the occurrence of chipping in the hard-coating layer is markedly suppressed and an excellent wear resistance is exhibited for a prolonged period of time.
(b) As for the conventional α-type Al 2 O 3 layer and the above heat-transformed α-type (Al, Zr) 2 O 3 layer, when an inclination angle frequency-distribution graph is obtained from the results of radiating electron beam onto crystal grains having a hexagonal crystal lattice in a measuring range of surfaces to be polished using a field-emission-type scanning electron microscope, as shown in schematic explanatory views of FIGS. 1( a ) and 1 ( b ), measuring an inclination angle of a normal line of a plane (0001) as a crystal plane in which each of the crystal grains is formed with respect to each of the polished surfaces, sorting the measured inclination angles in a range of 0 to 45 degrees among all the measured inclination angles into several intervals at a pitch of 0.25 degrees, and summing up the frequencies in each of the intervals, the conventional deposited α-type Al 2 O 3 layer, as illustrated in FIG. 6 , shows an inclination angle frequency-distribution graph on which the distribution of measured inclination angles of the plane (0001) is unbiased in a range of 0 to 45 degrees, whereas the heat-transformed α-type (Al, Zr) 2 O 3 layer, as illustrated in FIG. 2 , shows an inclination angle frequency-distribution graph on which a sharp and highest peak appears at a certain position in an inclination angle interval, and the position of the sharp and highest peak appearing in the inclination angle interval on an X-axis of the graph varies depending on the variation of value Y in the composition formula: TiO Y of the titanium oxide layer.
(c) According to the test results, when value Y in the composition formula: TiO Y of the titanium oxide layer is set to 1.2 to 1.9 in an atomic ratio as described above, there is obtained an inclination angle frequency-distribution graph on which the sharp and highest peak appears in an inclination angle range of 0 to 10 degrees, and the sum of frequencies in the range of 0 to 10 degrees occupies 45% or more of the total sum of frequencies on the inclination angle frequency-distribution graph. In a coated cermet tool of the present invention deposited using, as the upper layer of the hard coating layer, a heat-transformed α-type (Al, Zr) 2 O 3 layer which shows the resulting inclination angle frequency-distribution graph on which the inclination angle frequency in the range of 0 to 10 degrees occupies 45% or more, and the highest peak appears in the inclination angle interval in the range of 0 to 10 degrees with the presence of the titanium compound layer as the lower layer, the coated cermet tools of the present invention exhibit more excellent wear resistance without causing chipping in the cutting edge, in particular, in the high-speed intermittent cutting, as compared to the conventional cermet tool.
The present invention has been achieved based on the above research results (a) to (c).
According to the present invention, there is provided a surface-coated cermet cutting tool with a hard-coating layer exhibiting excellent chipping resistance, the surface-coated cermet cutting tool being formed by coating, on a surface of a tool substrate made of tungsten-carbide-based cemented carbide or titanium-carbonitride-based cermet, the hard-coating layer composed of the following upper and lower layers (a) and (b):
(a) as the lower layer, a titanium compound layer having at least one or two of a titanium carbide layer, a titanium nitride layer, a titanium carbonitride layer, a titanium carboxide layer and a titanium oxycarbonitride layer, all of which are deposited by chemical vapor deposition, the titanium compound layer having a total average layer thickness of 3 to 20 μm, and
(b) as the upper layer, a heat-transformed α-type (Al, Zr) 2 O 3 layer formed by carrying out a heat-transforming treatment in a state that a titanium oxide layer satisfying the composition formula: TiO Y , (where value Y is 1.2 to 1.9 in an atomic ratio to Ti when measured by Auger Electron Spectroscopy) and having an average layer thickness of 0.05 to 1.5 μm is chemically deposited on a surface of an (Al, Zr) 2 O 3 layer having a κ-type or θ-type crystal structure deposited by chemical vapor deposition and satisfying the composition formula: (Al 1-X Zr X ) 2 O 3 (where value X is 0.003 to 0.05 in an atomic ratio when measured by an electron probe micro-analyzer (EPMA)) to thereby transform the crystal structure of the (Al, Zr) 2 O 3 layer having the κ-type or θ-type crystal structure into an α-type crystal structure,
the heat-transformed α-type (Al, Zr) 2 O 3 layer showing an inclination angle frequency-distribution graph on which a highest peak appears in an inclination angle interval in a range of 0 to 10 degrees and the sum of frequencies in a range of 0 to 10 degrees occupies 45% or more of the total sum of frequencies on the inclination angle frequency-distribution graph, wherein the inclination angle frequency-distribution graph is obtained from results of radiating electron beam onto crystal grains having a hexagonal crystal lattice in a measuring range of surfaces to be polished using a field-emission-type scanning electron microscope, measuring an inclination angle of a normal line of the plane (0001) as a crystal plane in which each of the crystal grains is formed with respect to each of the polished surfaces, sorting the measured inclination angles in a range of 0 to 45 degrees among all the measured inclination angles into several intervals at a pitch of 0.25 degrees, and summing up the frequencies in each of the intervals,
and the heat-transformed α-type (Al, Zr) 2 O 3 layer having an average layer thickness of 1 to 15 μm.
The reasons for limiting the numerical values in the layers constituting the hard coating layer of the coated cermet layer of the present invention as described above will be described below.
(a) Average layer thickness of the lower layer (Ti compound layer)
A titanium compound layer inherently has excellent high temperature strength, and the hard-coating layer has high temperature strength by virtue of the existence of the titanium compound layer. In addition, the titanium compound layer is firmly adhered to both of the tool substrate and the heat-transformed α-type (Al, Zr) 2 O 3 layer that is the upper layer. Accordingly, it contributes to improving the adherence of the hard-coating layer to the tool substrate. However, when the total average layer thickness is less than 3 μm, the above function cannot be sufficiently obtained. On the other hand, when the total average layer thickness exceeds 20 μm, thermal plastic deformation is apt to occur, particularly in a high-speed intermittent cutting accompanied by the generation of high heat, which causes partial wear. Accordingly, the average layer thickness of a lower layer is preferably set to 3 to 20 μm.
(b) Composition and average layer thickness of titanium oxide layer (value Y)
As described above, by the operation of the titanium oxide layer a deposited κ-type or θ-type (Al, Zr) 2 O 3 layer is wholly and simultaneously transformed into a heat-transformed α-type (Al, Zr) 2 O 3 layer to thereby make cracks generated at the time of heating transformation fine and uniform. In addition, the titanium oxide layer functions to promote the heating transformation and to suppress the growth of crystal grains by shortening the processing time. Moreover, when value Y in the composition formula: TiO Y of the titanium oxide layer is set to 1.2 to 1.9 as described above, according to the test results, the titanium oxide layer functions to show an inclination angle frequency-distribution graph on which a highest peak of inclination angle frequency appears in an inclination angle interval range of 0 to 10 degrees, and the ratio of the sum of frequencies in the inclination angle frequency range of 0 to 10 degrees occupies 45% of the total sum of frequencies on the inclination angle frequency-distribution graph. Accordingly, when value Y is less than 1.2, the highest peak appears less in the range of 0 to 10 degrees on the inclination angle frequency-distribution graph of the heat-transformed α-type (Al, Zr) 2 O 3 layer. In other words, the ratio of the sum of frequencies in the range of 0 to 10 degrees may become less than 45% of the total sum of frequencies on the inclination angle frequency-distribution graph. In this case, as described above, a desired excellent high temperature strength cannot be secured in the heat-transformed α-type (Al, Zr) 2 O 3 layer, which leads to the failure in obtaining a desired chipping resistance. On the other hand, when value Y exceeds 1.9, the inclination angle interval in which the highest peak appears may deviates out of the range of 0 to 10 degrees. In this case, the desired high temperature strength cannot be secured in the heat-transformed α-type (Al, Zr) 2 O 3 layer. Thus, value Y is set to 1.2 to 1.9 in an atomic ratio to Ti.
Further, in this case, when the average layer thickness of the titanium oxide layer is less than 0.05 μm, the above-mentioned functions cannot be sufficiently obtained. On the other hand, since the above functions can be sufficiently obtained only with an average layer thickness of 1.5 μm, and the thickness beyond the limit is unnecessary, the average layer thickness of the titanium oxide layer is preferably set to 0.05 to 1.5 μm.
(c) Content ratio of Zr in the upper layer [a heat-transformed α-type (Al, Zr) 2 O 3 layer] and average layer thickness of the upper layer
The heat-transformed α-type (Al, Zr) 2 O 3 layer has excellent high temperature hardness and heat resistance by the presence of Al as a constituent element thereof, and has high temperature strength by the presence of Zr as a constituent element thereof. Thus, the heat-transformed α-type (Al, Zr) 2 O 3 layer exhibits excellent wear resistance and chipping resistance. However, when the content ratio (value X) of Zr is less than 0.003 in an atomic ratio occupied in the total amount with Al (this is true of the following ratios), a sufficiently enhanced high temperature strength cannot be secured. On the other hand, when the content ratio of Zr exceeds 0.05, instability is caused in the hexagonal crystal lattice, which makes it difficult to sufficiently transform an κ-type or θ-type crystal structure into an α-type crystal structure during the heat-transforming treatment. Thus, the content ratio (value X) of Zr is preferably set to 0.003 to 0.05.
Further, when the average layer thickness of the heat-transformed α-type (Al, Zr) 2 O 3 layer is less than 1 μm, the hard coating layer cannot be allowed to sufficiently exhibit wear resistance. On the other hand, when the average layer thickness of the heat-transformed α-type (Al, Zr) 2 O 3 layer is greater than 15 μm, chipping is apt to occur. Thus, the average layer thickness of the heat-transformed α-type (Al, Zr) 2 O 3 layer is preferably set to 1.15 μm.
Furthermore, for the purpose of identifying the cutting tool before and after the use thereof, a TiN layer having a gold color tone may be deposited, if desired. In this case, the average layer thickness of the TiN layer is preferably 0.1 to 1 μm. This is because, when the average layer thickness is less than 0.1 μm, a sufficient identification cannot be achieved, whereas the identification due to the TiN layer is sufficient with an average layer thickness of up to 1 μm.
Further, the inventors have obtained the following results (a) to (c) described below.
(a) On a surface of a tool substrate, the titanium compound layer as a lower layer is formed under normal conditions using a conventional chemical vapor deposition reactor. An Al—Cr oxide [hereinafter, referred to as an (Al, Cr) 2 O 3 layer having a κ-type or θ-type crystal structure and satisfying the composition formula: (Al 1-X Cr X ) 2 O 3 (where value X is 0.005 to 0.04 in an atomic ratio when measured by an electron probe micro-analyzer (EPMA)] is deposited under the same normal conditions.
Next, the surface of the (Al, Cr) 2 O 3 layer is processed using the chemical vapor deposition reactor under the following conditions:
Composition of a reaction gas: in volume%, TiCl 4 : 0.2 to 3%, CO 2 : 0.2 to 10%, Ar: 5 to 50%, and H 2 : balance,
Temperature of reaction atmosphere: 900 to 1020° C.,
Pressure of reaction atmosphere: 7 to 30 kPa, and
Time: 25 to 100 min.
Then, a titanium oxide layer satisfying the composition formula: TiO Y , (wherein value Y is 1.2 to 1.9 in an atomic ratio to Ti when measured by Auger Electron Spectroscopy) and having an average layer thickness 0.1 to 2 μm are formed on the surface of the (Al, Cr) 2 O 3 layer.
In this state, by carrying out a heat-transforming treatment in an atmosphere of Ar gas, preferably, under the following conditions: a pressure of 7 to 50 kPa, and a temperature of 1000 to 1200° C., to transform the (Al, Cr) 2 O 3 layer having the κ-type or θ-type crystal structure into the (Al, Cr) 2 O 3 layer having an α-type crystal structure. Then, by the operation of the titanium oxide layer formed on the surface of the (Al, Cr) 2 O 3 layer before the transformation the κ-type or θ-type crystal structure is wholly and simultaneously transformed into the α-type crystal structure and the progress of the heat transformation is markedly promoted. Thus, since cracks generated at the time of the transformation are simultaneously generated, the titanium oxide particulates are extremely finely, uniformly and dispersedly distributed, and the fineness of the cracks generated due to transformation is further promoted by the effect of Cr as a constituent element of the (Al, Cr) 2 O 3 layer. As a result, since the formed heat-transformed α-type (Al, Cr) 2 O 3 layer has a uniformed structure in which cracks generated by transformation process and crystal grains has fine characteristics over the entire layer, it has a very strong resistance against mechanical and thermal impacts and consequently excellent chipping resistance. Accordingly, in the coated cermet tool having a hard-coating layer composed of the heat-transformed α-type (Al, Cr) 2 O 3 layer as the upper layer and the titanium compound layer (this titanium compound layer does not exhibit any change during heat-transforming treatment under the above-mentioned conditions) as the lower layer, the heat-transformed α-type (Al, Cr) 2 O 3 layer exhibits excellent chipping resistance, even in the high-speed intermittent cutting accompanied with severe mechanical and thermal impacts, while it has the same high temperature hardness and heat resistance as the excellent high temperature hardness and heat resistance inherent to an α-type Al 2 O 3 layer. Thus, with the presence of the titanium compound layer having high strength, the occurrence of chipping in the hard-coating layer is markedly suppressed and the excellent wear resistance is exhibited for a prolonged period of time.
(b) As for the conventional α-type Al 2 O 3 layer and the above heat-transformed α-type (Al, Cr) 2 O 3 layer, when an inclination angle frequency-distribution graph is obtained from the results of radiating electron beam onto crystal grains having a hexagonal crystal lattice in a measuring range of surfaces to be polished using a field-emission-type scanning electron microscope, as shown in schematic explanatory views of FIGS. 1( a ) and 1 ( b ), measuring an inclination angle of a normal line of the plane (0001) as a crystal plane in which each of the crystal grains is formed with respect to each of the polished surfaces, sorting the measured inclination angles in a range of 0 to 45 degrees among all the measured inclination angles into several intervals at a pitch of 0.25 degrees, and summing up the frequencies in each of the intervals, the conventional deposited α-type Al 2 O 3 layer, as illustrated in FIG. 6 , shows an inclination angle frequency-distribution graph on which the distribution of measured inclination angles of the plane (0001) is unbiased in a range of 0 to 45 degrees, whereas the heat-transformed α-type (Al, Cr) 2 O 3 layer, as illustrated in FIG. 3 , shows an inclination angle frequency-distribution graph on which a sharp and highest peak appears at a certain position in an inclination angle interval and the position of the sharp and highest peak appearing in the inclination angle interval on an X-axis of the graph varies depending on the variation of value Y in the composition formula: TiO Y of the titanium oxide layer.
(c) According to the test results, when value Y in the composition formula: TiO Y of the titanium oxide layer is set to 1.2 to 1.9 in an atomic ratio to Ti as described above, there is obtained an inclination angle frequency-distribution graph on which the sharp and highest peak appears in an inclination angle range of 0 to 10 degrees, and the sum of frequencies (the sum of frequencies is proportional to the height of the highest peak) in the range of 0 to 10 degrees occupies 45% or more of the total sum of frequencies on the inclination angle frequency-distribution graph. In a coated cermet tool of the present invention deposited using, as the upper layer of the hard coating layer, a heat-transformed α-type (Al, Cr) 2 O 3 layer which shows the resulting inclination angle frequency-distribution graph on which the inclination angle frequency in the range of 0 to 10 degrees occupies 45% or more, and the highest peak appears in the inclination angle interval in the range of 0 to 10 degrees with the presence of the titanium compound layer as a lower layer, the coated cermet tools of the present invention exhibit more excellent wear resistance without causing chipping in a cutting edge, in particular, in the high-speed intermittent cutting, as compared to the conventional cermet tool.
The present invention has been achieved based on the above research results (a) to (c).
According to the present invention, there is provided a surface-coated cermet cutting tool with a hard-coating layer exhibiting excellent chipping resistance, the surface-coated cermet cutting tool being formed by coating, on a surface of a tool substrate made of tungsten carbide-based cemented carbide or titanium carbonitride-based cermet, the hard-coating layer composed of the following upper and lower layers (a) and (b):
(a) as the lower layer, a titanium compound layer having at least one or two of a titanium carbide layer, a titanium nitride layer, a titanium carbonitride layer, a titanium carboxide layer and a titanium oxycarbonitride layer, all of which are deposited by chemical vapor deposition, the titanium compound layer having a total average layer thickness of 3 to 20 μm, and
(b) as the upper layer, a heat-transformed α-type (Al, Cr) 2 O 3 layer formed by carrying out a heat-transforming treatment in a state that a titanium oxide layer satisfying the composition formula: TiO Y , (where value Y is 1.2 to 1.9 in an atomic ratio to Ti when measured by Auger Electorn Spectroscopy) and having an average layer thickness of 0.1 to 2 μm is chemically deposited on a surface of an (Al, Cr) 2 O 3 layer having a κ-type or θ-type crystal structure deposited by chemical vapor deposition and satisfying the composition formula: (Al 1-X Cr X ) 2 O 3 (where value X is 0.005 to 0.04 in an atomic ratio when measured by an electron probe micro-analyzer (EPMA)) to thereby transform the crystal structure of the (Al, Cr) 2 O 3 layer having the κ-type or θ-type crystal structure into an α-type crystal structure,
the heat-transformed α-type (Al, Cr) 2 O 3 layer showing an inclination angle frequency-distribution graph on which a highest peak appears in an inclination angle interval in a range of 0 to 10 degrees and the sum of frequencies in a range of 0 to 10 degrees occupies 45% or more of the total sum of frequencies on the inclination angle frequency-distribution graph wherein the inclination angle frequency-distribution graph is obtained from the results of radiating electron beam onto crystal grains having a hexagonal crystal lattice in a measuring range of surfaces to be polished using a field-emission-type scanning electron microscope, measuring an inclination angle of a normal line of the plane (0001) as a crystal plane in which each of the crystal grains is formed with respect to each of the polished surfaces, sorting the measured inclination angles in a range of 0 to 45 degrees among all the measured inclination angles into several intervals at a pitch of 0.25 degrees, and summing up the frequencies in each of the intervals,
and the heat-transformed α-type (Al, Cr) 2 O 3 layer having an average layer thickness of 1 to 15 μm.
The reasons for limiting the numerical values in the layers constituting the hard coating layer of the coated cermet layer of the present invention as described above will be described below.
(a) Average layer thickness of the lower layer (a titanium compound layer)
A titanium compound layer inherently has excellent high temperature strength, and the hard-coating layer has high temperature strength by virtue of the existence of the titanium compound layer. In addition, the titanium compound layer is firmly adhered to both of the tool substrate and the heat-transformed α-type (Al, Cr) 2 O 3 layer that is the upper layer. Accordingly, it contributes to improving the adherence of the hard-coating layer to the tool substrate. However, when the total average layer thickness is less than 3 μm, the above function cannot be sufficiently obtained. On the other hand, when the total average layer thickness exceeds 20 μm, thermal plastic deformation is apt to occur, particularly in the high-speed intermittent cutting accompanied by the generation of high heat, which causes partial wear. Accordingly, the average layer thickness of a lower layer is preferably set to 3 to 20 μm.
(b) Composition and average layer thickness of titanium oxide layer (value Y)
As described above, by the operation of the titanium oxide layer a deposited κ-type or θ-type (Al, Cr) 2 O 3 layer is wholly and simultaneously transformed into a heat-transformed α-type (Al, Cr) 2 O 3 layer to thereby make cracks generated at the time of heating transformation fine and uniform. In addition, the titanium oxide layer functions to promote the heating transformation and to suppress the growth of crystal grains by shortening the processing time. Moreover, when value Y in the composition formula: TiO Y of the titanium oxide layer is set to 1.2 to 1.9 as described above, according to the test results, the titanium oxide layer functions to show an inclination angle frequency-distribution graph on which a highest peak of inclination angle frequency appears in an inclination angle interval range of 0 to 10 degrees, and the ratio of the sum of frequencies in the inclination angle frequency range of 0 to 10 degrees occupies 45% of the total sum of frequencies on the inclination angle frequency-distribution graph. Accordingly, when value Y is less than 1.2, the highest peak appear less in the range of 0 to 10 degrees on the inclination angle frequency-distribution graph of the heat-transformed α-type (Al, Cr) 2 O 3 layer. In other words, the ratio of the sum of frequencies in the range of 0 to 10 degrees may become less than 45% of the total sum of frequencies on the inclination angle frequency-distribution graph. In this case, as described above, a desired excellent high temperature strength cannot be secured in the heat-transformed α-type (Al, Cr) 2 O 3 layer, which leads to the failure in obtaining a desired chipping resistance. On the other hand, when value Y exceeds 1.9, the inclination angle interval in which the highest peak appears may deviates out of the range of 0 to 10 degrees. In this case, the desired high temperature strength cannot be secured in the heat-transformed α-type (Al, Cr) 2 O 3 layer. Thus, value Y is preferably set to 1.2 to 1.9 in an atomic ratio to Ti.
Further, in this case, when the average layer thickness of the titanium oxide layer is less than 0.1 μm, the above-mentioned functions cannot be sufficiently obtained. On the other hand, since the above functions can be sufficiently obtained only with an average layer thickness of 2 μm, and the thickness beyond the limit is unnecessary, the average layer thickness of the titanium oxide layer is preferably set to 0.1 to 2 μm.
(c) Content ratio and average layer thickness of Cr in the upper layer [heat-transformed α-type (Al, Cr) 2 O 3 layer]
The heat-transformed α-type (Al, Cr) 2 O 3 layer has excellent high temperature hardness and heat resistance by the presence of Al as a constituent element thereof. On the other hand, when Cr as a constituent element coexists with the titanium oxide layer, it functions to still further promote the fineness of fine cracks due to transformation, which is generated at the time of a deposited α-type (Al, Cr) 2 O 3 layer into a heat-transformed α-type (Al, Cr) 2 O 3 layer. However, when the content ratio (value X) of Cr is less than 0.005 in an atomic ratio occupied in the total amount with Al (this is true of the following ratios), an effect to further promote the fineness of cracks due to transformation cannot be secured. On the other hand, when the content ratio of Cr exceeds 0.04, instability is caused in the hexagonal crystal lattice, which makes it difficult to sufficiently perform a κ-type or θ-type crystal structure into an α-type crystal structure during the heat-transforming treatment. Thus, the content ratio (value X) of Cr is set to 0.005 to 0.04, preferably, 0.012 to 0.035.
Further, when the average layer thickness of the heat-transformed α-type (Al, Cr) 2 O 3 layer is less than 1 μm, the hard coating layer cannot be allowed to sufficiently exhibit wear resistance. On the other hand, when the average layer thickness of the heat-transformed α-type (Al, Cr) 2 O 3 layer is greater than 15 μm, chipping is apt to occur. Thus, the average layer thickness of the heat-transformed α-type (Al, Cr) 2 O 3 layer is preferably set to 1 to 15 μm.
Furthermore, for the purpose of identifying the cutting tool before and after the use thereof, a TiN layer having a gold color tone may be deposited, if desired. In this case, the average layer thickness of the TiN layer is preferably 0.1 to 1 μm. This is because, when the average layer thickness is less than 0.1 μm, sufficient identification cannot be achieved, whereas the identification due to the TiN layer is sufficient with an average layer thickness of up to 1 μm.
Further, the inventors have obtained the following results (a) to (c) described below.
(a) On a surface of a tool substrate, the titanium compound layer as a lower layer is formed under normal conditions using a conventional chemical vapor deposition reactor. An Al—Ti oxide layer [hereinafter, referred to as an (Al, Ti) 2 O 3 layer having a κ-type or θ-type crystal structure and satisfying the composition formula: (Al 1-X Ti X ) 2 O 3 (where value X is 0.01 to 0.05 in an atomic ratio when measured by an electron probe micro-analyzer (EPMA)] is deposited under the same normal conditions.
Next, the surface of the (Al, Ti) 2 O 3 layer is processed using the chemical vapor deposition reactor under the following conditions:
Composition of a reaction gas: in volume %, TiCl 4 : 0.2 to 3%, CO 2 : 0.2 to 10%, Ar: 5 to 50%, and H 2 : balance,
Temperature of reaction atmosphere: 900 to 1020° C.,
Pressure of reaction atmosphere: 7 to 30 kPa, and
Time: 25 to 100 min.
Then, a titanium oxide layer satisfying the composition formula: TiO Y , (wherein value Y is 1.2 to 1.9 in an atomic ratio to Ti when measured by Auger Electron Spectroscopy) and having an average layer thickness 0.05 to 1.5 μm are formed on the surface of the (Al, Zr) 2 O 3 layer. In this state, by carrying out a heat-transforming treatment in an atmosphere of Ar gas, preferably, under the following conditions: a pressure of 7 to 50 kPa, a temperature of 1000 to 1200° C., and a holding duration of 10 to 120 minutes, to transform the (Al, Ti) 2 O 3 layer having the κ-type or θ-type crystal structure into the (Al, Ti) 2 O 3 layer having an α-type crystal structure. Then, by the operation of the titanium oxide layer formed on the surface of the (Al, Ti) 2 O 3 layer before the transformation the κ-type or θ-type crystal structure is wholly and simultaneously transformed into the α-type crystal structure and the progress of the heat transformation is markedly promoted. Thus, since cracks generated at the time of the transformation are simultaneously generated, the titanium oxide particulates are extremely finely, uniformly and dispersedly distributed, and the crystal growth at the time of the heat transformation is suppressed by the effect of Ti as a constituent element of the (Al, Ti) 2 O 3 layer and the crystal becomes preferably fine. As a result, since the formed heat-transformed α-type (Al, Ti) 2 O 3 layer has a uniformed structure in which cracks generated by the transformation process and crystal grains become fine over the entire layer, it has a very strong resistance against mechanical and thermal impacts and consequently excellent chipping resistance. Accordingly, in the coated cermet tool having a hard-coating layer composed of the heat-transformed α-type (Al, Ti) 2 O 3 layer as the upper layer and the titanium compound layer (this titanium compound layer does not exhibit any change by heat-transforming treatment under the above-mentioned conditions) as the lower layer, the heat-transformed α-type (Al, Ti) 2 O 3 layer exhibits excellent chipping resistance, even in the high-speed intermittent cutting accompanied with severe mechanical and thermal impacts, while it has the same high temperature hardness and heat resistance as the excellent high temperature hardness and heat resistance inherent to the α-type Al 2 O 3 layer. Thus, with the presence of the titanium compound layer having high strength, the occurrence of chipping in the hard-coating layer is markedly suppressed and the excellent wear resistance is exhibited for a prolonged period of time.
(b) As for the conventional α-type Al 2 O 3 layer and the above heat-transformed α-type (Al, Ti) 2 O 3 layer, when an inclination angle frequency-distribution graph is obtained from the results of radiating electron beam onto crystal grains having a hexagonal crystal lattice in a measuring range of surfaces to be polished using a field-emission-type scanning electron microscope, as shown in schematic explanatory views of FIGS. 1( a ) and 1 ( b ), measuring an inclination angle of a normal line of the plane (0001) as a crystal plane in which each of the crystal grains is formed with respect to each of the polished surfaces, sorting the measured inclination angles in a range of 0 to 45 degrees among all the measured inclination angles into several intervals at a pitch of 0.25 degrees, and summing up the frequencies in each of the intervals, the conventional deposited α-type Al 2 O 3 layer, as illustrated in FIG. 6 , shows an inclination angle frequency-distribution graph on which the distribution of measured inclination angles of the plane (0001) is unbiased in a range of 0 to 45 degrees, whereas the heat-transformed α-type (Al, Ti) 2 O 3 layer, as illustrated in FIG. 4 , shows an inclination angle frequency-distribution graph on which a sharp and highest peak appears at a certain position in an inclination angle interval and the position of the sharp and highest peak appearing in the inclination angle interval on an X-axis of the graph varies depending on the variation of value Y in the composition formula: TiO Y of the titanium oxide layer.
(c) According to the test results, when value Y in the composition formula: TiO Y of the titanium oxide layer is set to 1.2 to 1.9 in an atomic ratio to Ti as described above, there is obtained an inclination angle frequency-distribution graph on which the sharp and highest peak appears in an inclination angle range of 0 to 10 degrees, and the sum of frequencies (the sum of frequencies is proportional to the height of the highest peak) in the range of 0 to 10 degrees occupies 45% or more of the total sum of frequencies on the inclination angle frequency-distribution graph. In a coated cermet tool of the present invention deposited using, as the upper layer of the hard coating layer, a heat-transformed α-type (Al, Ti) 2 O 3 layer which shows the resulting inclination angle frequency-distribution graph on which the inclination angle frequency in the range of 0 to 10 degrees occupies 45% or more, and the highest peak appears in the inclination angle interval in the range of 0 to 10 degrees with the presence of the titanium compound layer as the lower layer, the coated cermet tool of the present invention exhibits more excellent wear resistance without causing chipping in a cutting edge, in particular, in the high-speed intermittent cutting, as compared to the conventional cermet tool.
The present invention has been achieved based on the above research results (a) to (c).
According to the present invention, there is provided a surface-coated cermet cutting tool with a hard-coating layer exhibiting excellent chipping resistance, the surface-coated cermet cutting tool being formed by coating, on a surface of a tool substrate made of tungsten carbide-based cemented carbide or titanium carbonitride-based cermet, the hard-coating layer composed of the following upper and lower layers (a) and (b):
(a) as the lower layer, a titanium compound layer having at least one or two of a titanium carbide layer, a titanium nitride layer, a titanium carbonitride layer, a titanium carboxide layer and a titanium oxycarbonitride layer, all of which are deposited by chemical vapor deposition, and the titanium compound layer having a total average layer thickness of 3 to 20 μm, and
(b) as the upper layer, a heat-transformed α-type (Al, Ti) 2 O 3 layer formed by carrying out a heat-transforming treatment in a state that a titanium oxide layer satisfying the composition formula: TiO Y , (where value Y is 1.2 to 1.9 in an atomic ratio to Ti when measured by Auger Electron Spectroscopy) and having an average layer thickness of 0.05 to 1.5 μm is chemically deposited on a surface of an (Al—Ti) 2 O 3 layer having a κ-type or θ-type crystal structure deposited by chemical vapor deposition and satisfying the composition formula: (Al 1-X Ti X ) 2 O 3 (where value X is 0.01 to 0.05 in an atomic ratio when measured by an electron probe micro-analyzer (EPMA)) to thereby transform the crystal structure of the (Al, Ti) 2 O 3 layer having the κ-type or θ-type crystal structure into an α-type crystal structure,
the heat-transformed α-type (Al, Ti) 2 O 3 layer showing an inclination angle frequency-distribution graph on which a highest peak appears in an inclination angle interval in a range of 0 to 10 degrees and the sum of frequencies in a range of 0 to 10 degrees occupies 45% or more of the total sum of frequencies on the inclination angle frequency-distribution graph wherein the inclination angle frequency-distribution graph is obtained from results of radiating electron beam onto crystal grains having a hexagonal crystal lattice in a measuring range of surfaces to be polished using a field-emission-type scanning electron microscope, measuring an inclination angle of a normal line of the plane (0001) as a crystal plane in which each of the crystal grains is formed with respect to each of the polished surfaces, sorting the measured inclination angles in a range of 0 to 45 degrees among all the measured inclination angles into several intervals at a pitch of 0.25 degrees, and summing up the frequencies in each of the intervals,
and the heat-transformed α-type (Al, Ti) oxide layer having an average layer thickness of 1 to 15 μm.
The reason for limiting the numerical values in the layers constituting a hard coating layer of the coated cermet layer of the present invention as described above will be described below.
(a) Average layer thickness of the lower layer (titanium compound layer)
A titanium compound layer inherently has excellent high strength, and the hard-coating layer has high strength by virtue of the existence of the titanium compound layer. In addition, the titanium compound layer is firmly adhered to both of the tool substrate and the heat-transformed α-type (Al, Ti) 2 O 3 layer that is the upper layer. Accordingly, it contributes to improving the adherence of the hard-coating layer to the tool substrate. However, when the total average layer thickness is less than 3 μm, the above function cannot be sufficiently obtained. On the other hand, when the total average layer thickness exceeds 20 μm, thermal plastic deformation is apt to occur, particularly in a high-speed intermittent cutting accompanied by the generation of high heat, which causes partial wear. Accordingly, the total average layer thickness is preferably set to 3 to 20 μm.
(b) Composition and average layer thickness of titanium oxide layer (value Y)
As described above, by the operation of the titanium oxide layer a deposited κ-type or θ-type (Al, Ti) 2 O 3 layer is wholly and simultaneously transformed into a heat-transformed α-type (Al, Ti) 2 O 3 layer to thereby make cracks generated at the time of heating transformation fine and uniform. In addition, the titanium oxide layer functions to promote the heating transformation and to suppress the growth of crystal grains by shortening the processing time. Moreover, when value Y in the composition formula: TiO Y of the titanium oxide layer is set to 1.2 to 1.9 as described above, according to the test results, the titanium oxide layer functions to show an inclination angle frequency-distribution graph on which a highest peak of inclination angle frequency appears in an inclination angle interval range of 0 to 10 degrees, and the ratio of the sum of frequencies in the inclination angle frequency range of 0 to 10 degrees occupies 45% of the total sum of frequencies on the inclination angle frequency-distribution graph. Accordingly, when value Y is less than 1.2, the highest peak appears less in the range of 0 to 10 degrees on the inclination angle frequency-distribution graph of the heat-transformed α-type (Al, Ti) 2 O 3 layer. In other words, the ratio of the sum of frequencies in the range of 0 to 10 degrees may become less than 45% of the total sum of frequencies on the inclination angle frequency-distribution graph. In this case, as described above, a desired excellent high temperature strength cannot be secured in the heat-transformed α-type (Al, Ti) 2 O 3 layer, which leads to the failure in obtaining a desired chipping resistance. On the other hand, when value Y exceeds 1.9, the inclination angle interval in which the highest peak appears may deviates out of the range of 0 to 10 degrees. In this case, desired excellent high temperature strength cannot be secured in the heat-transformed α-type (Al, Ti) 2 O 3 layer. Thus, value Y is set to 1.2 to 1.9 in an atomic ratio to Ti.
Further, in this case, when the average layer thickness of the titanium oxide layer is less than 0.05 μm, the above-mentioned functions cannot be sufficiently obtained. On the other hand, since the above functions can be sufficiently obtained only with an average layer thickness of 1.5 μm, and the thickness beyond the limit is unnecessary, the average layer thickness of the titanium oxide layer is preferably set to 0.05 to 1.5 μm.
(c) Content ratio of Ti in the upper layer [a heat-transformed α-type (Al, Ti) 2 O 3 layer] and average layer thickness of the upper layer
The heat-transformed α-type (Al, Ti) 2 O 3 layer has excellent high temperature hardness and heat resistance by the presence of Al as a constituent element thereof, and has high temperature strength by the presence of Ti as a constituent element thereof. Thus, the heat-transformed α-type (Al, Ti) 2 O 3 layer exhibits excellent wear resistance and chipping resistance. However, when the content ratio (value X) of Ti is less than 0.01 in an atomic ratio (this is true of the following ratios) occupied in the total amount with Al, an effect to make crystal sufficiently fine cannot be exhibited. On the other hand, when the content ratio of Ti exceeds 0.05, instability is caused in the hexagonal crystal lattice, which makes it difficult to sufficiently transform a κ-type or θ-type crystal structure into an α-type crystal structure during the heat-transforming treatment. Thus, the content ratio (value X) of Ti is preferably set to 0.01 to 0.05.
Further, when the average layer thickness of the heat-transformed α-type (Al, Ti) 2 O 3 layer is less than 1 μm, the hard coating layer cannot be allowed to sufficiently exhibit wear resistance. On the other hand, when the average layer thickness of the heat-transformed α-type (Al, Ti) 2 O 3 layer is greater than 15 μm, chipping is apt to occur. Thus, the average layer thickness of the heat-transformed α-type (Al, Ti) 2 O 3 layer is preferably set to 1.15 μm.
Furthermore, for the purpose of identifying the cutting tool before and after the use thereof, a TiN layer having a gold color tone may be deposited, if desired. In this case, the average layer thickness of the TiN layer is preferably 0.1 to 1 μm. This is because, when the average layer thickness is less than 0.1 μm, a sufficient identification cannot be achieved, whereas the identification due to the TiN layer is sufficient with an average layer thickness of up to 1 μm.
Further, the inventors have obtained the following results (a) to (c) described below.
(a) On a surface of a tool substrate, the titanium compound layer as a lower layer is formed under normal conditions using a conventional chemical vapor deposition reactor. An Al 2 O 3 (hereinafter, referred to as a deposited κ, θ-Al 2 O 3 ) layer having a κ-type or θ-type crystal structure in a state formed by vapor deposition is formed under the same normal conditions.
Next, the surface of the deposited κ, θ-Al 2 O 3 layer is processed using the chemical vapor deposition reactor under the following conditions:
Composition of a reaction gas: in volume %, TiCl 4 : 0.2 to 3%, CO 2 : 0.2 to 10%, Ar: 5 to 50%, and H 2 : balance,
Temperature of reaction atmosphere: 800 to 1100° C.,
Pressure of reaction atmosphere: 4 to 70 kPa, and
Time: 15 to 60 min.
Then, a titanium oxide layer satisfying the composition formula: TiO X , (where value X to Ti is 1.2 to 1.9 in an atomic ratio when measured by Auger Electron Spectroscopy) and having an average layer thickness 0.05 to 1 μm are formed on the surface of the Al 2 O 3 layer.
In this state, heat-transforming treatment is carried out in an atmosphere of Ar gas, preferably, under the following conditions: a pressure of 7 to 50 kPa and a temperature of 1000 to 1200° C., to transform the Al 2 O 3 layer having the deposited κ, θ-Al 2 O 3 layer into an Al 2 O 3 layer having an α-type crystal structure. Then, by the operation of the titanium oxide layer formed on the surface of the deposited κ, θ-Al 2 O 3 layer before the transformation the transformation of the κ-type or θ-type crystal structure is wholly and simultaneously transformed into the α-type crystal structure and the progress of the heat transformation is markedly promoted. Thus, since cracks generated at the time of the transformation are simultaneously formed, the titanium oxide particulates are extremely finely, uniformly and dispersedly distributed, and the growth of crystal grains is markedly suppressed by the shortening of the heat-transforming treatment time. As a result, since the formed heat-transformed α-type Al 2 O 3 layer has a uniformed structure in which cracks generated by the transformation and crystal grains becomes fine over the entire layer, it has very strong resistance against mechanical and thermal impacts. Accordingly, in the coated cermet tool having a hard-coating layer composed of the transformed α-Al 2 O 3 layer as the upper layer and the titanium compound layer (this titanium compound layer does not exhibit any change during heat-transforming treatment under the above-mentioned conditions) as the lower layer, the transformed α-Al 2 O 3 layer exhibits excellent chipping resistance with the presence of the titanium compound layer having high strength. Thus, the occurrence of chipping in the hard-coating layer is markedly suppressed and the excellent wear resistance is exhibited for a prolonged period of time.
(b) As for the conventional α-type Al 2 O 3 layer known as the upper layer of a hard coating layer and the transformed α-Al 2 O 3 layer described in (a), when an inclination angle frequency-distribution graph is obtained from results of radiating electron beam onto crystal grains having a hexagonal crystal lattice in a measuring range of surfaces to be polished using a field-emission-type scanning electron microscope, as shown in schematic explanatory views of FIGS. 1( a ) and 1 ( b ), measuring an inclination angle of a normal line of the plane (0001) as a crystal plane in which each of the crystal grains is formed with respect to each of the polished surfaces, sorting the measured inclination angles in a range of 0 to 45 degrees among all the measured inclination angles into several intervals at a pitch of 0.25 degrees, and summing up the frequencies in each of the intervals, the conventional deposited α-Al 2 O 3 layer, as illustrated in FIG. 6 , shows an inclination angle frequency-distribution graph on which the distribution of measured inclination angles of the plane (0001) is unbiased in a range of 0 to 45 degrees, whereas the transformed α-Al 2 O 3 layer, as illustrated in FIG. 5 , shows an inclination angle frequency-distribution graph on which a sharp and highest peak appears at a certain position in an inclination angle interval and the position of the sharp and highest peak appearing in the inclination angle interval on an X-axis of the graph varies depending on the variation of value X in the composition formula: TiO X of the titanium oxide layer.
(c) According to the test results, when value X to Ti in the composition formula: TiO X of the titanium oxide layer is set to 1.2 to 1.9 in an atomic ratio as described above, there is obtained an inclination angle frequency-distribution graph on which the sharp and highest peak appears in an inclination angle range of 0 to 10 degrees, and the sum of frequencies in the range of 0 to 10 degrees occupies 45% or more of the total sum of frequencies on the inclination angle frequency-distribution graph. In a coated cermet tool of the present invention deposited using, as the upper layer of the hard coating layer, a transformed α-Al 2 O 3 layer which shows the resulting inclination angle frequency-distribution graph on which the inclination angle frequency in the range of 0 to 10 degrees occupies 45% or more, and the highest peak appears in the inclination angle interval in the range of 0 to 10 degrees with the presence of the titanium compound layer as the lower layer, the coated cermet tool of the present invention exhibits more excellent wear resistance without causing chipping in a cutting edge, in particular, in the high-speed cutting, as compared to the conventional cermet tool.
The present invention has been achieved based on the above research results.
According to the present invention, there is provided a surface-coated cermet cutting tool with a hard-coating layer exhibiting excellent chipping resistance, the surface-coated cermet cutting tool being formed by coating, on a surface of a tool substrate made of tungsten carbide-based cemented carbide or titanium carbonitride-based cermet, the hard-coating layer composed of the following upper and lower layers (a) and (b):
(a) as the lower layer, a titanium compound layer having at least one or two of a titanium carbide layer, a titanium nitride layer, a titanium carbonitride layer, a titanium carboxide layer and a titanium oxycarbonitride layer, all of which are deposited by chemical vapor deposition, and the titanium compound layer having a total average layer thickness of 3 to 20 μm, and
(b) as the upper layer, a transformed α-Al 2 O 3 layer formed by carrying out a heat-transforming treatment in a state that a titanium oxide layer satisfying the composition formula: TiO X , (where value X is 1.2 to 1.9 in an atomic ratio to Ti when measured by Auger Electron Spectroscopy) is chemically deposited on a surface of a deposited κ, θ-Al 2 O 3 layer to thereby transform the crystal structure of the deposited κ, θ-Al 2 O 3 layer into an α-type crystal structure,
the transformed α-Al 2 O 3 layer showing an inclination angle frequency-distribution graph on which a highest peak appears in an inclination angle interval in a range of 0 to 10 degrees and the sum of frequencies in a range of 0 to 10 degrees occupies 45% or more of the total sum of frequencies on the inclination angle frequency-distribution graph wherein the inclination angle frequency-distribution graph is obtained from results of radiating electron beam onto crystal grains having a hexagonal crystal lattice in a measuring range of surfaces to be polished using a field-emission-type scanning electron microscope, measuring an inclination angle of a normal line of the plane (0001) as a crystal plane in which each of the crystal grains is formed with respect to each of the polished surfaces, sorting the measured inclination angles in a range of 0 to 45 degrees among all the measured inclination angles into several intervals at a pitch of 0.25 degrees, and summing up the frequencies in each of the intervals,
and the transformed α-Al 2 O 3 layer having an average layer thickness of 1 to 15 μm.
The reasons for limiting the numerical values in the layers constituting a hard coating layer of the coated cermet layer of the present invention as described above will be described below.
(a) Average layer thickness of a lower layer (Ti compound layer)
A titanium compound layer inherently has excellent high temperature strength, and the hard-coating layer has high temperature strength by virtue of the existence of the titanium compound layer. In addition, the titanium compound layer is firmly adhered to both of the tool substrate and the transformed α-type Al 2 O 3 layer that is the upper layer. Accordingly, it contributes to improving the adherence of the hard-coating layer to the tool substrate. However, when the total average layer thickness is less than 3 μm, the above function cannot be sufficiently obtained. On the other hand, when the total average layer thickness exceeds 20 μm, thermal plastic deformation is apt to occur, particularly in a high-speed intermittent cutting accompanied by the generation of high heat, which causes partial wear. Accordingly, the total average layer thickness is preferably set to 3 to 20 μm.
(b) Composition and average layer thickness of titanium oxide layer (value X)
As described above, by the operation of the titanium oxide layer the heating transformation of a deposited κ, θ-Al 2 O 3 layer is wholly and simultaneously transformed into an α-Al 2 O 3 layer to thereby make cracks generated at the time of heating transformation fine and uniform. In addition, the titanium oxide layer has a functions to promote the heating transformation and to suppress the growth of crystal grains by shortening the processing time. Moreover, when value X in the composition formula: TiO X of the titanium oxide layer is set to 1.2 to 1.9 as described above, according to the test results, the titanium oxide layer functions to show an inclination angle frequency-distribution graph on which a highest peak of inclination angle frequency appears in an inclination angle interval range of 0 to 10 degrees, and the ratio of the sum of frequencies in the inclination angle frequency range of 0 to 10 degrees occupies 45% of the total sum of frequencies on the inclination angle frequency-distribution graph. Accordingly, when value X is less than 1.2, the highest peak appears less in the range of 0 to 10 degrees on the inclination angle frequency-distribution graph of the transformed α-Al 2 O 3 layer. In other words, the ratio of the sum of frequencies in the range of 0 to 10 degrees may become less than 45% of the total sum of frequencies on the inclination angle frequency-distribution graph. In this case, as described above, desired excellent high temperature strength cannot be secured in the transformed α-Al 2 O 3 layer, which leads to the failure in obtaining a desired chipping resistance. On the other hand, when value X exceeds 1.9, the inclination angle interval in which the highest peak appears may deviates out of the range of 0 to 10 degrees. In this case, desired excellent high temperature strength cannot also be secured in the transformed α-Al 2 O 3 layer. Therefore, value X to Ti is preferably set to 1.2 to 1.9 in an atomic ratio.
Further, in this case, when the average layer thickness of the titanium oxide layer is less than 0.05 μm, the above-mentioned functions cannot be sufficiently obtained. On the other hand, since the above functions can be sufficiently obtained only with an average layer thickness of 1 μm, and the thickness beyond the limit is unnecessary, the average layer thickness of the titanium oxide layer is preferably set to 0.05 to 1 μm.
(c) Average layer thickness of an upper layer (a transformed α-Al 2 O 3 layer)
The transformed α-Al 2 O 3 layer functions to improve the wear resistance of the hard coating layer by virtue of the high temperature hardness and excellent heat resistance possessed by Al 2 O 3 itself and to markedly suppress the occurrence of chipping in the hard coating layer even in the high-speed cutting by virtue of its inherent excellent resistance against thermal or mechanical impacts (chipping resistance), as described above. However, when the average layer thickness of the transformed α-Al 2 O 3 layer is less than 1 μm, the above function cannot be sufficiently obtained. On the other hand, when the average layer thickness of the transformed α-Al 2 O 3 layer exceeds 15 μm, chipping is apt to occur. Accordingly, the average layer thickness of the transformed α-Al 2 O 3 layer is preferably set to 1 to 15 μm.
Furthermore, for the purpose of identifying the cutting tool before and after the use thereof, a TiN layer having a gold color tone may be deposited, if desired. In this case, the average layer thickness of the TiN layer is preferably 0.1 to 1 μm. This is because, when the average layer thickness is less than 0.1 μm, a sufficient identification cannot be obtained, whereas the identification due to the TiN layer is sufficient with an average layer thickness of up to 1 μm.
In the coated cermet tool according to the present invention, the heat-transformed α-type (Al, Zr) 2 O 3 layer constituting the upper layer of the hard-coating layer exhibits excellent high temperature hardness and heat resistance, and further excellent chipping resistance even in the high-speed intermittent cutting of steel or cast iron accompanied with very high mechanical and thermal impacts. Thus, the excellent wear resistance is exhibited without causing chipping in the hard coating layer.
In the coated cermet tool according to the present invention, the heat-transformed α-type (Al, Cr) 2 O 3 layer constituting the upper layer of the hard-coating layer exhibits excellent high temperature hardness and heat resistance, and further excellent chipping resistance even in the high-speed intermittent cutting of steel or cast iron accompanied with very high mechanical and thermal impacts. Thus, the excellent wear resistance is exhibited without causing chipping in the hard coating layer.
In the coated cermet tool according to the present invention, the heat-transformed α-type (Al, Ti) 2 O 3 layer constituting the upper layer of the hard-coating layer exhibits excellent high temperature hardness and heat resistance, and further excellent chipping resistance even in the high-speed intermittent cutting of steel or cast iron accompanied with very high mechanical and thermal impacts. Thus, the excellent wear resistance is exhibited without causing chipping in the hard coating layer.
In the coated cermet tool according to the present invention, the transformed α-Al 2 O 3 layer constituting the upper layer of the hard-coating layer exhibits excellent chipping resistance even in the high-speed intermittent cutting of steel or cast iron accompanied very high mechanical and thermal impacts and high heat generation. Thus, the excellent wear resistance is exhibited for a prolonged period of time.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic explanatory view illustrating a measuring range of an inclination angle of the plane (0001) of crystal grains in various kinds of a heat-transformed α-type (Al, Zr) 2 O 3 layer, a heat-transformed α-type (Al, Cr) 2 O 3 layer, a heat-transformed α-type (Al, Ti) 2 O 3 layer, a transformed α-Al 2 O 3 layer and a deposited α-type Al 2 O 3 layer, which constitute a hard coating layer;
FIG. 2 is an inclination angle frequency-distribution graph of the plane (0001) of a heat-transformed α-type (Al, Zr) 2 O 3 layer which constitutes a hard coating layer of a coated cermet tool 2 of the present invention as shown in Table 5;
FIG. 3 is an inclination angle frequency-distribution graph of the plane (0001) of a heat-transformed α-type (Al, Cr) 2 O 3 layer which constitutes a hard coating layer of a coated cermet tool 2 of the present invention as shown in Table 9;
FIG. 4 is an inclination angle frequency-distribution graph of the plane (0001) of a heat-transformed α-type (Al, Ti) 2 O 3 layer which constitutes a hard coating layer of a coated cermet tool 2 of the present invention as shown in Table 13;
FIG. 5 is an inclination angle frequency-distribution graph of the plane (0001) of a transformed α-Al 2 O 3 layer which constitutes a hard coating layer of a coated cermet tool 2 of the present invention as shown in Table 17; and
FIG. 6 is an inclination angle distribution graph of the plane (0001) of a deposited α-type Al 2 O 3 layer which constitutes a hard coating layer of a conventional coated cermet tool.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Hereinafter, coated cermet tools according to the present invention will be described in detail by examples with reference to the accompanying drawings.
EXAMPLE 1
The following powders, each having a mean particle size in a range of 1 to 3 μm, were prepared as raw materials for substrates: WC powder, TiC powder, ZrC powder, VC powder, TaC powder, NbC powder, Cr 3 C 2 powder, TiN powder, TaN powder and Co powder. Those raw powders were compounded with each other based on the compounding compositions shown in Table 1, mixed with each other in an acetone solution having wax added thereto for 24 hours using a ball mill and were dried under reduced pressure. Thereafter, the resulting powder mixtures were press-formed into green compacts having predetermined shape at a pressure of 98 Mpa. The green compacts were then sintered in a vacuum under the following conditions: a pressure of 5 Pa, a predetermined temperature in a range of 1370 to 1470° C., and a holding duration of 1 hour. After sintering, cutting edges were subjected to horning (R: 0.07 mm) to manufacture tool substrates A to F made of WC-based cemented carbide and having throwaway tip shapes defined in ISO•CNMG120408.
Further, the following powders, each having a mean particle size in a range of 0.5 to 2 μm, were prepared as raw materials for substrates: TiCN (TiC/TiN=50/50 in weight ratio) powder, Mo 2 C power, ZrC power, NbC powder, TaC powder, WC power, Co powder and Ni powder. Those raw powders were compounded with each other based on the compounding composition shown in Table 2, wet-mixed with each other for 24 hours using a ball mill and were dried. Thereafter, the resulting powder mixtures were press-formed into green compacts at a pressure of 98 MPa. The green compacts were then sintered in a nitrogen atmosphere under the following conditions: a pressure of 1.3 kPa, a temperature of 1540° C., and a holding duration of 1 hour. After sintering, cutting edges were subjected to horning (R:0.07 mm) to manufacture tool substrates a to f made of TiCN-based cermet and having tip shapes defined in ISO Standard•CNMG120412.
Next, by using a general chemical vapor deposition reactor, on the surfaces of the tool substrates A to F and a to f, titanium compound layers as lower layers of the hard-coating layers were deposited with combinations and target layer thickness shown in Table 5 under conditions shown in Table 3 (in Table 3, l-TiCN represents formation conditions of TiCN layers having a lengthwise growth crystal structure described in Japanese Unexamined Patent Application Publication No. 6-8010, and the others represent formation conditions of general granular crystal structure). Next, similarly, (Al, Zr) 2 O 3 layers having a κ-type or θ-type crystal structure were deposited with combinations and target layer thickness shown in Table 5 under conditions shown in Table 3. Subsequently, on a surface of each of the (Al, Zr) 2 O 3 layers having κ-type or θ-type crystal structure, a titanium oxide layer was deposited with a combination shown in Table 5 under conditions shown in Table 4. In this state, heat-transforming treatment was performed in an Ar atmosphere under the following conditions: a pressure of 30 kPa, a temperature of 1100° C., and a predetermined holding duration in a range of 20 to 100 minutes to transform the (Al, Zr) 2 O 3 layers having a κ-type or θ-type crystal structure into (Al, Zr) 2 O 3 layers having an α-type crystal structure. As a result, coated cermet tools 1 to 13 of the present invention having the heat-transformed α-type (Al, Zr) 2 O 3 layers as upper layers of the hard-coating layers were manufactured, respectively.
Furthermore, in manufacturing the coated cermet tools 1 to 13 of the present invention, separate test pieces are prepared, and those test pieces were loaded into the same chemical vapor deposition reactor. The test pieces were taken out of the chemical vapor deposition reactor at the time when the titanium oxide layers are formed on the surfaces of the test pieces, and compositions (value Y) and layer thickness of the titanium oxide layers were measured (the longitudinal sections of the layers were measured) using Auger Electron Spectroscopy or a scanning electron microscope. As a result, all the coated cermet tools showed substantially the same compositions and average layer thickness (the average value of values measured at five points) as the target compositions and target layer thickness.
For the purpose of comparison, as shown in Table 6, the deposited α-type Al 2 O 3 layers as upper layers of the hard-coating layers with target layer thickness shown in Table 6 were formed under the same conditions as those shown in Table 3. Then, the conventional cermet tools 1 to 13 were manufactured under the same conditions as the above ones except that the formation of the titanium oxide layers and the heat-transforming treatment under the conditions mentioned above were not performed.
Next, an inclination angle frequency-distribution graph of the heat-transformed α-type (Al, Zr) 2 O 3 layers and the deposited α-type Al 2 O 3 layers that constitute the hard-coating layers of the coated cermet tools of the present invention and conventional cermet tools was drawn up using a field-emission-type scanning electron microscope.
Specifically, the inclination angle frequency-distribution graphs were drawn up through the following steps. First, the test pieces are set in a lens-barrel of a field-emission-type scanning electron microscope, using the surfaces of the heat-transformed α-type (Al, Zr) 2 O 3 layers and deposited α-type Al 2 O 3 layers thereof as surfaces to be polished. Then, electron beam having an acceleration voltage of 15 kV are individually radiated on crystal grains having the hexagonal crystal lattice in a measuring range of the polished surfaces with an irradiating current of 1 nA at an incidence angle of 70 degrees with respect to the polished surfaces. Next, an inclination angle of a normal line of the plane (0001) as a crystal plane in which each of the crystal grains is formed with respect to a normal line of each of the polished surface was measured at an interval of 0.1 μm/step for an area of 30×50 μm, using an electron backscattering diffraction image device. Based on these measurement results, among all the measured inclination angles, the measured inclination angles in a range of 0 to 45 degrees are sorted into several intervals at a pitch of 0.25 degrees, and the frequencies in each sorted interval are summed up.
In the resulting inclination angle frequency-distribution graphs of the various heat-transformed α-type (Al, Zr) 2 O 3 layers and deposited α-type Al 2 O 3 layers, an inclination angle interval in which the plane (0001) shows the highest peak, and the ratio occupied by the inclination angle frequencies in an inclination angle interval ranging from 0 to 10 degrees to all the inclination angle frequencies on the inclination angle frequency-distribution graph is shown in Tables 5 and 6, respectively.
In the above various inclination angle frequency-distribution graphs, as shown in Tables 5 and 6, respectively, all the heat-transformed α-type (Al, Zr) 2 O 3 layers of the coated cermet tool of the present invention show an inclination angle frequency-distribution graph on which the measured inclination angle distribution of the plane (0001) shows the highest peak in the inclination angle interval in a range of 0 to 10 degrees and on which the ratio of the inclination angle frequencies in the inclination angle interval ranging from 0 to 10 degrees is 45% or more. To the contrary, all the deposited α-type Al 2 O 3 layers of the conventional coated cermet tools 1 to 13 show an inclination angle frequency-distribution graph on which the distribution of measured inclination angles of the plane (0001) is unbiased in a range of 0 to 45 degrees, the highest peak does not appear, and the ratio of the inclination angle frequencies in the inclination angle interval ranging from 0 to 10 degrees is 23% or less.
In addition, FIG. 2 illustrates an inclination angle frequency-distribution graph of the heat-transformed α-type (Al, Zr) 2 O 3 layer of the coated cermet tool 2 of the present invention, and FIG. 6 illustrates an angle frequency-distribution graph of the deposited α-type Al 2 O 3 layer of the conventional coated cermet tool 10 .
Moreover, as for the coated cermet tools 1 to 13 of the present invention and the conventional coated cermet tools 1 to 13 , when the layers that constitute the hard coating layers of the coated cermet tools are observed using an electron probe micro-analyzer (EPMA) or the Auger Electron Spectroscopy (when the longitudinal sections of the layers are observed), it was found that all the coated cermet tools 1 to 13 of the present invention are composed of a Ti compound layer and a heat-transformed α-type (Al, Zr) 2 O 3 layer, which have substantially the same compositions as the target compositions, and the Ti compound layer deposited before heat-transforming treatment also exists in the surfaces of the tools. On the other hand, it was found that all the conventional cermet tools 1 to 13 are composed of a Ti compound layer and a deposited α-type Al 2 O 3 layer, which have substantially the same compositions as the target compositions. Further, when the thickness of layers constituting the hard-coating layers of the coated cermet tools was measured by using a scanning electron microscope (similarly, the longitudinal sections of the layers were measured), all the coated cermet tools had substantially the same average layer thickness (the average value of values measured at five points) as the target layer thickness.
Next, in a state in which each of the above-mentioned various coated cermet tools was screw-fixed to a tip of a bite made of tool steel with a fixing jig, the coated cermet tools 1 to 13 of the present invention and the conventional coated cermet tools 1 to 13 were subjected to the following tests:
(1) a dry high-speed intermittent cutting test of alloyed steel (normal cutting speed is 200 m/min) under the following conditions:
Workpiece: a JIS•SCM 420 round bar having four longitudinal grooves equidistantly arranged in the longitudinal direction,
Cutting speed: 450 m/min,
Depth of cut: 1.5 mm,
Feed rate: 0.3 mm/rev,
Cutting time: 5 min,
(2) a dry high-speed intermittent cutting test of carbon steel (normal cutting speed is 250 m/min) under the following conditions:
Workpiece: a JIS•S25C round bar having four longitudinal grooves equidistantly arranged in the longitudinal direction,
Cutting speed: 450 m/min,
Depth of cut: 1.5 mm,
Feed rate: 0.35 mm/rev,
Cutting time: 5 min,
(3) a dry high-speed intermittent cutting test of cast iron (normal cutting speed is 250 m/min) under the following conditions:
Workpiece: a JIS•FC250 round bar having four longitudinal grooves equidistantly arranged in the longitudinal direction,
Cutting speed: 500 m/min,
Depth of cut: 1.5 mm,
Feed rate: 0.3 mm/rev,
Cutting time: 5 min,
Then, the width of flank wear of a cutting edge was measured in each test. The measurement results are shown in Table 7.
TABLE 1
Compounding Composition (mass %)
Type
Co
TiC
ZrC
VC
TaC
NbC
Cr 3 C 2
TiN
TaN
WC
Tool
A
7
—
—
—
—
—
—
—
—
Balance
Substrate
B
5.7
—
—
—
1.5
0.5
—
—
—
Balance
C
5.7
—
—
—
—
—
1
—
—
Balance
D
8.5
—
0.5
—
—
—
0.5
—
—
Balance
E
12.5
2
—
—
—
—
—
1
2
Balance
F
14
—
—
0.2
—
—
0.8
—
—
Balance
TABLE 2
Compounding Composition (mass %)
Type
Co
Ni
ZrC
TaC
NbC
Mo 2 C
WC
TiCN
Tool
a
13
5
—
10
—
10
16
Balance
Substrate
b
8
7
—
5
—
7.5
—
Balance
c
5
—
—
—
—
6
10
Balance
d
10
5
—
11
2
—
—
Balance
e
9
4
1
8
—
10
10
Balance
f
12
5.5
—
10
—
9.5
14.5
Balance
TABLE 3
Layer Constituting Hard
Formation Condition (kPa denotes pressure of
Coating Layer
reaction atmosphere, and ° C. denotes temperature
Target
thereof)
Composition
Reaction Gas Composition
Reaction Atmosphere
Type
(atomic ratio)
(volume %)
Pressure
Temperature
TiC
TiC
TiCl 4 : 4.2%, CH 4 : 8.5%,
7
1020
H 2 : Balance
TiN (First
TiN
TiCl 4 : 4.2%, N 2 : 30%, H 2 : Balance
30
900
Layer)
TiN (Other
TiN
TiCl 4 : 4.2%, N 2 : 35%, H 2 : Balance
50
1040
Layers)
l-TiCN
l-TiC 0.5 N 0.5
TiCl 4 : 4.2%, N 2 : 20%, CH 3 CN:
7
900
0.6%, H 2 : Balance
TiCN
TiC 0.5 N 0.5
TiCl 4 : 4.2%, N 2 : 20%, CH 4 : 4%,
12
1020
H 2 : Balance
TiCO
TiC 0.5 O 0.5
TiCl 4 : 4.2%, CO: 4%, H 2 : Balance
7
1020
TiCNO
TiC 0.3 N 0.3 O 0.4
TiCl 4 : 4.2%, CO: 3%, CH 4 : 3%,
20
1020
N 2 : 20%, H 2 : Balance
Deposited
α-Al 2 O 3
AlCl 3 : 2.2%, CO 2 : 5.5%, HCl:
7
1000
α-type
2.2%, H 2 S: 0.2%, H 2 : Balance
Al 2 O 3
Deposited
Zr (Value X):
AlCl 3 : 3.7%, ZrCl 4 : 0.03%, CO 2 :
7
950
κ-type
0.003
5.5%, HCl: 2.2%, H 2 S: 0.2%,
MO: A
H 2 : Balance
Deposited
Zr (Value X):
AlCl 3 : 3.6%, ZrCl 4 : 0.1%, CO 2 :
7
800
θ-type
0.01
5.5%, HCl: 2.2%, H 2 S: 0.2%,
MO: B
H 2 : Balance
Deposited
Zr (Value X):
AlCl 3 : 3.53% ZrCl 4 : 0.17%, CO 2 :
7
950
κ-type
0.017
5.5%, HCl: 2.2%, H 2 S: 0.2%,
MO: C
H 2 : Balance
Deposited
Zr (Value X):
AlCl 3 : 3.46%, ZrCl 4 : 0.24%, CO 2 :
7
800
θ-type
0.024
5.5%, HCl: 2.2%, H 2 S: 0.2%,
MO: D
H 2 : Balance
Deposited
Zr (Value X):
AlCl 3 : 3.4%, ZrCl 4 : 0.3%, CO 2 :
7
950
κ-type
0.03
5.5%, HCl: 2.2%, H 2 S: 0.2%,
MO: E
H 2 : Balance
Deposited
Zr (Value X):
AlCl 3 : 3.33%, ZrCl 4 : 0.37%, CO 2 :
7
800
θ-type
0.037
5.5%, HCl: 2.2%, H 2 S: 0.2%,
MO: F
H 2 : Balance
Deposited
Zr (Value X):
AlCl 3 : 3.27%, ZrCl 4 : 0.43%, CO 2 :
7
950
κ-type
0.043
5.5%, HCl: 2.2%, H 2 S: 0.2%,
MO: G
H 2 : Balance
Deposited
Zr (Value X):
AlCl 3 : 3.2%, ZrCl 4 : 0.5%, CO 2 :
7
800
θ-type
0.05
5.5%, HCl: 2.2%, H 2 S: 0.2%,
MO: H
H 2 : Balance
(In Table 3, MO denotes (Al, Zr) 2 O 3 .)
TABLE 4
Thin Ti Oxide Layer
Target
Formation Condition
Composition
Reaction Atmosphere
(atomic
Reaction Gas
Pressure
Temperature
Type
ratio)
Composition (volume %)
(kPa)
(° C.)
1
TiO 1.20
TiCl 4 : 0.5%, CO 2 : 0.2%,
30
1020
Ar: 40%, H 2 : Balance
2
TiO 1.35
TiCl 4 : 3%, CO 2 : 5%, Ar:
7
1000
40%, H 2 : Balance
3
TiO 1.50
TiCl 4 : 3%, CO 2 : 10%,
14
1000
Ar: 50%, H 2 : Balance
4
TiO 1.60
TiCl 4 : 1%, CO 2 : 4.5%,
7
1000
Ar: 40%, H 2 : Balance
5
TiO 1.75
TiCl 4 : 1%, CO 2 : 8%, Ar:
7
950
10%, H 2 : Balance
6
TiO 1.90
TiCl 4 : 0.2%, CO 2 : 5%,
7
900
Ar: 5%, H 2 : Balance
TABLE 5
Heat-Transformed α-type
Ti Oxide Layer
MO Layer
Hard Coating Layer (numeral in parentheses
Target
Inclination
Tool
denotes target layer thickness: μm)
Layer
Angle
Substrate
First
Second
Third
Fourth
Fifth
Thickness
Interval
Frequency
Type
Symbol
Layer
Layer
Layer
Layer
Layer
Symbol
(μm)
(degrees)
Ratio (%)
Coated
1
A
TiN (1)
l-TiCN (17.5)
TiN (1)
TiCNO
Deposited
IV
0.5
6.25-6.50
69
Cermet
(0.5)
θ-type
Tool of
MO: D (13)
Present
2
B
TiCN (1)
l-TiCN (8.5)
TiCO
Deposited
—
II
1
3.25-3.50
79
Invention
(0.5)
κ-type
MO: F (5)
3
C
TiN (1)
l-TiCN (4)
TiC (4)
TiCNO (1)
Deposited
V
0.05
0.00-0.25
75
κ-type
MO: H (15)
4
D
TiC (1)
l-TiCN (9)
Deposited
—
—
II
0.1
9.75-10.00
45
θ-type
MO: G (1)
5
E
TiN (1)
l-TiCN (4.5)
TiCO (0.5)
Deposited
—
I
0.5
2.00-2.25
85
κ-type
MO :A (5)
6
F
TiN (0.5)
l-TiCN (1.5)
TiC (0.5)
TiCNO
Deposited
III
1.5
1.75-2.00
88
(0.5)
κ-type
MO: B (3)
7
A
TiN (1)
l-TiCN (8)
TiCNO (0.5)
Deposited
—
III
0.5
2.50-2.75
90
κ-type
MO: C (8)
8
a
TiN (1)
TiCN (19)
Deposited
—
—
IV
1
0.75-1.00
76
κ-type
MO: E (10)
9
b
TiC (0.5)
l-TiCN (9)
TiCO (0.5)
Deposited
—
VI
0.05
8.25-8.50
51
θ-type
MO: H (4)
10
c
TiN (1)
TiC (1)
TiCN (7)
TiCO (1)
Deposited
III
1.5
7.00-7.25
68
θ-type
MO: F (15)
11
d
TiN (1)
TiC (1)
l-TiCN (8)
Deposited
—
V
0.1
4.00-4.25
82
κ-type
MO: E (7)
12
e
TiC (1)
l-TiCN (4)
TiCNO (1)
Deposited
—
VI
0.3
7.25-7.50
66
θ-type
MO: C (12)
13
f
TiCN (0.5)
TiC (2)
TiCNO (0.5)
Deposited
—
I
0.5
9.50-9.75
48
θ-type
MO: A (1)
[In Table 5, MO denotes (Al, Zr) 2 O 3 ; Inclination Angle Interval represents an inclination angle interval in which the plane (0001) shows the highest peak; Frequency Ratio represents a frequency ratio in an inclination angle interval of 0 to 10 degrees]
TABLE 6
Deposited α-type Al 2 O 3
Layer
Hard Coating Layer (numeral in parentheses
Inclination
Tool
denotes target layer thickness: μm)
Angle
Substrate
First
Second
Third
Fourth
Fifth
Interval
Frequency
Type
Symbol
Layer
Layer
Layer
Layer
Layer
(degrees)
Ratio (%)
Conventional
1
A
TiN (1)
l-TiCN (17.5)
TiN (1)
TiCNO (0.5)
Deposited
Non
11
Coated
α-type
existence
Cermet Tool
Al 2 O 3 (13)
2
B
TiCN (1)
l-TiCN (8.5)
TiCO (0.5)
Deposited
—
Non
18
α-type
existence
Al 2 O 3 (5)
3
C
TiN (1)
l-TiCN (4)
TiC (4)
TiCNO (1)
Deposited
Non
23
α-type
existence
Al 2 O 3 (15)
4
D
TiC (1)
l-TiCN (9)
Deposited
—
—
Non
10
α-type
existence
Al 2 O 3 (1)
5
E
TiN (1)
l-TiCN (4.5)
TiCO (0.5)
Deposited
—
Non
17
α-type
existence
Al 2 O 3 (5)
6
F
TiN (0.5)
l-TiCN (1.5)
TiC (0.5)
TiCNO (0.5)
Deposited
Non
20
α-type
existence
Al 2 O 3 (3)
7
A
TiN (1)
l-TiCN (8)
TiCNO (0.5)
Deposited
—
Non
11
α-type
existence
Al 2 O 3 (8)
8
a
TiN (1)
TiCN (19)
Deposited
—
—
Non
15
α-type
existence
Al 2 O 3 (10)
9
b
TiC (0.5)
l-TiCN (9)
TiCO (0.5)
Deposited
—
Non
21
α-type
existence
Al 2 O 3 (4)
10
c
TiN (1)
TiC (1)
TiCN (7)
TiCO (1)
Deposited
Non
23
α-type
existence
Al 2 O 3 (15)
11
d
TiN (1)
TiC (1)
l-TiCN (8)
Deposited
—
Non
12
α-type
existence
Al 2 O 3 (7)
12
e
TiC (1)
l-TiCN (4)
TiCNO (1)
Deposited
—
Non
16
α-type
existence
Al 2 O 3 (12)
13
f
TiCN (0.5)
TiC (2)
TiCNO (0.5)
Deposited
—
Non
18
α-type
existence
Al 2 O 3 (1)
[In Table 6, Inclination Angle Interval represents an inclination angle interval in which the plane (0001) shows the highest peak; Frequency Ratio represents a frequency ratio in an inclination angle interval of 0 to 10 degrees]
TABLE 7
Width of Flank Wear
(mm)
Cutting Test Result
Alloy
Carbon
Cast
Alloy
Carbon
Type
Steel
Steel
Iron
Type
Steel
Steel
Cast Iron
Coated Cermet
1
0.17
0.16
0.17
Conventional
1
Usable life of
Usable life of
Usable life of
Tool of Present
Coated Cermet
1.6 minutes
1.5 minutes
1.8 minutes
Invention
2
0.13
0.11
0.14
Tool
2
Usable life of
Usable life of
Usable life of
1.7 minutes
1.5 minutes
1.9 minutes
3
0.11
0.12
0.12
3
Usable life of
Usable life of
Usable life of
1.5 minutes
1.4 minutes
1.6 minutes
4
0.21
0.18
0.20
4
Usable life of
Usable life of
Usable life of
1.9 minutes
1.8 minutes
2.0 minutes
5
0.15
0.14
0.16
5
Usable life of
Usable life of
Usable life of
2.1 minutes
2.2 minutes
1.9 minutes
6
0.17
0.16
0.18
6
Usable life of
Usable life of
Usable life of
2.3 minutes
2.5 minutes
1.8 minutes
7
0.12
0.10
0.12
7
Usable life of
Usable life of
Usable life of
1.8 minutes
1.7 minutes
1.8 minutes
8
0.11
0.11
0.13
8
Usable life of
Usable life of
Usable life of
0.6 minutes
0.7 minutes
0.8 minutes
9
0.20
0.19
0.21
9
Usable life of
Usable life of
Usable life of
1.3 minutes
1.4 minutes
1.3 minutes
10
0.17
0.16
0.18
10
Usable life of
Usable life of
Usable life of
0.8 minutes
0.7 minutes
0.9 minutes
11
0.13
0.12
0.15
11
Usable life of
Usable life of
Usable life of
1.1 minutes
1.0 minutes
1.2 minutes
12
0.19
0.17
0.20
12
Usable life of
Usable life of
Usable life of
1.0 minutes
1.1 minutes
1.0 minutes
13
0.25
0.23
0.27
13
Usable life of
Usable life of
Usable life of
1.4 minutes
1.3 minutes
1.1 minutes
(In Table 7, usable life is caused from chipping generated on hard coating layer.)
As apparent from the results shown in Tables 5 to 7, in all the cermet tools 1 to 13 of the present invention in which the upper layers of the hard coating layers are composed of a heat-transformed α-type (Al, Zr) 2 O 3 showing an inclination angle frequency-distribution graph on which the inclination angle of the plane (0001) shows the highest peak in an inclination angle interval in a range of 0 to 10 degrees and the ratio of the sum of frequencies in the inclination angle interval ranging from 0 to 10 degrees occupy 45% or more, the heat-transformed α-type (Al, Zr) 2 O 3 layers exhibit excellent chipping resistance in high-speed intermittent cutting of steel or cast iron accompanied with very high mechanical and thermal impacts and high heat generation. As a result, occurrence of chipping in cutting edges is suppressed markedly and the excellent wear resistance is exhibited. To the contrary, in all the conventional coated cermet tools 1 to 13 in which the upper layers of the hard coating layers are composed of a deposited α-type Al 2 O 3 layer showing an inclination angle frequency-distribution graph on which the distribution of measured inclination angles of the plane (0001) is unbiased in a range from 0 to 45 degrees, and the highest peak does not appear, the deposited α-type Al 2 O 3 layers could not resist to severe mechanical and thermal impacts in high-speed intermittent cutting to generate chipping in the cutting edges, consequently shortening the usable life of the conventional cermet cutting tools.
EXAMPLE 2
The following powders, each having a mean particle size in a range of 1 to 3 μm, were prepared as raw materials for substrates: WC powder, TiC powder, ZrC powder, VC powder, TaC powder, NbC powder, Cr 3 C 2 powder, TiN powder, TaN powder and Co powder. Those raw powders were compounded with each other based on the compounding compositions shown in Table 1, mixed with each other in an acetone solution having wax added thereto for 24 hours using a ball mill and were dried under reduced pressure. Thereafter, the resulting powder mixtures were press-formed into green compacts having predetermined shape at a pressure of 98 Mpa. The green compacts were then sintered in a vacuum under the following conditions: a pressure of 5 Pa, a predetermined temperature in a range of 1370 to 1470° C., and a holding duration of 1 hour. After sintering, cutting edges were subjected to horning (R: 0.07 mm) to manufacture tool substrates A to F made of WC-based cemented carbide and having throwaway tip shapes defined in ISO•CNMG120408.
Further, the following powders, each having a mean particle size in a range of 0.5 to 2 μm, were prepared as raw materials for substrates: TiCN (TiC/TiN=50/50 in weight ratio) powder, Mo 2 C power, ZrC power, NbC powder, TaC powder, WC power, Co powder and Ni powder. Those raw powders were compounded with each other based on the compounding composition shown in Table 2, wet-mixed with each other for 24 hours using a ball mill and were dried. Thereafter, the resulting powder mixtures were press-formed into green compacts at a pressure of 98 MPa. The green compacts were then sintered in a nitrogen atmosphere under the following conditions: a pressure of 1.3 kPa, a temperature of 1540° C., and a holding duration of 1 hour. After sintering, cutting edges were subjected to horning (R: 0.07 mm) to manufacture tool substrates a to f made of TiCN-based cermet and having tip shapes defined in ISO Standard•CNMG120412.
Next, by using a general chemical vapor deposition reactor, on the surfaces of the tool substrates A to F and a to f, titanium compound layers as lower layers of the hard-coating layers were deposited with combinations and target layer thickness shown in Table 9 under conditions shown in Table 8 (in Table 8, l-TiCN represents formation conditions of TiCN layers having a lengthwise growth crystal structure described in Japanese Unexamined Patent Application Publication No. 6-8010, and the others represent formation conditions of general granular crystal structure). Next, similarly, (Al, Cr) 2 O 3 layers having a κ-type or θ-type crystal structure were deposited with combinations and target layer thickness shown in Table 9 under conditions shown in Table 8. Subsequently, on the surfaces of the (Al, Cr) 2 O 3 layers having a κ-type or θ-type crystal structure, a titanium oxide layer was deposited with combinations shown in Table 9 under conditions shown in Table 4. In this state, heat-transforming treatment was performed in an Ar atmosphere under the following conditions: a pressure of 30 kPa, a temperature of 1100° C., and a predetermined holding duration in a range of 20 to 100 minutes to transform the (Al, Cr) 2 O 3 layers having a κ-type or θ-type crystal structure into (Al, Cr) 2 O 3 layers having an α-type crystal structure. As a result, coated cermet tools 1 to 13 of the present invention having the heat-transformed α-type (Al, Cr) 2 O 3 layers as upper layers of the hard-coating layers were manufactured, respectively.
Furthermore, in manufacturing the coated cermet tools 1 to 13 of the present invention, separate test pieces are prepared, and those test pieces were loaded into the same chemical vapor deposition reactor. The test pieces were taken out of the chemical vapor deposition reactor at the time when the titanium oxide layers are formed on the surfaces of the test pieces, and compositions (value Y) and layer thickness of the titanium oxide layers were measured (the longitudinal sections of the layers were measured) using Auger Electron Spectroscopy or a scanning electron microscope. As a result, all the coated cermet tools showed substantially the same compositions and average layer thickness (the average value of values measured at five points) as the target compositions and target layer thickness.
For the purpose of comparison, as shown in Table 10, the deposited α-type Al 2 O 3 layers as upper layers of the hard-coating layers with target layer thickness shown in Table 10 were formed under the same conditions as those shown in Table 8. Then, conventional cermet tools 1 to 13 were manufactured under the same conditions as the above ones except that the formation of the titanium oxide layer and the heat-transforming treatment under the conditions mentioned above were not performed.
Next, an inclination angle frequency-distribution graph of the heat-transformed α-type (Al, Cr) 2 O 3 layers and the deposited α-type Al 2 O 3 layers that constitute the hard-coating layers of the coated cermet tools of the present invention and conventional cermet tools was drawn up using a field-emission-type scanning electron microscope.
Specifically, the inclination angle frequency-distribution graphs were drawn up through the following steps. First, the test pieces tools are set in a lens-barrel of a field-emission-type scanning electron microscope, using the surfaces of the heat-transformed α-type (Al, Cr) 2 O 3 layers and deposited α-type Al 2 O 3 layers thereof as surfaces to be polished. Then, electron beam having an acceleration voltage of 15 kV are individually radiated on crystal grains having the hexagonal crystal lattice in a measuring range of the polished surfaces with an irradiating current of 1 nA at an incidence angle of 70 degrees with respect to the polished surfaces. Next, an inclination angle of a normal line of the plane (0001) as a crystal plane in which each of the crystal grains is formed with respect to a normal line of each of the polished surface was measured at an interval of 0.1 μm/step for an area of 30×50 μm, using an electron backscattering diffraction image device. Based on these measurement results, among all the measured inclination angles, the measured inclination angles in a range of 0 to 45 degrees are sorted into several intervals at a pitch of 0.25 degrees, and the frequencies in each sorted interval are summed up.
In the resulting inclination angle frequency-distribution graphs of the various heat-transformed α-type (Al, Cr) 2 O 3 layers and deposited α-type Al 2 O 3 layers, an inclination angle interval in which the plane (0001) shows the highest peak, and the ratio occupied by the inclination angle frequencies in an inclination angle interval ranging from 0 to 10 degrees to all the inclination angle frequencies on the inclination angle frequency-distribution graph is shown in Tables 9 and 10, respectively.
In the above various inclination angle frequency-distribution graphs, as shown in Tables 9 and 10, respectively, all the heat-transformed α-type (Al, Cr) 2 O 3 layers of the coated cermet tool of the present invention show an inclination angle frequency-distribution graph on which the measured inclination angle distribution of the plane (0001) shows the highest peak in the inclination angle interval in a range of 0 to 10 degrees and on which the ratio of the inclination angle frequencies in the inclination angle interval ranging from 0 to 10 degrees is 45% or more. To the contrary, all the deposited α-type Al 2 O 3 layers of the conventional coated cermet tools 1 to 13 show an inclination angle frequency-distribution graph on which the distribution of measured inclination angles of the plane (0001) is unbiased in a range of 0 to 45 degrees, the highest peak does not appear, and the ratio of the inclination angle frequencies in the inclination angle interval ranging from 0 to 10 degrees is 25% or less.
In addition, FIG. 3 illustrates an inclination angle frequency-distribution graph of the heat-transformed α-type (Al, Cr) 2 O 3 layer of the coated cermet tool 2 of the present invention, and FIG. 6 illustrates an angle frequency-distribution graph of the deposited α-type Al 2 O 3 layer of the conventional coated cermet tool 10 .
Moreover, as for the coated cermet tools 1 to 13 of the present invention and the conventional coated cermet tools 1 to 13 , when the layers that constitute the hard coating layers of the coated cermet tools are observed using an electron probe micro-analyzer (EPMA) or the Auger electron Spectroscopy (when the longitudinal sections of the layers are observed), it was found that all the coated cermet tools 1 to 13 of the present invention are composed of a Ti compound layer and a heat-transformed α-type (Al, Cr) 2 O 3 layer, which have substantially the same compositions as the target compositions, and the Ti compound layer deposited before heat-transforming treatment also exists in the surface of the tools. On the other hand, it was found that all the conventional cermet tools 1 to 13 are composed of a Ti compound layer and a deposited α-type Al 2 O 3 layer, which have substantially the same compositions as the target compositions. Further, when the thickness of layers constituting the hard-coating layers of the coated cermet tools was measured by using a scanning electron microscope (similarly, the longitudinal sections of the layers were measured), all the coated cermet tools had substantially the same average layer thickness (the average value of values measured at five points) as the target layer thickness.
Next, in a state in which each of the above-mentioned various coated cermet tools was screw-fixed to a tip of a bite made of tool steel with a fixing jig, the coated cermet tools 1 to 13 of the present invention and the conventional coated cermet tools 1 to 13 were subjected to the following tests:
(1) a dry high-speed intermittent cutting test of alloyed steel (normal cutting speed is 200 m/min) under the following conditions:
Workpiece: a JIS•SCM 440 round bar having four longitudinal grooves equidistantly arranged in the longitudinal direction,
Cutting speed: 350 m/min,
Depth of cut: 1.5 mm,
Feed rate: 0.2 mm/rev,
Cutting time: 10 min,
(2) a dry high-speed intermittent cutting test of carbon steel (normal cutting speed is 250 m/min) under the following conditions:
Workpiece: a JIS•S30C round bar having four longitudinal grooves equidistantly arranged in the longitudinal direction,
Cutting speed: 450 m/min,
Depth of cut: 2.0 mm,
Feed rate: 0.3 mm/rev,
Cutting time: 10 min,
(3) a dry high-speed intermittent cutting test of cast iron (normal cutting speed is 250 m/min) under the following
TABLE 8
Formation Condition (kPa denotes pressure of
Layer Constituting Hard Coating
reaction atmosphere, and ° C. denotes
Layer
temperature thereof)
Target Composition
Reaction Gas Composition
Reaction Atmosphere
Type
(atomic ratio)
(volume %)
Pressure
Temperature
TiC
TiC
TiCl 4 : 4.2%, CH 4 : 8.5%,
7
1020
H 2 : Balance
TiN (First
TiN
TiCl 4 : 4.2%, N 2 : 30%, H 2 :
30
900
Layer)
Balance
TiN (Other
TiN
TiCl 4 : 4.2%, N 2 : 35%, H 2 :
50
1040
Layers)
Balance
l-TiCN
l-TiC 0.5 N 0.5
TiCl 4 : 4.2%, N 2 : 20%,
7
900
CH 3 CN: 0.6%, H 2 : Balance
TiCN
TiC 0.5 N 0.5
TiCl 4 : 4.2%, N 2 : 20%, CH 4 :
12
1020
4%, H 2 : Balance
TiCO
TiCC 0.5 O 0.5
TiCl 4 : 4.2%, CO: 4%, H 2 :
7
1020
Balance
TiCNO
TiC 0.3 N 0.3 O 0.4
TiCl 4 : 4.2%, CO: 3%, CH 4 :
20
1020
3%, N 2 : 20%, H 2 : Balance
Deposited α-
α-Al 2 O 3
AlCl 3 : 2.2%, CO 2 : 5.5%,
7
1000
type Al 2 O 3
HCl: 2.2%, H 2 S: 0.2%, H 2 :
Balance
Deposited κ-
Cr (Value X): 0.005
AlCl 3 : 2.5%, CrCl 3 : 0.05%,
1
950
type MO: A
CO 2 : 2.2%, HCl: 3%, H 2 S:
0.1%, H 2 : Balance
Deposited θ-
Cr (Value X): 0.012
AlCl 3 : 2.5%, CrCl 3 : 0.08%,
1
800
type MO: B
CO 2 : 2.2%, HCl: 3%, H 2 S:
0.3%, H 2 : Balance
Deposited κ-
Cr (Value X): 0.02
AlCl 3 : 2.3% CrCl 3 : 0.08%,
7
950
type MO: C
CO 2 : 2.2%, HCl: 3%, H 2 S:
0.1%, H 2 : Balance
Deposited θ-
Cr (Value X): 0.025
AlCl 3 : 2.3%, CrCl 3 : 0.1%,
7
800
type MO: D
CO 2 : 2.2%, HCl: 3%, H 2 S:
0.3%, H 2 : Balance
Deposited κ-
Cr (Value X): 0.03
AlCl 3 : 2.2%, CrCl 3 : 0.1%,
7
950
type MO: E
CO 2 : 2%, HCl: 3%, H 2 S:
0.1%, H 2 : Balance
Deposited θ-
Cr (Value X): 0.035
AlCl 3 : 2.2%, CrCl 3 : 0.12%,
7
800
type MO: F
CO 2 : 2%, HCl: 3%, H 2 S:
0.3%, H 2 : Balance
Deposited κ-
Cr (Value X): 0.04
AlCl 3 : 2.2%, CrCl 3 : 0.15%,
7
950
type MO: G
CO 2 : 2%, HCl: 3%, H 2 S:
0.1%, H 2 : Balance
[In Table 8, MO denotes (Al, Cr) 2 O 3 ]
TABLE 9
Heat-Transformed α-
Ti Oxide Layer
type MO Layer
Hard Coating Layer (numeral in parentheses
Target
Inclination
Tool
denotes target layer thickness: μm)
Layer
Angle
Substrate
First
Second
Third
Fourth
Fifth
Thickness
Interval
Frequency
Type
Symbol
Layer
Layer
Layer
Layer
Layer
Symbol
(μm)
(degrees)
Ratio (%)
Coated
1
A
TiN (1)
l-TiCN (17.5)
TiN (1)
TiCNO
Deposited
III
0.5
9.75-10.00
45
Cermet
(0.5)
θ-type
Tool of
MO: B (15)
Present
2
B
TiCN (1)
l-TiCN (8.5)
TiCO (0.5)
Deposited
—
IV
1.5
3.25-3.50
77
Invention
κ-type
MO: A (9)
3
C
TiN (1)
l-TiCN (4)
TiC (4)
TiCNO (1)
Deposited
V
0.1
1.25-1.50
71
κ-type
MO: C (15)
4
D
TiC (1)
l-TiCN (9)
Deposited
—
—
II
0.8
0.00-0.25
69
θ-type
MO: D (3)
5
E
TiN (1)
l-TiCN (4.5)
TiCO
Deposited
—
I
1
4.25-4.50
89
κ-type
MO: E (5)
6
F
TiN (0.5)
l-TiCN (1.5)
TiC (0.5)
TiCNO
Deposited
III
2
5.75-6.00
83
(0.5)
κ-type
MO: G (3)
7
A
TiN (1)
l-TiCN (8)
TiCNO (0.5)
Deposited
—
VI
0.2
6.50-6.75
85
κ-type
MO: A (1)
8
a
TiN (1)
TiCN (19)
Deposited
—
—
IV
1.2
8.25-8.50
50
κ-type
MO: E (15)
9
b
TiC (0.5)
l-TiCN (9)
TiCO (0.5)
Deposited
—
V
1
4.75-5.00
79
κ-type
MO: D (10)
10
c
TiN (1)
TiC (1)
TiCN (7)
TiCO (1)
Deposited
III
0.2
8.50-8.75
53
θ-type
MO: D (15)
11
d
TiN (1)
TiC (1)
l-TiCN (8)
Deposited
—
VI
1.8
7.00-7.25
59
κ-type
MO: C (3)
12
e
TiC (1)
l-TiCN (4)
TiCNO (1)
Deposited
—
I
1.5
5.00-5.25
80
θ-type
MO: F (5)
13
f
TiCN (0.5)
TiC (2)
TiCNO (0.5)
Deposited
—
II
0.4
3.00-3.25
73
θ-type
MO: B (3)
[In Table 9, MO denotes (Al, Cr) 2 O 3 ; Inclination Angle Interval represents an inclination angle interval in which the plane (0001) shows the highest peak; Frequency Ratio represents a frequency ratio in an inclination angle interval of 0 to 10 degrees]
TABLE 10
Deposited α-type Al 2 O 3
Layer
Hard Coating Layer (numeral in parentheses
Inclination
Tool
denotes target layer thickness: μm)
Angle
Substrate
First
Second
Third
Fourth
Fifth
Interval
Frequency
Type
Symbol
Layer
Layer
Layer
Layer
Layer
(degrees)
Ratio (%)
Conventional
1
A
TiN (1)
l-TiCN (17.5)
TiN (1)
TiCNO (0.5)
Deposited
Non
13
Coated
α-type
existence
Cermet Tool
Al 2 O 3 (15)
2
B
TiCN (1)
l-TiCN (8.5)
TiCO (0.5)
Deposited
—
Non
20
α-type
existence
Al 2 O 3 (9)
3
C
TiN (1)
l-TiCN (4)
TiC (4)
TiCNO (1)
Deposited
Non
22
α-type
existence
Al 2 O 3 (15)
4
D
TiC (1)
l-TiCN (9)
Deposited
—
—
Non
10
α-type
existence
Al 2 O 3 (3)
5
E
TiN (1)
l-TiCN (4.5)
TiCO (0.5)
Deposited
—
Non
15
α-type
existence
Al 2 O 3 (5)
6
F
TiN (0.5)
l-TiCN (1.5)
TiC (0.5)
TiCNO
Deposited
Non
25
(0.5)
α-type
existence
Al 2 O 3 (3)
7
A
TiN (1)
l-TiCN (8)
TiCNO (0.5)
Deposited
—
Non
10
α-type
existence
Al 2 O 3 (1)
8
a
TiN (1)
TiCN (19)
Deposited
—
—
Non
21
α-type
existence
Al 2 O 3 (15)
9
b
TiC (0.5)
l-TiCN (9)
TiCO (0.5)
Deposited
—
Non
17
α-type
existence
Al 2 O 3 (10)
10
c
TiN (1)
TiC (1)
TiCN (7)
TiCO (1)
Deposited
Non
23
α-type
existence
Al 2 O 3 (15)
11
d
TiN (1)
TiC (1)
l-TiCN (8)
Deposited
—
Non
16
α-type
existence
Al 2 O 3 (3)
12
e
TiC (1)
l-TiCN (4)
TiCNO (1)
Deposited
—
Non
16
α-type
existence
Al 2 O 3 (5)
13
f
TiCN (0.5)
TiC (2)
TiCNO (0.5)
Deposited
—
Non
22
α-type
existence
Al 2 O 3 (3)
[In Table 10, Inclination Angle Interval represents an inclination angle interval in which the plane (0001) shows the highest peak; Frequency Ratio represents a frequency ratio in an inclination angle interval of 0 to 10 degrees]
TABLE 11
Width of Flank Wear
(mm)
Cutting Test Result
Alloy
Carbon
Cast
Alloy
Carbon
Type
Steel
Steel
Iron
Type
Steel
Steel
Cast Iron
Coated Cermet
1
0.40
0.47
0.48
Conventional
1
Usable life of
Usable life of
Usable life of
Tool of Present
Coated Cermet
3.2 minutes
3.5 minutes
3.9 minutes
Invention
2
0.18
0.20
0.22
Tool
2
Usable life of
Usable life of
Usable life of
5.3 minutes
6.0 minutes
6.5 minutes
3
0.21
0.23
0.24
3
Usable life of
Usable life of
Usable life of
4.9 minutes
5.7 minutes
6.1 minutes
4
0.26
0.28
0.30
4
Usable life of
Usable life of
Usable life of
4.7 minutes
5.2 minutes
5.8 minutes
5
0.20
0.22
0.23
5
Usable life of
Usable life of
Usable life of
5.0 minutes
5.8 minutes
6.3 minutes
6
0.32
0.34
0.36
6
Usable life of
Usable life of
Usable life of
4.5 minutes
5.0 minutes
5.4 minutes
7
0.35
0.41
0.43
7
Usable life of
Usable life of
Usable life of
3.8 minutes
4.0 minutes
4.2 minutes
8
0.28
0.30
0.33
8
Usable life of
Usable life of
Usable life of
4.6 minutes
5.0 minutes
5.6 minutes
9
0.22
0.24
0.25
9
Usable life of
Usable life of
Usable life of
4.8 minutes
5.5 minutes
6.0 minutes
10
0.39
0.45
0.46
10
Usable life of
Usable life of
Usable life of
3.2 minutes
3.8 minutes
4.0 minutes
11
0.35
0.40
0.42
11
Usable life of
Usable life of
Usable life of
4.0 minutes
4.5 minutes
4.8 minutes
12
0.24
0.25
0.27
12
Usable life of
Usable life of
Usable life of
4.7 minutes
5.3 minutes
6.0 minutes
13
0.34
0.37
0.39
13
Usable life of
Usable life of
Usable life of
4.4 minutes
4.7 minutes
5.0 minutes
(In Table 11, usable life is caused from chipping generated on hard coating layer.)
As apparent from the results shown in Tables 9 to 11, in all the cermet tools 1 to 13 of the present invention in which the upper layers of the hard coating layers are composed of a heat-transformed α-type (Al, Cr) 2 O 3 showing an inclination angle frequency-distribution graph on which the inclination angle of the plane (0001) shows the highest peak in an inclination angle interval in a range of 0 to 10 degrees and the ratio of the sum of frequencies in the inclination angle interval ranging from 0 to 10 degrees occupy 45% or more, the heat-transformed α-type (Al, Cr) 2 O 3 layers exhibit excellent chipping resistance in high-speed intermittent cutting of steel or cast iron accompanied with very high mechanical and thermal impacts and high heat generation. As a result, occurrence of chipping in cutting edges is suppressed markedly and the excellent wear resistance is exhibited. To the contrary, in all the conventional coated cermet tools 1 to 13 in which the upper layers of the hard coating layers are composed of a deposited α-type Al 2 O 3 layer showing an inclination angle frequency-distribution graph on which the distribution of measured inclination angles of the plane (0001) is unbiased in a range from 0 to 45 degrees, and the highest peak does not appear, the deposited α-type Al 2 O 3 layers could not resist to severe mechanical and thermal impacts in high-speed intermittent cutting to generate chipping in the cutting edges, consequently shortening the usable life of the conventional cermet cutting tools.
EXAMPLE 3
The following powders, each having a mean particle size in a range of 1 to 3 μm, were prepared as raw materials for substrates: WC powder, TiC powder, ZrC powder, VC powder, TaC powder, NbC powder, Cr 3 C 2 powder, TiN powder, TaN powder and Co powder. Those raw powders were compounded with each other based on the compounding compositions shown in Table 1, mixed with each other in an acetone solution having wax added thereto for 24 hours using a ball mill and were dried under reduced pressure. Thereafter, the resulting powder mixtures were press-formed into green compacts having predetermined shape at a pressure of 98 Mpa. The green compacts were then sintered in a vacuum under the following conditions: a pressure of 5 Pa, a predetermined temperature in a range of 1370 to 1470° C., and a holding duration of 1 hour. After sintering, cutting edges were subjected to horning (R: 0.07 mm) to manufacture tool substrates A to F made of WC-based cemented carbide and having throwaway tip shapes defined in ISO•CNMG120408.
Further, the following powders, each having a mean particle size in a range of 0.5 to 2 μm, were prepared as raw materials for substrates: TiCN (TiC/TiN=50/50 in weight ratio) powder, Mo 2 C power, ZrC power, NbC powder, TaC powder, WC power, Co powder and Ni powder. Those raw powders were compounded with each other based on the compounding composition shown in Table 2, wet-mixed with each other for 24 hours using a ball mill and were dried. Thereafter, the resulting powder mixtures were press-formed into green compacts at a pressure of 98 MPa. The green compacts were then sintered in a nitrogen atmosphere under the following conditions: a pressure of 1.3 kPa, a temperature of 1540° C., and a holding duration of 1 hour. After sintering, cutting edges were subjected to horning (R: 0.07 mm) to manufacture tool substrates a to f made of TiCN-based cermet and having tip shapes defined in ISO•Standard CNMG120412.
Next, by using a general chemical vapor deposition reactor, on the surfaces of the tool substrates A to F and a to f, titanium compound layers as lower layers of the hard-coating layers were deposited with combinations and target layer thickness shown in Table 13 under conditions shown in Table 12 (in Table 12, l-TiCN represents formation conditions of TiCN layers having a lengthwise growth crystal structure described in Japanese Unexamined Patent Application Publication No. 6-8010, and the others represent formation conditions of general granular crystal structure). Next, similarly, (Al, Ti) 2 O 3 layers having a κ-type or θ-type crystal structure were deposited with combinations and target layer thickness shown in Table 13 under conditions shown in Table 12. Subsequently, on the surfaces of the (Al, Ti) 2 O 3 layers having a κ-type or θ-type crystal structure, a titanium oxide layer was deposited with combinations shown in Table 13 under conditions shown in Table 4. In this state, heat-transforming treatment was performed in an Ar atmosphere under the following conditions: a pressure of 30 kPa, a temperature of 1100° C., and a predetermined holding duration in a range of 20 to 100 minutes to transform the (Al, Ti) 2 O 3 layers having a κ-type or θ-type crystal structure into (Al, Ti) 2 O 3 layers having an α-type crystal structure. As a result, coated cermet tools 1 to 13 of the present invention having the heat-transformed α-type (Al, Ti) 2 O 3 layers as upper layers of the hard-coating layers were manufactured, respectively.
Furthermore, in manufacturing the coated cermet tools 1 to 13 of the present invention, separate test pieces are prepared, and those test pieces were loaded into the same chemical vapor deposition reactor. The test pieces were taken out of the chemical vapor deposition reactor at the time when the titanium oxide layers are formed on the surfaces of the test pieces, and compositions (value Y) and layer thickness of the titanium oxide layers were measured (the longitudinal sections of the layers were measured) using Auger Electron Spectroscopy or a scanning electron microscope. As a result, all the coated cermet tools showed substantially the same compositions and average layer thickness (the average value of values measured at five points) as the target compositions and target layer thickness.
For the purpose of comparison, as shown in Table 14, the deposited α-type Al 2 O 3 layers as upper layers of the hard-coating layers with target layer thickness shown in Table 14 were formed under the same conditions as those shown in Table 12. Then, conventional cermet tools 1 to 13 were manufactured under the same conditions as the above ones except that the formation of the titanium oxide layer and the heat-transforming treatment under the conditions mentioned above were not performed.
Next, an inclination angle frequency-distribution graph of the heat-transformed α-type (Al, Ti) 2 O 3 layers and the deposited α-type Al 2 O 3 layers that constitute the hard-coating layers of the coated cermet tools of the present invention and conventional cermet tools was drawn up using a field-emission-type scanning electron microscope.
Specifically, the inclination angle frequency-distribution graphs were drawn up through the following steps. First, the test pieces tools are set in a lens-barrel of a field-emission-type scanning electron microscope, using the surfaces of the heat-transformed α-type (Al, Ti) 2 O 3 layers and deposited α-type Al 2 O 3 layers thereof as surfaces to be polished. Then, electron beam having an acceleration voltage of 15 kV are individually radiated on crystal grains having the hexagonal crystal lattice in a measuring range of the polished surfaces with an irradiating current of 1 nA at an incidence angle of 70 degrees with respect to the polished surfaces. Next, an inclination angle of a normal line of the plane (0001) as a crystal plane in which each of the crystal grains is formed with respect to a normal line of each of the polished surface was measured at an interval of 0.1 μm/step for an area of 30×50 μm, using an electron backscattering diffraction image device. Based on these measurement results, among all the measured inclination angles, the measured inclination angles in a range of 0 to 45 degrees are sorted into several intervals at a pitch of 0.25 degrees, and the frequencies in each sorted interval are summed up.
In the resulting inclination angle frequency-distribution graphs of the various heat-transformed α-type (Al, Ti) 2 O 3 layers and deposited α-type Al 2 O 3 layers, an inclination angle interval in which the plane (0001) shows the highest peak, and the ratio occupied by the inclination angle frequencies in an inclination angle interval ranging from 0 to 10 degrees to all the inclination angle frequencies on the inclination angle frequency-distribution graph is shown in Tables 13 and 14, respectively.
In the above various inclination angle frequency-distribution graphs, as shown in Tables 13 and 14, respectively, all the heat-transformed α-type (Al, Ti) 2 O 3 layers of the coated cermet tool of the present invention show an inclination angle frequency-distribution graph on which the measured inclination angle distribution of the plane (0001) shows the highest peak in the inclination angle interval in a range of 0 to 10 degrees and on which the ratio of the inclination angle frequencies in the inclination angle interval ranging from 0 to 10 degrees is 45% or more. To the contrary, all the deposited α-type Al 2 O 3 layers of the conventional coated cermet tools 1 to 13 show an inclination angle frequency-distribution graph on which the distribution of measured inclination angles of the plane (0001) is unbiased in a range of 0 to 45 degrees, the highest peak does not appear, and the ratio of the inclination angle frequencies in the inclination angle interval ranging from 0 to 10 degrees is 25% or less.
In addition, FIG. 4 illustrates an inclination angle frequency-distribution graph of the heat-transformed α-type (Al, Ti) 2 O 3 layer of the coated cermet tool 2 of the present invention, and FIG. 6 illustrates an angle frequency-distribution graph of the deposited α-type Al 2 O 3 layer of the conventional coated cermet tool 10 .
Moreover, as for the coated cermet tools 1 to 13 of the present invention and the conventional coated cermet tools 1 to 13 , when the layers that constitute the hard coating layers of the coated cermet tools are measured using an electron probe micro-analyzer (EPMA) or the Auger Electron Spectroscopy (when the longitudinal sections of the layers are observed), it was found that all the coated cermet tools 1 to 13 of the present invention are composed of a Ti compound layer and a heat-transformed α-type (Al, Ti) 2 O 3 layer, which have substantially the same compositions as the target compositions, and the Ti compound layer deposited before heat-transforming treatment also exists in the surfaces of the tools. On the other hand, it was found that all the conventional cermet tools 1 to 13 are composed of a Ti compound layer and a deposited α-type Al 2 O 3 layer, which have substantially the same compositions as the target compositions. Further, when the thickness of layers constituting the hard-coating layers of the coated cermet tools was measured by using a scanning electron microscope (similarly, the longitudinal sections of the layers were measured), all the coated cermet tools had substantially the same average layer thickness (the average value of values measured at five points) as the target layer thickness.
Next, in a state in which each of the above-mentioned various coated cermet tools was screw-fixed to a tip of a bite made of tool steel with a fixing jig, the coated cermet tools 1 to 13 of the present invention and the conventional coated cermet tools 1 to 13 were subjected to the following tests:
(1) a dry high-speed intermittent cutting test of alloyed steel (normal cutting speed is 200 m/min) under the following conditions:
Workpiece: a JIS•SCM 415 round bar having four longitudinal grooves equidistantly arranged in the longitudinal direction,
Cutting speed: 400 m/min,
Depth of cut: 1.5 mm,
Feed rate: 0.35 mm/rev,
Cutting time: 5 min,
(2) a dry high-speed intermittent cutting test of carbon steel (normal cutting speed is 250 m/min) under the following conditions:
Workpiece: a JIS•S35C round bar having four longitudinal grooves equidistantly arranged in the longitudinal direction,
Cutting speed: 450 m/min,
Depth of cut: 1.5 mm,
Feed rate: 0.25 mm/rev,
Cutting time: 5 min,
(3) a dry high-speed intermittent cutting test of cast iron (normal cutting speed is 250 m/min) under the following conditions:
Workpiece: a JIS•FC150 round bar having four longitudinal grooves equidistantly arranged in the longitudinal direction,
Cutting speed: 550 m/min,
Depth of cut: 1.5 mm,
Feed rate: 0.3 mm/rev,
Cutting time: 5 min,
Then, the width of flank wear of a cutting edge was measured in each test. The measurement results are shown in Table 15.
TABLE 12
Layer Constituting Hard
Formation Condition (kPa denotes pressure of
Coating Layer
reaction atmosphere, and ° C. denotes temperature
Target
thereof)
Composition
Reaction Gas Composition
Reaction Atmosphere
Type
(atomic ratio)
(volume %)
Pressure
Temperature
TiC
TiC
TiCl 4 : 4.2%, CH 4 : 8.5%, H 2 :
7
1020
Balance
TiN (First
TiN
TiCl 4 : 4.2%, N 2 : 30%, H 2 :
30
900
Layer)
Balance
TiN (Other
TiN
TiCl 4 : 4.2%, N 2 : 35%, H 2 :
50
1040
Layers)
Balance
l-TiCN
l-TiC 0.5 N 0.5
TiCl 4 : 4.2%, N 2 : 20%, CH 3 CN:
7
900
0.6%, H 2 : Balance
TiCN
TiC 0.5 N 0.5
TiCl 4 : 4.2%, N 2 : 20%, CH 4 : 4%,
12
1020
H 2 : Balance
TiCO
TiC 0.5 O 0.5
TiCl 4 : 4.2%, CO: 4%, H 2 :
7
1020
Balance
TiCNO
TiC 0.3 N 0.3 O 0.4
TiCl 4 : 4.2%, CO: 3%, CH 4 : 3%,
20
1020
N 2 : 20%, H 2 : Balance
Deposited α-type
α-Al 2 O 3
AlCl 3 : 2.2%, CO 2 : 5.5%, HCl:
7
1000
Al 2 O 3
2.2%, H 2 S: 0.2%, H 2 : Balance
Deposited κ-type
Ti (Value X):
AlCl 3 : 3.27%, TiCl 4 : 0.03%,
7
950
MO: A
0.01
CO 2 : 5.5%, HCl: 2.2%, H 2 S:
0.2%, H 2 : Balance
Deposited θ-type
Ti (Value X):
AlCl 3 : 4.24%, TiCl 4 : 0.07%,
7
800
MO: B
0.015
CO 2 : 5.5%, HCl: 2.2%, H 2 S:
0.2%, H 2 : Balance
Deposited κ-type
Ti (Value X):
AlCl 3 : 3.23% TiCl 4 : 0.07%,
7
950
MO: C
0.02
CO 2 : 5.5%, HCl: 2.2%, H 2 S:
0.2%, H 2 : Balance
Deposited θ-type
Ti (Value X):
AlCl 3 : 4.19%, TiCl 4 : 0.11%,
7
800
MO: D
0.025
CO 2 : 5.5%, HCl: 2.2%, H 2 S:
0.2%, H 2 : Balance
Deposited κ-type
Ti (Value X):
AlCl 3 : 3.20%, TiCl 4 : 0.10%,
7
950
MO: E
0.03
CO 2 : 5.5%, HCl: 2.2%, H 2 S:
0.2%, H 2 : Balance
Deposited θ-type
Ti (Value X):
AlCl 3 : 4.15%, TiCl 4 : 0.15%,
7
800
MO: F
0.035
CO 2 : 5.5%, HCl: 2.2%, H 2 S:
0.2%, H 2 : Balance
Deposited κ-type
Ti (Value X):
AlCl 3 : 3.17%, TiCl 4 : 0.13%,
7
950
MO: G
0.04
CO 2 : 5.5%, HCl: 2.2%, H 2 S:
0.2%, H 2 : Balance
Deposited θ-type
Ti (Value X):
AlCl 3 : 4.09%, TiCl 4 : 0.22%,
7
800
MO: H
0.05
CO 2 : 5.5%, HCl: 2.2%, H 2 S:
0.2%, H 2 : Balance
[In Table 12, MO denotes (Al, Ti) 2 O 3 ]
TABLE 13
Heat-Transformed α-type
Ti Oxide Layer
MO Layer
Hard Coating Layer (numeral in parentheses
Target
Inclination
Tool
denotes target layer thickness: μm)
Layer
Angle
Substrate
First
Second
Third
Fourth
Fifth
Thickness
Interval
Frequency
Type
Symbol
Layer
Layer
Layer
Layer
Layer
Symbol
(μm)
(degrees)
Ratio (%)
Coated
1
A
TiN (1)
l-TiCN (17.5)
TiN (1)
TiCNO
Deposited
I
0.25
8.50-8.75
55
Cermet
(0.5)
θ-type
Tool of
MO: B (15)
Present
2
B
TiCN (1)
l-TiCN (8.5)
TiCO (0.5)
Deposited
—
IV
0.5
3.25-3.50
77
Invention
κ-type
MO: A (9)
3
C
TiN (1)
l-TiCN (4)
TiC (4)
TiCNO (1)
Deposited
VI
0.65
0.00-0.25
65
κ-type
MO: C (15)
4
D
TiC (1)
l-TiCN (9)
Deposited
—
—
II
0.05
7.75-8.00
60
θ-type
MO: D (3)
5
E
TiN (1)
l-TiCN (4.5)
TiCO (0.5)
Deposited
—
I
1.2
2.50-2.75
68
κ-type
MO: E (5)
6
F
TiN (0.5)
l-TiCN (1.5)
TiC (0.5)
TiCNO
Deposited
III
1.5
3.50-3.75
83
(0.5)
κ-type
MO: G (3)
7
A
TiN (1)
l-TiCN (8)
TiCNO (0.5)
Deposited
—
II
0.1
0.75-1.00
81
κ-type
MO: A (1)
8
a
TiN (1)
TiCN (19)
Deposited
—
—
IV
0.9
4.00-4.25
88
κ-type
MO: G (15)
9
b
TiC (0.5)
l-TiCN (9)
TiCO (0.5)
Deposited
—
V
0.75
9.75-10.00
45
κ-type
MO: H (10)
10
c
TiN (1)
TiC (1)
TiCN (7)
TiCO (1)
Deposited
III
1.5
9.25-9.50
50
θ-type
MO: D (15)
11
d
TiN (1)
TiC (1)
l-TiCN (8)
Deposited
—
V
1
6.25-6.50
72
κ-type
MO: C (3)
12
e
TiC (1)
l-TiCN (4)
TiCNO (1)
Deposited
—
III
0.5
8.25-8.50
58
θ-type
MO: F (5)
13
f
TiCN (0.5)
TiC (2)
TiCNO (0.5)
Deposited
—
VI
1.1
9.00-9.25
48
θ-type
MO: B (3)
[In Table 13, MO denotes (Al, Ti) 2 O 3 ; Inclination Angle Interval represents an inclination angle interval in which the plane (0001) shows the highest peak; Frequency Ratio represents a frequency ratio in an inclination angle interval of 0 to 10 degrees]
TABLE 14
Deposited α-type Al 2 O 3
Layer
Hard Coating Layer (numeral in parentheses
Inclination
Tool
denotes target layer thickness: μm)
Angle
Substrate
First
Second
Third
Fourth
Fifth
Interval
Frequency
Type
Symbol
Layer
Layer
Layer
Layer
Layer
(degrees)
Ratio (%)
Conventional
1
A
TiN (1)
l-TiCN (17.5)
TiN (1)
TiCNO
Deposited
Non
12
Coated
(0.5)
α-type
existence
Cermet Tool
Al 2 O 3 (15)
2
B
TiCN (1)
l-TiCN (8.5)
TiCO (0.5)
Deposited
—
Non
17
α-type
existence
Al 2 O 3 (9)
3
C
TiN (1)
l-TiCN (4)
TiC (4)
TiCNO (1)
Deposited
Non
20
α-type
existence
Al 2 O 3 (15)
4
D
TiC (1)
l-TiCN (9)
Deposited
—
—
Non
25
α-type
existence
Al 2 O 3 (3)
5
E
TiN (1)
l-TiCN (4.5)
TiCO (0.5)
Deposited
—
Non
10
α-type
existence
Al 2 O 3 (5)
6
F
TiN (0.5)
l-TiCN (1.5)
TiC (0.5)
TiCNO
Deposited
Non
19
(0.5)
α-type
existence
Al 2 O 3 (3)
7
A
TiN (1)
l-TiCN (8)
TiCNO (0.5)
Deposited
—
Non
13
α-type
existence
Al 2 O 3 (1)
8
a
TiN (1)
TiCN (19)
Deposited
—
—
Non
22
α-type
existence
Al 2 O 3 (15)
9
b
TiC (0.5)
l-TiCN (9)
TiCO (0.5)
Deposited
—
Non
15
α-type
existence
Al 2 O 3 (10)
10
c
TiN (1)
TiC (1)
TiCN (7)
TiCO (1)
Deposited
Non
23
α-type
existence
Al 2 O 3 (15)
11
d
TiN (1)
TiC (1)
l-TiCN (8)
Deposited
—
Non
21
α-type
existence
Al 2 O 3 (3)
12
e
TiC (1)
l-TiCN (4)
TiCNO (1)
Deposited
—
Non
20
α-type
existence
Al 2 O 3 (5)
13
f
TiCN (0.5)
TiC (2)
TiCNO (0.5)
Deposited
—
Non
11
α-type
existence
Al 2 O 3 (3)
[In FIG. 14, Inclination Angle Interval represents an inclination angle interval in which the plane (0001) shows the highest peak; Frequency Ratio represents a frequency ratio in an inclination angle interval of 0 to 10 degrees]
TABLE 15
Width of Flank Wear
(mm)
Cutting Test Result
Alloy
Carbon
Cast
Alloy
Carbon
Type
Steel
Steel
Iron
Type
Steel
Steel
Cast Iron
Coated
1
0.15
0.14
0.17
Conventional
1
Usable
Usable
Usable
Cermet
Coated
life of
life of
life of
Tool of
Cermet
1.5
1.6
1.8
Present
Tool
minutes
minutes
minutes
Invention
2
0.10
0.10
0.11
2
Usable
Usable
Usable
life of
life of
life of
1.5
1.5
1.7
minutes
minutes
minutes
3
0.12
0.11
0.13
3
Usable
Usable
Usable
life of
life of
life of
1.3
1.4
1.7
minutes
minutes
minutes
4
0.18
0.16
0.19
4
Usable
Usable
Usable
life of
life of
life of
1.7
1.8
2.0
minutes
minutes
minutes
5
0.15
0.14
0.15
5
Usable
Usable
Usable
life of
life of
life of
2.0
2.2
2.1
minutes
minutes
minutes
6
0.17
0.17
0.19
6
Usable
Usable
Usable
life of
life of
life of
2.5
2.7
2.5
minutes
minutes
minutes
7
0.14
0.13
0.15
7
Usable
Usable
Usable
life of
life of
life of
1.6
1.6
1.8
minutes
minutes
minutes
8
0.11
0.10
0.12
8
Usable
Usable
Usable
life of
life of
life of
0.8
0.9
0.8
minutes
minutes
minutes
9
0.16
0.15
0.17
9
Usable
Usable
Usable
life of
life of
life of
1.2
1.2
1.4
minutes
minutes
minutes
10
0.13
0.12
0.13
10
Usable
Usable
Usable
life of
life of
life of
1.1
1.2
1.3
minutes
minutes
minutes
11
0.17
0.15
0.18
11
Usable
Usable
Usable
life of
life of
life of
1.5
1.6
1.7
minutes
minutes
minutes
12
0.19
0.18
0.20
12
Usable
Usable
Usable
life of
life of
life of
1.6
1.7
1.9
minutes
minutes
minutes
13
0.23
0.20
0.24
13
Usable
Usable
Usable
life of
life of
life of
1.8
1.9
2.1
minutes
minutes
minutes
(In Table 15, usable life is caused from chipping generated on hard coating layer.)
As apparent from the results shown in Tables 13 to 15, in all the cermet tools 1 to 13 of the present invention in which the upper layers of the hard coating layers are composed of a heat-transformed α-type (Al, Ti) 2 O 3 showing an inclination angle frequency-distribution graph on which the inclination angle of the plane (0001) shows the highest peak in an inclination angle interval in a range of 0 to 10 degrees and the ratio of the sum of frequencies in the inclination angle interval ranging from 0 to 10 degrees occupy 45% or more, the heat-transformed α-type (Al—Ti) 2 O 3 layers exhibit excellent chipping resistance in high-speed intermittent cutting of steel or cast iron accompanied with very high mechanical and thermal impacts and high heat generation. As a result, occurrence of chipping in cutting edges is suppressed markedly and the excellent wear resistance is exhibited. To the contrary, in all the conventional coated cermet tools 1 to 13 in which the upper layers of the hard coating layers are composed of a deposited α-type Al 2 O 3 layer showing an inclination angle frequency-distribution graph on which the distribution of measured inclination angles of the plane (0001) is unbiased in a range from 0 to 45 degrees, and the highest peak does not appear, the deposited α-type Al 2 O 3 layers could not resist to severe mechanical and thermal impacts in high-speed intermittent cutting to generate chipping in the cutting edges, consequently shortening the usable life of the conventional cermet cutting tools.
EXAMPLE 4
The following powders, each having a mean particle size in a range of 1 to 3 μm, were prepared as raw materials for substrates: WC powder, TiC powder, ZrC powder, VC powder, TaC powder, NbC powder, Cr 3 C 2 powder, TiN powder, TaN powder and Co powder. Those raw powders were compounded with each other based on the compounding compositions shown in Table 1, mixed with each other in an acetone solution having wax added thereto for 24 hours using a ball mill and were dried under reduced pressure. Thereafter, the resulting powder mixtures were press-formed into green compacts having predetermined shape at a pressure of 98 Mpa. The green compacts were then sintered in a vacuum under the following conditions: a pressure of 5 Pa, a predetermined temperature in a range of 1370 to 1470° C., and a holding duration of 1 hour. After sintering, cutting edges were subjected to horning (R: 0.07 mm) to manufacture tool substrates A to F made of WC-based cemented carbide and having throwaway tip shapes defined in ISO•CNMG120408.
Further, the following powders, each having a mean particle size in a range of 0.5 to 2 μm, were prepared as raw materials for substrates: TiCN (TiC/TiN=50/50 in weight ratio) powder, Mo 2 C power, ZrC power, NbC powder, TaC powder, WC power, Co powder and Ni powder. Those raw powders were compounded with each other based on the compounding composition shown in Table 2, wet-mixed with each other for 24 hours using a ball mill and were dried. Thereafter, the resulting powder mixtures were press-formed into green compacts at a pressure of 98 MPa. The green compacts were then sintered in a nitrogen atmosphere under the following conditions: a pressure of 1.3 kPa, a temperature of 1540° C., and a holding duration of 1 hour. After sintering, cutting edges were subjected to horning (R: 0.07 mm) to manufacture tool substrates a to f made of TiCN-based cermet and having tip shapes defined in ISO Standard•CNMG120412.
Next, by using a general chemical vapor deposition reactor, on the surfaces of the tool substrates A to F and a to f, titanium compound layers as lower layers of the hard-coating layers were deposited with combinations and target layer thickness shown in Table 17 under conditions shown in Table 16 (in Table 16, l-TiCN represents formation conditions of TiCN layers having a lengthwise growth crystal structure described in Japanese Unexamined Patent Application Publication No. 6-8010, and the others represent formation conditions of general granular crystal structure). Next, similarly, the deposited κ, θ-Al 2 O 3 layers were deposited with combinations and target layer thickness shown in Table 17 under conditions shown in Table 16. Subsequently, on the surfaces of the deposited κ, θ-Al 2 O 3 layers, a titanium oxide thin layer was deposited with combinations shown in Table 17 under conditions shown in Table 4. Heat-transforming treatment was performed in an Ar atmosphere under the following conditions: a pressure of 30 kPa, a temperature of 1100° C., and a predetermined holding duration in a range of 10 to 60 minutes to transform the deposited κ, θ-Al 2 O 3 layers into Al 2 O 3 layers having an α-type crystal structure. As a result, coated cermet tools 1 to 13 of the present invention having the transformed α-Al 2 O 3 layers as upper layers of the hard coating layers were manufactured, respectively.
Furthermore, in manufacturing the coated cermet tools 1 to 13 of the present invention, separate test pieces are prepared, and those test pieces were loaded into the same chemical vapor deposition reactor. The test pieces were taken out of the chemical vapor deposition reactor at the time when the thin titanium oxide thin layers are formed on the surfaces of the test pieces, and compositions (value X) and average layer thickness (μm) of the thin titanium oxide thin layer were measured (the longitudinal sections of the layers were measured) using Auger Electron Spectroscopy or a transmission electron microscope.
For the purpose of comparison, as shown in Table 18, the deposited α-type Al 2 O 3 layers as upper layers of the hard-coating layers with target layer thickness shown in Table 18 were formed under the same conditions as those shown in Table 16. Then, conventional cermet tools 1 to 13 were manufactured under the same conditions as the above ones except that the formation of the titanium oxide thin layer and the heat-transforming treatment under the conditions mentioned above were not performed.
Next, an inclination angle frequency-distribution graph of the heat-transformed α-type Al 2 O 3 layers and the deposited α-type Al 2 O 3 layers that constitute the hard-coating layers of the coated cermet tools of the present invention and conventional cermet tools was drawn up using a field-emission-type scanning electron microscope.
Specifically, the inclination angle frequency-distribution graphs were drawn up through the following steps. First, the test pieces tools are set in a lens-barrel of a field-emission-type scanning electron microscope, using the surfaces of the transformed α-Al 2 O 3 layers and deposited α-Al 2 O 3 layers thereof as surfaces to be polished. Then, electron beam having an acceleration voltage of 15 kV are individually radiated on crystal grains having the hexagonal crystal lattice in a measuring range of the polished surfaces with an irradiating current of 1 nA at an incidence angle of 70 degrees with respect to the polished surfaces. Next, an inclination angle of a normal line of the plane (0001) as a crystal plane in which each of the crystal grains is formed with respect to a normal line of each of the polished surface was measured at an interval of 0.1 μm/step for an area of 30×50 μm, using an electron backscattering diffraction image device. Based on these measurement results, among all the measured inclination angles, the measured inclination angles in a range of 0 to 45 degrees are sorted into several intervals at a pitch of 0.25 degrees, and the frequencies in each sorted interval are summed up.
In the resulting inclination angle frequency-distribution graphs of the various heat-transformed α-Al 2 O 3 layers and deposited α-Al 2 O 3 layers, an inclination angle interval in which the plane (0001) shows the highest peak, and the ratio occupied by the inclination angle frequencies in an inclination angle interval ranging from 0 to 10 degrees to all the inclination angle frequencies on the inclination angle frequency-distribution graph is shown in Tables 17 and 18, respectively.
In the above various inclination angle frequency-distribution graphs, as shown in Tables 17 and 18, respectively, all the α-Al 2 O 3 layers of the coated cermet tool of the present invention show an inclination angle frequency-distribution graph on which the measured inclination angle distribution of the plane (0001) shows the highest peak in the inclination angle interval in a range of 0 to 10 degrees and on which the ratio of the inclination angle frequencies in the inclination angle interval ranging from 0 to 10 degrees is 45% or more. To the contrary, all the deposited α-Al 2 O 3 layers of the conventional coated cermet tools 1 to 13 show an inclination angle frequency-distribution graph on which the distribution of measured inclination angles of the plane (0001) is unbiased in a range of 0 to 45 degrees, the highest peak does not appear, and the ratio of the inclination angle frequencies in the inclination angle interval ranging from 0 to 10 degrees is 25% or less.
In addition, FIG. 5 illustrates an inclination angle frequency-distribution graph of the transformed α-Al 2 O 3 layer of the coated cermet tool 9 of the present invention, and FIG. 6 illustrates an angle frequency-distribution graph of the deposited α-Al 2 O 3 layer of the conventional coated cermet tool 10 .
Moreover, as for the resulting coated cermet tools 1 to 13 of the present invention and the resulting conventional coated cermet tools 1 to 13 , when the layers that constitute the hard coating layers of the coated cermet tools are measured using the Auger Electron Spectroscopy (when the longitudinal sections of the layers are observed), it was found that all the coated cermet tools 1 to 13 of the present invention are composed of a Ti compound layer and a transformed α-Al 2 O 3 layer, which have substantially the same compositions as the target compositions, and the Ti compound layer deposited in the surfaces of the tools before heat-transforming treatment also has the substantially the same compositions in the above measurement as the target compositions. On the other hand, it was found that all the conventional cermet tools 1 to 13 are composed of a Ti compound layer and a deposited α-type Al 2 O 3 layer, which have substantially the same compositions as the target compositions. Moreover, when the thickness of layers constituting the hard coating layers of the coated cermet tools was measured by using a scanning electron microscope (similarly, the longitudinal sections of the layers were measured), all the coated cermet tools had substantially the same average layer thickness (the average value of values measured at five points) as the target layer thickness.
Next, in a state in which each of the above-mentioned various coated cermet tools was screw-fixed to a tip of a bite made of tool steel with a fixing jig, the coated cermet tools 1 to 13 of the present invention and the conventional coated cermet tools 1 to 13 were subjected to the following tests:
(1) a dry high-speed intermittent cutting test of alloyed steel (normal cutting speed is 200 m/min) under the following conditions:
Workpiece: a JIS•SCr 420H round bar having four longitudinal grooves equidistantly arranged in the longitudinal direction,
Cutting speed: 380 m/min,
Depth of cut: 1.5 mm,
Feed rate: 0.2 mm/rev,
Cutting time: 10 min,
(2) a dry high-speed intermittent cutting test of carbon steel (normal cutting speed is 200 m/min) under the following conditions:
Workpiece: a JIS•S40C round bar having four longitudinal grooves equidistantly arranged in the longitudinal direction,
Cutting speed: 350 m/min,
Depth of cut: 1.0 mm,
Feed rate: 0.25 mm/rev,
Cutting time: 10 min,
(3) a dry high-speed intermittent cutting test of cast iron (normal cutting speed is 200 m/min) under the following conditions:
Workpiece: a JIS•FCD450 round bar having four longitudinal grooves equidistantly arranged in the longitudinal direction,
Cutting speed: 400 m/min,
Depth of cut: 1.5 mm,
Feed rate: 0.3 mm/rev,
Cutting time: 10 min,
Then, the width of flank wear of a cutting edge was measured in each test. The measurement results are shown in Table 19.
TABLE 16
Layer Constituting Hard
Formation Condition (kPa denotes pressure of
Coating Layer
reaction atmosphere, and ° C. denotes temperature
Target
thereof)
Composition
Reaction Gas Composition
Reaction Atmosphere
Type
(atomic ratio)
(volume %)
Pressure
Temperature
TiC
TiC
TiCl 4 : 4.2%, CH 4 : 8.5%,
7
1020
H 2 : Balance
TiN (First
TiN
TiCl 4 : 4.2%, N 2 : 30%, H 2 :
30
900
Layer)
Balance
TiN (Other
TiN
TiCl 4 : 4.2%, N 2 : 35%, H 2 :
50
1040
Layers)
Balance
l-TiCN
l-TiC 0.5 N 0.5
TiCl 4 : 4.2%, N 2 : 20%,
7
900
CH 3 CN: 0.6%, H 2 : Balance
TiCN
TiC 0.5 N 0.5
TiCl 4 : 4.2%, N 2 : 20%, CH 4 :
12
1020
4%, H 2 : Balance
TiCO
TiC 0.5 O 0.5
TiCl 4 : 4.2%, CO: 4%, H 2 :
7
1020
Balance
TiCNO
TiC 0.3 N 0.3 O 0.4
TiCl 4 : 4.2%, CO: 3%, CH 4 :
20
1020
3%, N 2 : 20%, H 2 : Balance
Deposited
α-Al 2 O 3
AlCl 3 : 2.2%, CO 2 : 5.5%,
7
1000
α-Al 2 O 3
HCl: 2.2%, H 2 S: 0.2%, H 2 :
Balance
Deposited
κ-Al 2 O 3
AlCl 3 : 3.3%, CO 2 : 5.5%,
7
950
κ-Al 2 O 3
HCl: 2.2%, H 2 S: 0.2%, H 2 :
Balance
Deposited
θ-Al 2 O 3
AlCl 3 : 4.3%, CO 2 : 5.5%,
7
800
θ-Al 2 O 3
HCl: 1.2%, H 2 S: 0.2%, H 2 :
Balance
TABLE 17
Thin Ti Oxide
Layer
Transformed α-Al 2 O 3 Layer
Hard Coating Layer (numeral in parentheses
Target
Inclination
Tool
denotes target layer thickness: μm)
Layer
Angle
Substrate
First
Second
Third
Fourth
Fifth
Thickness
Interval
Frequency
Type
Symbol
Layer
Layer
Layer
Layer
Layer
Symbol
(μm)
(degrees)
Ratio (%)
Coated
1
A
TiN
l-TiCN
TiN (1)
TiCNO
Deposited
III
0.25
6.50-6.75
69
Cermet
(1)
(17.5)
(0.5)
α-Al 2 O 3
Tool of
(15)
Present
2
B
TiCN
l-TiCN
TiCO
Deposited
—
IV
0.70
4.25-4.50
70
Invention
(1)
(8.5)
(0.5)
κ-Al 2 O 3
(9)
3
C
TiN
l-TiCN
TiC (4)
TiCNO (1)
Deposited
I
0.30
8.00-8.25
53
(1)
(4)
κ-Al 2 O 3
(15)
4
D
TiC
l-TiCN
Deposited
—
—
VI
0.05
0.25-0.50
90
(1)
(9)
θ-Al 2 O 3 (3)
5
E
TiN
l-TiCN
TiCO
Deposited
—
II
0.80
7.75-8.00
61
(1)
(4.5)
(0.5)
κ-Al 2 O 3 (5)
6
F
TiN
l-TiCN
TiC (0.5)
TiCNO
Deposited
V
0.65
3.00-3.25
79
(0.5)
(1.5)
(0.5)
κ-Al 2 O 3
(3)
7
A
TiN
l-TiCN
TiCNO
Deposited
—
II
0.25
8.75-9.00
48
(1)
(8)
(0.5)
κ-Al 2 O 3
(1)
8
a
TiN
TiCN
Deposited
—
—
IV
0.55
5.50-5.75
68
(1)
(19)
κ-Al 2 O 3
(15)
9
b
TiC
l-TiCN
TiCO
Deposited
—
V
0.40
3.25-3.50
77
(0.5)
(9)
(0.5)
κ-Al 2 O 3
(10)
10
c
TiN
TiC
TiCN (7)
TiCO (1)
Deposited
II
0.70
7.75-8.00
59
(1)
(1)
θ-Al 2 O 3
(15)
11
d
TiN
TiC
l-TiCN
Deposited
—
VI
0.85
1.50-1.75
86
(1)
(1)
(8)
κ-Al 2 O 3
(3)
12
e
TiC
l-TiCN
TiCNO (1)
Deposited
—
I
0.15
9.75-10.00
45
(1)
(4)
κ-Al 2 O 3
(5)
13
f
TiCN
TiC
TiCNO
Deposited
—
III
1.00
4.25-4.50
66
(0.5)
(2)
(0.5)
θ-Al 2 O 3 (3)
(In Table 17, Inclination Angle Interval represents an inclination angle interval in which the plane (0001) shows the highest peak;
Frequency Ratio represents a frequency ratio in an inclination angle interval of 0 to 10 degrees)
TABLE 18
Deposited α-Al 2 O 3 Layer
Hard Coating Layer (numeral in parentheses
Inclination
Tool
denotes target layer thickness: μm)
Angle
Substrate
First
Second
Third
Fourth
Fifth
Interval
Frequency
Type
Symbol
Layer
Layer
Layer
Layer
Layer
(degrees)
Ratio (%)
Conventional
1
A
TiN
l-TiCN
TiN (1)
TiCNO
Deposited
Non
5
Coated
(1)
(17.5)
(0.5)
α-Al 2 O 3
existence
Cermet
(15)
Tool
2
B
TiCN
l-TiCN
TiCO
Deposited
—
Non
15
(1)
(8.5)
(0.5)
α-Al 2 O 3
existence
(9)
3
C
TiN
l-TiCN
TiC (4)
TiCNO (1)
Deposited
Non
12
(1)
(4)
α-Al 2 O 3
existence
(15)
4
D
TiC
l-TiCN
Deposited
—
—
Non
21
(1)
(9)
α-Al 2 O 3
existence
(3)
5
E
TiN
l-TiCN
TiCO
Deposited
—
Non
11
(1)
(4.5)
(0.5)
α-Al 2 O 3
existence
(5)
6
F
TiN
l-TiCN
TiC (0.5)
TiCNO
Deposited
Non
20
(0.5)
(1.5)
(0.5)
α-Al 2 O 3
existence
(3)
7
A
TiN
l-TiCN
TiCNO
Deposited
—
Non
3
(1)
(8)
(0.5)
α-Al 2 O 3
existence
(1)
8
a
TiN
TiCN
Deposited
—
—
Non
6
(1)
(19)
α-Al 2 O 3
existence
(15)
9
b
TiC
l-TiCN
TiCO
Deposited
—
Non
8
(0.5)
(9)
(0.5)
α-Al 2 O 3
existence
(10)
10
c
TiN
TiC
TiCN (7)
TiCO (1)
Deposited
Non
23
(1)
(1)
α-Al 2 O 3
existence
(15)
11
d
TiN
TiC
l-TiCN
Deposited
—
Non
19
(1)
(1)
(8)
α-Al 2 O 3
existence
(3)
12
e
TiC
l-TiCN
TiCNO (1)
Deposited
—
Non
20
(1)
(4)
α-Al 2 O 3
existence
(5)
13
f
TiCN
TiC
TiCNO
Deposited
—
Non
25
(0.5)
(2)
(0.5)
α-Al 2 O 3
existence
(3)
[In Table 18, Inclination Angle Interval represents an inclination angle interval in which the plane (0001) shows the highest peak;
Frequency Ratio represents a frequency ratio in an inclination angle interval of 0 to 10 degrees]
TABLE 19
Width of Flank Wear
(mm)
Cutting Test Result
Alloy
Carbon
Cast
Alloy
Carbon
Type
Steel
Steel
Iron
Type
Steel
Steel
Cast Iron
Coated
1
0.34
0.34
0.28
Conventional
1
Usable
Usable
Usable
Cermet
Coated
life of
life of
life of
Tool of
Cermet
2.2
2.5
2.8
Present
Tool
minutes
minutes
minutes
Invention
2
0.29
0.31
0.26
2
Usable
Usable
Usable
life of
life of
life of
3.2
3.6
3.1
minutes
minutes
minutes
3
0.32
0.36
0.29
3
Usable
Usable
Usable
life of
life of
life of
2.0
2.1
2.6
minutes
minutes
minutes
4
0.39
0.40
0.37
4
Usable
Usable
Usable
life of
life of
life of
2.5
2.4
2.7
minutes
minutes
minutes
5
0.32
0.34
0.30
5
Usable
Usable
Usable
life of
life of
life of
2.7
2.9
3.2
minutes
minutes
minutes
6
0.33
0.35
0.31
6
Usable
Usable
Usable
life of
life of
life of
3.0
2.8
3.5
minutes
minutes
minutes
7
0.30
0.33
0.27
7
Usable
Usable
Usable
life of
life of
life of
2.1
2.3
2.9
minutes
minutes
minutes
8
0.37
0.40
0.35
8
Usable
Usable
Usable
life of
life of
life of
2.3
2.5
2.9
minutes
minutes
minutes
9
0.31
0.33
0.26
9
Usable
Usable
Usable
life of
life of
life of
2.9
3.0
3.1
minutes
minutes
minutes
10
0.35
0.38
0.30
10
Usable
Usable
Usable
life of
life of
life of
2.4
2.5
3.3
minutes
minutes
minutes
11
0.36
0.40
0.34
11
Usable
Usable
Usable
life of
life of
life of
2.6
2.5
3.0
minutes
minutes
12
0.34
0.36
0.29
12
Usable
Usable
Usable
life of
life of
life of
2.7
2.9
3.1
minutes
minutes
minutes
13
0.36
0.36
0.30
13
Usable
Usable
Usable
life of
life of
life of
2.5
2.9
3.2
minutes
minutes
minutes
(In Table 19, usable life is caused from chipping generated on hard coating layer.)
As apparent from the results shown in Tables 17 to 19, in all the cermet tools 1 to 13 of the present invention in which the upper layers of the hard coating layers are composed of a transformed α-Al 2 O 3 showing an inclination angle frequency-distribution graph on which the inclination angle of the plane (0001) shows the highest peak in an inclination angle interval in a range of 0 to 10 degrees and the ratio of the sum of frequencies in the inclination angle interval ranging from 0 to 10 degrees occupy 45% or more, the transformed α-Al 2 O 3 layers exhibit excellent chipping resistance in high-speed intermittent cutting of steel or cast iron accompanied with very high mechanical and thermal impacts and high heat generation. As a result, occurrence of chipping in cutting edges is suppressed markedly and the excellent wear resistance is exhibited. To the contrary, in all the conventional coated cermet tools 1 to 13 in which the upper layers of the hard coating layers are composed of a deposited α-Al 2 O 3 layer showing an inclination angle frequency-distribution graph on which the distribution of measured inclination angles of the plane (0001) is unbiased in a range from 0 to 45 degrees, and the highest peak does not appear, the deposited α-Al 2 O 3 layers could not resist to severe mechanical and thermal impacts in high-speed intermittent cutting to generate chipping in the cutting edges, consequently shortening the usable life of the conventional cermet cutting tools.
As described above, the coated cermet tools of the present invention exhibit excellent chipping resistance not only in continuous cutting or intermittent cutting of various materials such as steel and cast iron under normal conditions but also in high-speed intermittent cutting work having severe cutting conditions, and exhibit excellent cutting performance for a prolonged period of time. Accordingly, it is possible to sufficiently and satisfactorily cope with the demand for high performance of a cutting device, labor saving and energy saving in cutting work, and cost reduction.
Further, the coated cermet tools of the present invention exhibit excellent chipping resistance not only in continuous cutting or intermittent cutting of various materials such as steel and cast iron under normal conditions but also in high-speed intermittent cutting under the severest cutting condition accompanied with very high mechanical and thermal impacts and high heat generation, and exhibit excellent cutting performance for a prolonged period of time. Accordingly, it is possible to sufficiently and satisfactorily cope with the demand for high performance of a cutting device, labor saving and energy saving in cutting work, and cost reduction. | A surface-coated cermet cutting tool with a hard-coating layer having excellent chipping resistance. The hard coating layer is formed on a surface of a tool substrate that constitutes the surface-coated cermet cutting tool. The hard coating layer includes(a) as the lower layer, a titanium compound layer having at least one or two of a titanium carbide layer, a titanium nitride layer, a titanium carbonitride layer, a titanium carboxide layer and a titanium oxycarbonitride layer, and (b) as the upper layer, a heat-transformed α-type Al—Zr oxide layer formed by carrying out a heat-transforming treatment in a state that a titanium oxide layer satisfying the composition formula: TiO Y , ¥ The heat-transformed α-type Al—Zr oxide layer is chemically deposited on a surface of an Al—Zr oxide layer having a κ-type or θ-type crystal structure and satisfying the composition formula: (Al 1−X Zr X ) 2 O 3 to transform the crystal structure of the Al—Zr oxide layer having the κ-type or θ-type crystal structure into an α-type crystal structure. | 8 |
CROSS REFERENCES TO RELATED APPLICATIONS
This application is a divisional of application Ser. No. 08/657,754, filed May 30, 1996, which is a continuation-in-part of application Ser. No. 08/527,048, filed Sep. 12, 1995, now U.S. Pat. No. 5,600,898.
STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT
BACKGROUND OF THE INVENTION
This invention relates to dryers used in papermaking in general. More particularly, this invention relates to dryers of the single tier type.
Paper is made by forming a mat of fibers, normally wood fibers, on a moving wire screen. The fibers are in a dilution with water constituting more than ninety-nine percent of the mix. As the paper web leaves the forming screen, it may be still over eighty percent water. The paper web travels from the forming or wet end of the papermaking machine and enters a pressing section where, with the web supported on a dryer fabric, the moisture content of the paper is reduced by pressing the web to a fiber content of between forty-two and forty-five percent. After the pressing section, the paper web is dried on a large number of steam heated dryer rolls, so the moisture content of the paper is reduced to about five percent.
The dryer section makes up a considerable part of the length of a papermaking machine. The web as it travels from the forming end to the take-up roll may extend a quarter of a mile in length. A major fraction of this length is taken up in the dryer section. As the paper industry has moved to higher web speeds, upwards of four- to five-thousand feet per minute, the dryer section has had to become proportionately longer because less drying is accomplished at each dryer as the paper moves more quickly through the dryers.
One type of dryer, known as a two-tier dryer, has two rows of steam heated dryer rolls four to seven feet in diameter. The dryer rolls in the upper and lower rows are staggered. The paper web runs in a meandering fashion from an upper dryer roll to a lower dryer roll and then on to an upper roll over as many rolls as is required. An upper dryer fabric backs the web as it travels over the upper dryer rolls, and leaves the paper web as it travels to the lower rolls. The upper dryer fabric is turned by dryer fabric reversing rolls spaced between the upper rolls. On the lower dryer rolls the web is supported by a lower dryer fabric, which is also turned between lower dryer rolls by lower dryer fabric reversing rolls. This apparatus advantageously dries first one side and then the other of the web, however, the paper web is unsupported for a length as it passes from the upper dryer rolls to the lower dryer rolls, and from the lower rolls to the upper rolls. Unsupported paper webs present a problem as web speed increases. At higher web speeds, the paper interacts with the air and can begin to flutter. This fluttering can wrinkle and crease the paper web, seriously damaging the quality of the paper produced. Further, the fluttering can lead to tears and web failure, with all the cost and downtime associated with paper lost during the rethreading operation.
A first approach to overcoming this problem was to use a single dryer fabric or a wire which traveled with the paper web over both the upper and lower dryers so that the paper was supported through the open draws. This approach limited paper flutter in the open draws, but, because the blanket was disposed between the paper web to be dried and the lower dryer rolls, the effectiveness of the lower dryer rolls was substantially diminished.
A further dryer development is the single tier of dryer rolls with vacuum reversing rolls disposed therebetween. The vacuum rolls, such as those shown in U.S. Pat. No. 4,882,854 (Wedel, et al.), use vacuum to clamp the edges of the paper to the reversing roll to prevent edge flutter, and use central grooves to allow passage of the trapped boundary layer between the blanket and the reversing rolls.
Single tier dryer systems are successful in increasing the drying rate and shortening the dryer section of a papermaking machine. It is necessary in order to dry both sides of the web effectively to employ both top felted and bottom felted single tiers of dryers. Bottom felted dryers have the disadvantage in that removing broke from between the dryer fabric and the dryer can be a difficult and time consuming operation. On the other hand, in the top felted dryers, when the dryer fabrics are loosened, broke drops with relative ease out from between the dryer fabric and the dryer rolls. A further possible problem with single tier dryers is the sequential drying of first one side and then the other. When both sides of the sheet are not dried simultaneously curl can develop in the paper due to the effect of drying on the dimensions of the fibers on one side of the sheet as opposed to the still wet fibers on the other which can produce a tendency for the paper web to curl both in the cross machine and in the machine direction.
Problems with curling of the paper web as it moves through the dryer section also arise from the known tendency of a paper web to dry more rapidly at the edges as opposed to the center of the web. This problem of varying moisture profile in a drying paper web has in the past been dealt with by providing additional drying to the center of the web by for example using infrared radiators divided into zones. Alternatively, the edges of the paper have been sprayed with water to increase the moisture content of the edges to that of the center of the web. Another approach is the placement of a steam box which extends across the width of paper web and is connected to a source of steam for applying the width of paper web and is connected to a source of steam for applying steam to the web to equalize the properties of the web.
When a papermaking machine dries a web unevenly in the cross machine direction the paper shrinks more at the dyer edges, producing an uneven tension profile which can contribute to a tendency for the web to curl when formed into sheets. Curling of paper is a highly undesirable property particularly in fine paper which is used with new printing and copying methods. Laser printers and photo copiers heat the paper rapidly from a single side. If this heating produces curl in the paper a paper jam may result when the paper is attempted to be fed by the printer or photo copier machine.
What is needed is a shorter dyer section which dries both sides of the web simultaneously and actively controls paper moisture profile in the cross machine direction.
SUMMARY OF THE INVENTION
The paper dryer section of this invention employs a single tier of all top felted dryers. The dryer rolls are preferably of increased diameter, 8-20 feet in diameter, as opposed to the usual 6 foot diameter. The single tier arrangement, together with the top felting, assists in the removal of broke. Air caps are employed over the dryer rolls to simultaneously dry both sides of the web to prevent curl and to increase drying rates. The air caps employ blown air at a temperature of 200-900 degrees Fahrenheit and air speeds of 8,000-40,000 feet per minute. The dryer fabric employed is foraminous with a permeability of between 400-1200 cubic feet per minute per square foot and is designed to withstand peak temperatures of up to 900 degrees Fahrenheit and average temperatures of between 500-600 degrees Fahrenheit. Either one, or more advantageously, two vacuum rolls in a vacuum box are disposed between the dryer rolls to maximize the circumferential wrap of the web and, at the same time, support and transport the web between dryer rolls.
An alternative dryer section employs single tier top felted dryer rolls in combination with single tier bottom felted dryers. Air caps are positioned over or under the single tier dryer. The alternative dryer section may further employ air caps which are segmented in the cross machine direction. The segmented air caps allow cross machine profiling of the amount and temperature of the air applied to the web through the dryer fabric to achieve uniform cross machine direction moisture content. A beta sensor is used to detect moisture content of the web as the web leaves the dryer section. A controller utilizes the moisture profile generated by the beta sensor to control the amount of drying each cross machine direction portion of the web receives.
It is a feature of the present invention to provide a papermaking dryer apparatus which provides an increased rate of drying of a paper web.
It is another feature of the present invention to provide a more compact papermaking dryer section.
It is a further feature of the present invention to provide a papermaking dryer which prevents the formation of curl in the paper web being dried.
It is an additional feature of the present invention to provide a dryer section which actively controls the cross machine direction moisture content of the paper web.
It is yet another feature of the present invention to provide a dryer section of a papermaking machine which controls curl and maximizes onesideness of the paper formed.
Further objects, features and advantages of the invention will be apparent from the following detailed description when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic side elevational view of the dryer section of this invention employing two reversing rolls.
FIG. 2 is a somewhat schematic side elevational view of the dryer section of this invention employing a single reversing roll.
FIGS. 3A and 3B comprise a schematic view of a papermaking machine employing the dryer section of FIG. 1.
FIGS. 4A and 4B comprise a schematic view of an alternative embodiment papermaking machine with dryer section of this invention.
FIG. 5 is an isometric view, partially cut-away of a dryer air cap with multiple partitions in the cross machine direction.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring more particularly to FIGS. 1-5 wherein like numbers refer to similar parts, a papermaking machine 20 is illustrated in FIGS. 3A-3B. The papermaking machine employs a dryer section 22. The dryer section is composed of dryer rolls 24 which are internally steam heated and will preferably have a diameter of eight to as large as twenty feet as opposed to conventional dryer rolls of six feet in diameter. The dryer rolls rotate about axes 26, the axes lying substantially in a single plane. Such an arrangement of dryer rolls is known as a single tier dryer section.
As shown in FIGS. 3A and 3B, a paper web 28 is wrapped onto the dryer rolls 24 by first a first dryer fabric 30, then a second dryer fabric 32, and finally a third dryer fabric 34 in sequence, as the paper web moves through the dryer section 22. Each dryer roll 24 has a dryer surface 36. The dryer roll surface 36 defines a cylinder, and thus the dryer roll has a circular cross-section. The circular cross-section has an uppermost or zenith point 38 and a lowermost or nadir point 40 at the bottom of each dryer roll 24. The dryer fabrics 30, 32, 34 wrap the dryer rolls 24 so the tops or zenith points 38 of the rolls are covered but the nadir 40 or bottom of the rolls are not overwrapped. This application of the dryer fabrics is referred to as top felting.
A top felted dryer section 22 has an advantage over bottom felted dryer systems in which the dryer fabrics wrap the bottom or nadir points of the dryer rolls, in that broke may much more easily be cleared from a top felted dryer section should a web break occur.
A papermaking machine 20 such as illustrated in FIGS. 3A-3B can operate in the range of 6,500 feet per minute. Paper breaks, while being highly undesirable on papermaking machines, are an inevitable occurrence particularly when the machine is changing between various grades of paper or when extensive maintenance and dryer fabric changes have been made. The high speed of the papermaking machine leads to an accumulation of a considerable quantity of broke or paper within the papermaking machine when a break occurs before the break can be detected and the machine shut down. The result is that the broken paper web will often wrap around individual dryer rolls. With top felting, the dryer fabrics can be slacked off from the dryer rolls 24 and any accumulated paper readily removed from and dropped down from the dryer rolls. This is in contrast to bottom felted single tier dryers where it is necessary to fish the broke out from between the dryer fabric and the dryer rolls, the dryer fabrics forming pockets about the dryer rolls which can accumulate and retain broken paper.
The disadvantage of single tier top felted dryers is that typically the paper web is dried from only a single side. This unidirectional drying of the paper web results in dimensional changes between the dryer side and the dryer fabric side of the web which, in turn, results in a permanent set or curling in the paper web which is an undesirable result. The dryer section 22 overcomes this problem by employing air caps 42 to dry the dryer fabric side of the web. The air caps 42 are hoods which overlie the upper portions 44 of the dryer rolls 24 and blow high velocity hot air through the dryer fabrics to dry the upper surface of the web simultaneously and preferably at the same rate as the roll side of the paper is dried by the steam heat transmitted to the surface 36 of the dryer rolls 24.
In order to allow the passage of air through the dryer fabrics 30, 32, 34 the dryer fabrics must be of a porous or foraminous nature. Thus, the dryer fabrics employed in the dryer section 22 will have a porosity in the range of four-hundred to twelve-hundred cubic feet per minute per square foot at one-half inches of water as typically measured by those skilled in the art of the design and construction of papermaking dryer fabrics. The air supplied by the air caps 42 may have a temperature range of two-hundred-and-fifty to nine-hundred degrees Fahrenheit and be blown at a velocity of between eight-thousand and forty-thousand feet per minute. The high air temperatures require dryer fabrics which can withstand up to nine-hundred degrees Fahrenheit for brief periods of time and steady state temperatures in the range of five-hundred to six-hundred degrees Fahrenheit.
Dryer fabrics of this nature may be constructed of metal, high temperature plastics such as polyetheretherketone (PEEK), or polyphenylene Sulfide (PPS) also sold as Ryton® fibers and manufactured by Phillips Petroleum Company, or other high temperature materials such as Nomex® fiber produced by E. I. Du Pont de Nemours Corporation, 1007 Market St., Wilmington Del., which can be formed into the necessary fibers.
As shown in FIGS. 3A-3B, multiple dryer fabrics 30, 32, 34 are employed. An exemplary transfer system, is of the so-called lick-down web transfer wherein the paper web 28 is supported on the dryer roll unbacked by dryer fabric over a short region 46 as it transits between the first dryer fabric 30 and the second dryer fabric 32 or the second dryer fabric 32 and the third dryer fabric 34. The air caps 48 adjacent to the lick-down transfers 47 do not blow on the unbacked short region 46 so the unbacked web is not blown off the dryer roll surface 36.
The web 28 is transferred between the multiple dryer rolls 24 of the single tier. Because only a single tier of dryer rolls 24 is employed in the dryer section 22, reversing rolls 50 are used to transfer the paper web 28 from the surface 36 of one dryer roll 24 to the surface of an adjacent dryer roll. In order to maximize the amount of drying achieved per dryer roll 24 it is desirable that the web be wrapped about the maximum portion practical of the dryer surface 38 of each dryer roll. As shown in FIGS. 1 and 3A-3B the employment of two spaced apart reversing rolls 50 maximizes the portion 52 of the roll surface 36 which is wrapped by the dryer fabrics 30, 32, 34 and the web 28. The dryer fabrics wrap a portion 52 comprising approximately eighty percent of the dryer roll surface 36, corresponding to approximately 290 degrees of the roll surface.
As shown in FIG. 1, where dual reversing rolls 50 are employed it is desirable to support the web 28 as it moves around the reversing rolls 50 to prevent fluttering and thus paper breaks. A vacuum chamber 54 is formed by a rigid metal structure 58 located between gaps 56 between dryer rolls 24. The vacuum chamber 54 is formed by a metal cover 58 which is sealed against the moving dryer fabrics 30, 32, 34 to define an internal volume on which reduced pressure is drawn. The cover 58 is comprised of two side plates 60, one of which is shown in FIG. 1. The side plates 60 are joined along the top by a top plate 62. Each side plate 60 has two clearance openings 64 which are smaller in diameter than the reversing rolls 50. Although vacuum is preferably drawn on the vacuum box 54, a similar effect can be achieved with a blowing box. However, a blowing box produces less clamping effect as the pressure reductions obtainable by blowing boxes are limited.
The reversing rolls 50 preferably are formed with circumferential grooves which facilitate holding the paper web and the dryer fabrics to the reversing roll 50. The reversing rolls 50 are rotatably mounted within the vacuum chamber 54. The openings 64 provide clearance for the side wall extensions of the shafts (not shown) on which the rolls 50 are mounted. The side plates 60 oppose each other and are perpendicular to the central axes 26 of the dryer roll 24. A hole (not shown) is cut through the side plate 60 which allows for the drawing of a vacuum on the vacuum chamber 54 by an external vacuum means (not shown). Each side plate 60 has an upper segment 66 which extends above the grooved rolls 50 and a downwardly extending tab 68 which blocks escaping air to the sides of the grooved rolls. A lower horizontal edge 70 of the tab 68 engages with the dryer fabric 30, 32, 34 as it passes between the two grooved rollers 50. Stiffening ribs (not shown) may project inwardly from the inner perimeter of the side plates 60 to prevent excessive deflection of the plates by the application of vacuum. Two inclined flanges 72 extend from the top plate 62 between the side plates 60. Each inclined flange 72 extends upward of the top plate 62 and inward towards the center of the top plate 60, thereby forming an acute angle with the top plate 62. The net result of the grooved rollers 50 and the vacuum box 54 is to restrain the web and the backing dryer fabric from fluttering as it transfers from one dryer roll to the next whilst preventing paper breaks.
As shown in FIG. 2, an alternative dryer section 122 employs dryer rolls 124 and air caps 142. The dryer section 124 is similar to the dryer section 24 of FIG. 1, except that only a single reversing roll 150 is employed to transfer the web 128 and dryer fabric 130 between dryer rolls 124. The result of employing a single reversing roll reduces the complexity of the dryer section 122. However, the use of a single reversing roll results in a wrapped portion 152 which is a somewhat smaller percentage of the total surface area 136 of the roll when compared to the wrapped percentage of the dryer section 22 of FIG. 1.
The reversing rolls 50 and 150 are preferably placed as close to the dryer rolls as possible to minimize the portion of the web which is not firmly clamped to the dryer fabric or dryer surface. Constraining the web as it moves through a dryer section improves sheet properties. Shrinkage in the machine direction can be controlled by the tension in the web resulting from control of the dryer speeds. Shrinkage in the cross machine direction can only be controlled by clamping the web to the dryer surface with dryer fabric tension and holding the web on the dryer fabric as it moves around the reversing rolls with vacuum. Thus the importance of restraining the web as much as possible. Using dryer rolls of eight to twenty feet in diameter means that the tension in the dryer fabric must be increased if the clamping force on the dryer roll surface is to remain constant. Increasing dryer fabric tension increases the loads on the dryer rolls, the reversing rolls and other rolls which handle the dryer fabrics, which in turn requires increased roll stiffness and roll bearings of greater strength. For example, the tension applied to the dryer fabric is between about ten and about twenty pounds per linear inch for a six foot diameter dryer and which the tension is increased proportional to the dryer diameter up to a diameter of twenty feet.
The reversing rolls 50 and 150 however can not be too close to the dryer rolls because in the event of a paper break the web can become wrapped around a dryer which will then destructively engage an adjacent reversing roll. In practice the minimum spaces between the reversing rolls and the dryer rolls depends on the paper thickness being made, the speed with which a paper break is automatically detected and the web is diverted from the dryer section, and whether or not the reversing rolls are mounted to pivot away from the dryer rolls. The usual result is that the reversing rolls are placed one to five inches away from the dryer rolls with the choice in a particular situation being up to the paper mill operator.
An exemplary paper machine 20 employing the dryer section 22 is shown in FIGS. 3A-3B. The papermaking machine 20 illustrated can be used to produce twenty-eight pound newsprint with a wire width of four-hundred-and-twenty inches and operating at a speed of sixty-five-hundred feet-per-minute. The papermaking machine 20 employs a former 88 which has a vertically oriented headbox 80 which has a slice opening 82 which injects a stream of pulp between a first forming wire 84 and a second forming wire 86 which comprises the twin wire former 88. The paper web 28 is transferred to a press section 90 where a single extended nip press 92 accomplishes the pressing function. The web 28 is then wrapped onto the first dryer fabric 30 and transferred to the dryer section 22. After transiting the dryer section 22 the web is calendered with high temperature soft nip calenders 94 and 95. Following calendering the web is wound onto reels by a winder 96.
The soft nip calender 94 has an upper heated press roll 98 and a lower compliant backing roll 100. The calender 94 is of the temperature gradient type where the web is not preheated and thus only the surface in contact with the heated roll is deformed in passing through the calender 94. The second soft nip calender 95 has a lower heated press roll 102 and an upper backing roll 104. The heated press rolls 98 and 102 engage opposite sides of the web 28. Thus by varying the temperature of the upper heated press roll 98 versus the temperature at the lower heated press roll, and by varying the pressing pressure in the first calender 94 versus the pressure in the second calender 95, the surfaces of the web 28 can be treated differently to compensate for twosidedness produced by the dryer section 22.
One preferred system will employ components manufactured by Beloit Corporation of Beloit, Wis. The twin wire former may be a Bel-Bai RCB type enclosed jet former obtainable from Beloit Corporation. The headbox used will preferably be the concept IV-MH headbox employing consistency profiling, also available from Beloit Corporation. Press sections, high temperature soft nip calenders and reels are also available from Beloit Corporation.
The papermaking machine 22 employing the dryer section 24 may be observed to be of compact design with relatively few dryer rolls as well as few rolls of any type. Because of the high cost of individual rolls, together with their bearings and support system, a papermaking machine such as the one illustrated in FIGS. 3A-3B contributes to improved cost, reliability, and performance.
An alternative embodiment papermaking machine 220 with dryer section 222 is shown in FIGS. 4A and 4B. The papermaking machine 220 has a former 224 which is similar to the former 88. The former 224 has a headbox 226 with a slice 228 which directs a stream of stock between a first wire 230 and a second wire 232. A lumpbreaker press 234 is formed of a lower press roll 236 and an upper backing roll 238. The lower press roll 236 is contained within a loop formed by the second wire 232.
The upper backing roll 238 is contained within a loop formed by the press felt 240. Utilization of a lumpbreaker press 234 increases the fiber content of a web 242 formed by the former 224 from sixteen percent dry weight to about twenty-two percent dry weight. The lumpbreaker press 234 can be positioned before the press felt 240 engages the second forming wire 232. This has the advantage of minimizing the amount of water pressed into the press felt 240. The lower press roll 236 and the upper backing roll 238 will preferably have elastic coverings to minimize the impression on the web formed by the forming wire 224.
A pressing section 244 employing a single concave shoe press 246 such as an Extended Nip® type press manufactured by Beloit Corporation, follows the former 224. The dryer section 248 shown in FIG. 4B is a variation on the dryer section 22. The dryer section 248 employs single tier dryers. However the first fabric group 250 is without air caps and is typical of a variation on dryer section 22 necessitated by retrofitting air caps onto a existing machine where space limitations may dictate leaving air caps off the dryer rolls adjacent to the pressing section. Further the first fabric group of dryer rolls 250 as shown in FIG. 4B contains fewer dryer rolls and thus the lack of air caps is less critical on the shorter dryer section. The first fabric group of dryer rolls employs dryer rolls 252 which rotate about axes 254.
A "fabric group" of dryer rolls is defined as a group of dryer rolls substantially in a single plane which are engaged by a single dryer fabric. The second fabric group of dryer rolls 256 employs air caps 258 over the tops of the dryer rolls 260. Reversing rolls 262 between each pair of dryer rolls 260 conduct the dryer fabric 264 with the paper web 242 clamped by vacuum drawn through the dryer fabric 264. Each dryer roll 260 has a zenith point 266 and a nadir point 268. The dryer rolls 260 are top felted in that the dryer fabric 264 wraps the tops of the dryer rolls including the zenith points 266 but not the nadir points 268. Although top felted dryer rolls are preferred because of their operational advantages in handling broke, in some circumstance it may be desirable to employ one or more bottom felted dryer rolls 270 in order to achieve better onesideness of the paper web 242.
The last dryer roll 272 in the fabric group 256 prior to the bottom-felted dryer rolls 270 is without an air cap because of space considerations, and leads into an S-web transfer 274 which is shown in FIG. 4B without the web 242 and with a small gap between the transfer dryer fabrics for clarity. The S-web transfer holds the web between the dryer top felt 264 and a bottom dryer felt 276. The S-web transfer provides a means for transferring the web from the first dryer section to the second dryer section in which the web 242 is transferred without an open draw from the top felted dryer fabric group 256 and to the fabric group of bottom felted dryer rolls 278. The S-web transfer defines a joint run of the dryer top dryer fabric 264 and the bottom dryer fabric 276 such that the web is conveyed by the top dryer fabric in close conformity with the bottom dryer fabric. Subsequently, the top dryer fabric diverges from the web and the web is carried by the bottom dryer fabric.
The bottom felted dryer rolls 270 in FIG. 4B are shown with air caps 280 but depending on the paper being dried could be used without air caps. The advantage of employing bottom felted dryer rolls 270 is their ability to improve onesideness of the web 242. This advantage offsets in some circumstances the problem associated with removing broke from bottom felted dryer rolls. An additional fabric group 282 of top felted dryer rolls following the bottom felted fabric group 278 may be utilized as required to achieve the desired dryness of the paper web 242.
One major problem in drying a paper web is the tendency for the web to dry more rapidly in some locations than in other locations in the cross machine direction. As shown in FIG. 5, an air cap 283 which is divided by baffles 288 into partitioned compartments 284 can be used to control web moisture content in the cross machine direction. A sensor 286 for measuring web moisture, shown schematically in FIG. 4B, is mounted to traverse the web and provide moisture profile data on the web as it is formed. A typical sensor utilizes beta radiation to monitor moisture content in the web.
A computer or controller (not shown) utilizes the output of the sensor to control air velocity and/or air temperature which is introduced into each partitioned compartment 284 of the air caps 283. The controller thus responds to the moisture profile in the treated web to adjust treatment of subsequent portions of the web. In practice air of a single temperature is directed into each partition 284 by a series of dampers (not shown) which control the amount of heating air supplied to each partitioned compartment 284 under the control of the computer or controller. The compartments 284 are formed by baffles 288 which divide the air cap 283 into regions in which the air flow can be separately controlled. The baffles 288 extend in the machine direction and the compartments 284 are aligned in the cross machine direction. Baffles 288 can be used together with moisture profiling with any of the air caps 258, 280, 42, 122 illustrated in FIGS. 1-4B. The air cap 283 is schematic to show the position of the air cap over a typical dryer roll 290. The additional ductwork and gas firing units are omitted for clarity.
It should be understood that the invention depicted in FIGS. 4A-4B would typically be constructed as a new papermaking machine, yet the embodiment as illustrated incorporates various structures which may be required in retrofitting an old machine. In particular, some of the dryer rolls as shown do not employ air caps, whereas preferably in an all newly constructed papermaking machine, where maximum drying capability is desired, each dryer roll would have an air cap. Where space limitations associated with dryer fabric transfers prevent a complete air cap from being positioned over the a dryer roll, partial air caps may be employed.
It should be understood that the air temperature used in the dryer air caps may be varied between the wet end and the dry end of the dryer with the higher temperature air being used at the wet end.
It should also be understood that an exemplary air velocity of twenty-eight-thousand feet per minute and an air temperature of seven-hundred-and-fifty degrees may be employed. In general the air temperature should be greater than two hundred and fifty degrees Fahrenheit with an air velocity of greater than twelve thousand feet per minute.
The permeability of the dryer fabrics, sometimes referred to in the trade as dryer felts or dryer canvas, should be greater than a typical dryer fabric which has a permeability of between ninety and one-hundred twenty cubic feet per minute per square foot at a pressure of one-half inches of water. Preferably the permeability of the dryer fabrics will be greater than two-hundred to three-hundred cubic feet per minute per square foot at a pressure of one-half inches of water. The preferred permeability is in the range of three-hundred to twelve-hundred cubic feet per minute per square foot at a pressure of one-half inches of water.
It should be understood that greater dryer surface for a given floorprint may be achieved by using larger dryer rolls and that dryer technology used in the manufacturer of Yankee dryers assures that dryer rolls as large as twenty feet can be constructed.
It should also be understood that a further advantage of the dryer section 22 of this invention is that when all the dryer rolls are in a single tier it is possible to mount the dryer section directly to the mill floor without the necessity of constructing basements under the dryer. This relatively simple and more rigid mounting is preferred.
It should also be understood that although three dryer fabrics are shown, more or fewer dryer fabrics could be used. The advantages of employing greater numbers of dryer fabrics are threefold. One, the paper lengthens and shortens slightly as the drying process is accomplished and therefore the dryer rolls are required to run more rapidly as the paper progresses through the dryer section 22. The more drying fabrics, the more stages in which the paper speed can be increased. Secondly, changing dryer fabrics prevents a single dryer fabric from impressing a pattern onto the surface of the web. Thirdly, it is to be understood that shorter dryer fabrics are more easily changed.
It is understood that the invention is not limited to the particular construction and arrangement of parts herein illustrated and described, but embraces such modified forms thereof as come within the scope of the following claims. | The dryer section in a papermaking machine has a single tier of all top felted dryer rolls six to nine feet in diameter. Air caps are employed over the dryer rolls to simultaneously dry both sides of the web to prevent curl and to increase drying rates. The air caps employ blown air at a temperature of 250-900 degrees Fahrenheit and air speeds of 8,000-40,000 feet per minute. The dryer fabric employed is foraminous with a permeability of between 300-1,200 cubic feet per minute per square foot and is designed to withstand peak temperatures of up to 900 degrees Fahrenheit and average temperatures of between 500-600 degrees Fahrenheit. A single transfer roll, or more advantageously, two grooved vacuum rolls in a vacuum box are disposed between the dryer rolls to maximize the circumferential wrap of the web and, at the same time, support and transport the web between dryer rolls. | 3 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to construction materials for upholstery and, more specifically, to a kind of cushion blocks for use in setting a build-up surface, such as wooden flooring, wooden wall or wooden ceiling.
2. Description of the Related Art
Build-up wooden flooring is commonly seen in upholstery. When paving a build-up wooden flooring, wooden strips coupled to one another by engaging the coupling flange of one wooden strip into the coupling groove of another wooden strip and then the flooring board thus obtained is fastened to the floor wall or wooden racks at the floor wall by iron nails. This wooden flooring paving procedure is complicated and time-consuming. Further, the nailing work requires a special technique. Only an experienced person can do the job well. Because wooden strips are fixedly fastened to the floor wall or wooden racks by iron nails and abutted against one another, they cannot expand freely. Therefore, the wooden strips tend to curve upwards or to break when absorbed a certain amount of moisture from the air. Recently, bamboo strips are popularly invited for flooring. However, bamboo strips have relatively higher absorptive power than wooden strips. The curving or breaking problem due to absorption of moisture will occur more easily in bamboo strips.
SUMMARY OF THE INVENTION
It is one object of the present invention to provide a cushion block for a build-up flooring, wall, ceiling and the like which is easy to install without special techniques and, saves much flooring cost.
It is another object of the present invention to provide a cushion block for a build-up flooring, wall, ceiling and the like which compensates the expansion of wooden strips due to absorption of moisture.
To achieve these objects of the present invention, the cushion block comprises a first coupling device at one end thereof, a second coupling device at an opposite end thereof corresponding to the first coupling device, the first coupling device and the second coupling device being made such that multiple cushion blocks are connectable in a line in a linking direction by engaging the first coupling device of one cushion block into the second coupling device of another cushion block, a retaining device protruded from one side thereof and adapted to secure strips to the corresponding side of the cushion block, and a deformable body connected between the first coupling device and the second coupling device and deformable in the linking direction to compensate expansion of strips due to absorption of moisture.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a cushion block according to a preferred embodiment of the present invention.
FIG. 2 is a top plain view of the cushion block according to the preferred embodiment of the present invention.
FIG. 3 is a sectional view taken along line 3 — 3 of FIG. 2 .
FIG. 4 illustrates the connection of multiple cushion blocks according to the preferred embodiment of the present invention.
FIG. 5 is an applied view of the present invention.
FIG. 6 is side view in section in an enlarged scale of FIG. 5 .
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1 , a cushion block 10 is a flat rectangular block molded from synthetic resin (for example, polyacrylic resin or polyethylene resin) in integrity, having a base 20 disposed at one end, two male coupling devices 40 arranged in parallel at the other end, a deformable body 30 connected between the base 20 and the male coupling devices 40 , two female coupling devices 50 arranged in parallel in an outer side of the base 20 remote from the deformable body 30 , a retaining device 60 located on the top side of the base 20 and spaced between the deformable body 30 and the female coupling devices 50 , and two pairs of springy supporting devices 70 located on the top side of the base 20 and symmetrically disposed at two sides of the retaining device 60 .
The retaining device 60 projects upwards from the top side of the base 20 . Except the retaining device 60 , the top sides of the other parts of the cushion block 10 are maintained in flush (the springy supporting devices 70 are normally disposed in a sloping position partially protruding over the top side of the base 20 , however they become flush with the top side of the base 20 when forced downwards).
According to the present preferred embodiment, the thickness of the cushion block 10 is about 1 cm (the height of the protruding retaining device 60 excluded). The length of the cushion block 10 (i.e., the length front the outer end of the male coupling device 40 to the outer end of the female coupling devices 50 ) is about 10 cm. The width of the cushion block 10 is about 7 cm. For easy understanding of the present invention, the direction passing through the male coupling devices 40 and the female coupling devices 50 is defined as “linking direction”.
The base 20 is shaped like a flat rectangular block. The deformable body 30 extends outwards from one vertical peripheral side of the base 20 to the male coupling devices 40 opposite to the female coupling devices 50 , and is formed of a latticed grid having rhombic meshes 31 in it. Each rhombic mesh 31 has two opposite acute angles aligned in the linking direction, and two opposite obtuse angles aligned in a direction across the linking direction. Further, Each acute angle of each rhombic mesh 31 forms a substantially C-shaped arched portion 32 having the open side facing the inside of the respective rhombic mesh 31 . Because of the latticed grid structural design, the deformable body 30 can be compressed and stretched in the linking direction. Further, the deformable body 30 does not wear easily with use because it is molded from synthetic resin.
The male coupling devices 40 are respectively outwardly extended from one side of the deformable body 30 remote from the base 20 , each having three vertical positioning ribs 41 symmetrically disposed at two sides, a vertical through hole 42 , and a retaining notch 43 disposed at an outer side at a lower elevation than the top side of the cushion block 10 .
The female coupling devices 50 are recessed coupling devices formed in the side of the base 20 and extended to one vertical peripheral side of the base 20 opposite to the deformable body 30 and adapted to accommodate the male coupling devices 40 respectively, each having four vertical positioning grooves 51 symmetrically disposed at two sides, and an upright springy hook 52 adapted to engage the retaining notches 43 of the male coupling devices 40 .
The retaining device 60 is an elongated retaining bar raised from the top side of the base 20 and extending across the linking direction between two opposite vertical peripheral sides of the base 20 . The cross section of the retaining device 60 is a T-shaped cross section, i.e., the retaining device 60 has an elongated top flange 62 , defining two elongated coupling grooves 61 at two sides below the top flange 62 .
The bottom side of the base 20 is a hollow structure (see FIG. 3 ). Two springy tongues 72 are formed of a part of the top wall of the base 20 by making two substantially U-shaped crevices 71 in the top wall of the base 20 at two sides of the retaining device 60 . The top side of each springy tongue 72 obliquely upwardly extends from the fixed end toward the free end (see FIG. 3 ). The crevices 71 and the springy tongues 72 form the aforesaid springy supporting devices 70 .
Referring to FIG. 4 , by means of fastening the male coupling devices 40 of one cushion block 10 to the female coupling devices 50 of another, a plurality of cushion blocks 10 are connected in a series, forming an elongated rack 80 for supporting wooden strips. When fastening the male coupling devices 40 of one cushion block 10 to the female coupling devices 50 of another, the three vertical positioning ribs 41 at one side of each male coupling device 40 can selectively be forced into engagement with the front three or rear three of the corresponding four vertical positioning grooves 51 of the matching female coupling device 50 . Therefore, each two cushion blocks 10 can be alternatively connected between two sizes. After insertion of the respective male coupling devices 40 into the respective female coupling devices 50 , the upright springy hooks 52 of the respective female coupling devices 50 are respectively hooked in the retaining notches 43 of the respective male coupling devices 40 .
Referring to FIGS. 5 and 6 , multiple cushion blocks 10 are used with multiple wooden strips 90 to make a wooden flooring. The wooden strips 90 are rectangular strips, each having a longitudinal coupling tongue 91 and a longitudinal coupling groove 92 respectively extended along the two opposite long sides, two longitudinal locating grooves 93 respectively extended along the two opposite long sides below the longitudinal coupling tongue 91 and the longitudinal coupling groove 92 , and two longitudinal locating flanges 94 longitudinally disposed in the two opposite long sides below the longitudinal locating grooves 93 . The length of each wooden strip 90 is about 1 meter. The maximum width (including the width of the longitudinal coupling tongue 91 ) of each wooden strip 90 is about 10 cm corresponding to the length of each cushion block 10 . The thickness of each wooden strip 90 is about 1.5 cm.
When paving the desired down flooring, arrange multiple cushion blocks 10 into parallel racks 80 at a pitch corresponding to the length of the wooden strips 90 , and then mount the wooden strips 90 on each two adjacent racks 80 , enabling the two ends of the major axis of each wooden strip 90 to be supported on one half of the area of the top side of a respective cushion block 10 between the retaining devices 60 of two symmetrical pairs of cushion blocks 10 . When set into position, the longitudinal coupling tongue 91 of one wooden strip 90 is engaged into the longitudinal coupling groove 92 of another, and the longitudinal locating grooves 93 and longitudinal locating flanges 94 of the wooden strips 90 are respectively forced into engagement with the elongated top flange 62 and elongated coupling grooves 61 of the retaining devices 60 of the cushion blocks 10 . Because the cushion blocks 10 are deformable in the linking direction, inserting one wooden strip 90 in between the retaining devices 60 of two cushion blocks 10 causes the two cushion blocks 10 to be reversely expanded outwards in the linking direction for enabling the respective wooden strip 90 to be set into position. When the respective wooden strip 90 set into position, the respective cushion blocks 10 return to their former shape, thereby causing the retaining devices 60 of the respective two cushion blocks 10 to hold down the respective wooden strip 90 . Normally, the springy supporting devices 70 of each cushion block 10 have the respective top side partially protruding over the top side of the respective cushion block 10 . When the wooden strips 90 pressed on the top side of the cushion blocks 10 are set in position, the springy supporting devices 70 impart an upward pressure to the wooden strips 90 , thereby causing the longitudinal locating flanges 94 to be positively stopped against the elongated top flanges 62 of the retaining devices 60 at the bottom side, preventing vibration of the wooden strips 90 .
The length and width of the desired wooden flooring may not be able to be divided by the length and width of the wooden strips 90 . In this case, the wooden strips 90 for the border area may have to be cut to a particular size. During wooden flooring paving work, the two cushion blocks 10 at the ends of each rack 80 may be cut (for example, along the bottom side of the respective retaining device 60 ) subject to the cutting status of the bordering wooden strips 90 . When abutting one short side of each wooden strip 90 against the wall of the room, the corresponding racks 80 are arranged with one corresponding long side abutted against the wall of the room, thus the corresponding wooden strips 90 can wholly be supported on the corresponding racks 80 without cutting.
FIG. 5 shows simply one wooden flooring paving example according to the present invention. According to this wooden flooring paving example, the wooden strips 90 are longitudinally and transversely aligned. Alternatively, the wooden strips 90 can so arranged that the respective long sides are aligned, and the respective short sides are staggered. Other paving methods as used in the bonding of bricks may be employed. For example, the pitch between two racks 80 can be one half of the length of the wooden strips 90 , i.e., three racks 80 are arranged in parallel to support the ends and middle part of the respective wooden strips 90 .
The aforesaid example explains the paving of a wooden flooring. However, the invention can also be used in paving any type of the build-up surface, such as bamboo flooring, wooden ceiling, wooden wall panel, etc. When a wooden flooring or wooden ceiling is constructed according to the present invention, elongated open spaces are left in the wooden flooring or wooden ceiling between the wooden strips and the floor or wall surface and between each two adjacent racks for electric wiring. | A cushion block for using in a build-up surface formed by strips has two male coupling devices at one end, two female coupling devices at an opposite end corresponding to the male coupling devices, a retaining device protruded from one side thereof and adapted to secure the strip to the corresponding side of the cushion block, and a deformable body connected between the male coupling devices and the female coupling device. The male and female coupling devices are so made such that multiple cushion blocks are connectable in a line in a linking direction by engaging the male coupling devices of one cushion block into the female coupling devices of another. The deformable body is deformable in the linking direction to compensate expansion of the strips due to absorption of moisture. | 4 |
FIELD OF THE INVENTION
[0001] This invention relates to novel compositions of matter that are aqueous suspensions of pentabromobenzyl acrylate (PBBMA) and to a process for making them.
BACKGROUND OF THE INVENTION
[0002] Pentabromobenzyl acrylate (PBBMA) is an acrylic monomer, which is useful in many applications, especially but not exclusively, in the field of fire retardants for plastic compositions. It can be polymerized easily by known techniques such as bulk polymerization, solution polymerization etc., or by mechanical compounding or extrusion. In mechanical compounding or extrusion, it may be grafted onto existing polymer backbones, or added to unsaturated loci on polymers.
[0003] All these properties render PBBMA a particularly useful tool in the hands of experienced compounders. However, it has been impossible, so far, to carry out aqueous manipulations with PBBMA, in spite of their desirability, because, on the one hand, PBBMA is insoluble in water, and on the other hand, because of its high bromine content, it has a high specific gravity, about 2.7, —and therefore does not lend itself to the preparation and use of aqueous suspensions.
[0004] It is a purpose of this invention to provide stable dispersions or suspensions of PBBMA, which are new compositions of matter. Dispersions and suspensions are to be considered synonyms, as used herein.
[0005] It is another purpose of this invention to provide such dispersions or suspensions that are aqueous dispersions or suspensions.
[0006] It is a further purpose of this invention to provide a process for preparing such suspensions.
[0007] It is a further purpose of this invention to provide suspensions of PBBMA for particular applications in industry.
[0008] It is a still further purpose of this invention to provide suspensions of PBBMA together with additional compounds, such as synergists for increasing the fire-retarding efficiency of compositions obtained from PBBMA.
[0009] It is a still further purpose of this invention to provide processes comprising the polymerization and/or copolymerization of PBBMA for the production of particular products.
[0010] Other purposes and advantages of the invention will appear as the description proceeds.
SUMMARY OF THE INVENTION
[0011] The suspension of PBBMA, according to the invention, is characterized in that it comprises PBBMA in the form of finely ground particles, having a size smaller than 50 μm and preferably smaller than 10 μm and more preferably from 0.3.□m to 10 μm, and contains suspending agents chosen from among xanthene gums, anionic or nonionic purified, sodium modified montmorilonite, naphthalene sulfonic acid-formaldehyde condensate sodium salt, sodium or calcium or ammonium salts of sulfonated lignin, acrylic acids/acrylic acids ester copolymer neutralized—sodium polycarboxyl, and wetting agents chosen from among alkyl ether, alkylaryl ether, fatty acid diester and sorbitan monoester types, polyoxyethylene (POE) compounds. The POE compounds are preferably chosen from among:
[0012] POE allyl ethers N—5; 10; 20;
[0013] POE lauryl ethers N—5; 10; 20;
[0014] POE acetylphenyl ethers N—3; 5; 10; 20;
[0015] POE nonylphenyl ethers N—3; 4; 5; 6; 7; 10; 12; 15; 20;
[0016] POE dinonylphenyl ethers N—5; 10; 20;
[0017] POE oleate—N—9, 18, 36;
[0018] Sorbitan monooleate N—3; 5; 10; 20.
[0019] Alkyl naphthalene sulfonates or their sodium salts.
[0020] N is the number of ethylene oxide units.
[0021] Said suspension is typically, though not necessarily, an aqueous one.
[0022] The suspension according to the invention may also include nonionic or anionic surface active agents or wetting agents, which can be chosen by persons skilled in the art. For example, nonionic agents may be polyoxyethylene (POE) alkyl ether type, preferably NP-6 (Nonylphenol ethoxylate, 6 ethyleneoxide units) Anionic agents may be free acids or organic phosphate esters or the dioctyl ester of sodium sulfosuccinic acid. It may, also, include other additives which function both as dispersing agents and suspending agents commonly used by skilled persons like sodium or calcium or ammonium salts of sulfonated lignin, acrylic acids/acrylic acids ester copolymer neutralized—sodium polycarboxyl, preferably naphthalene sulfonic acid—formaldehyde condensate sodium salt. The suspension according to the invention may also include defoaming or antifoaming agents, which can be chosen by persons skilled in the art. For example, emulsion of mineral oils or emulsion of natural oils or preferably emulsion of silicon oils like AF-52™.
[0023] The invention further comprises a method of preparing a suspension of PBBMA, which comprises grinding the PBBMA together with wetting agent and preferably also dispersing agent to the desired particle size adding it to the suspending medium, consisting of water containing suspension stabilizing agents, with slow stirring, preferably at 40 to 400 rpm. Grinding is preferably carried out with simultaneous cooling. The order of the addition of the wetting agents, the dispersing agents and the suspending agents is important.
[0024] Preserving or stabilizing agents such as Formaldehyde, and preferably a mixture of methyl and propyl hydroxy benzoates, can also be added to the suspension .
[0025] Typical size distributions of PBBMA both before grinding and as they are when present in suspensions according to the invention, are listed hereinafter. “D” indicates the diameter of the particles in μm and S.A. indicates the surface area in square meters per gram. “v” designates volume and 0.25 means 25% by volume.
D(v, 0.1) D(v, 0.5) D(v, 0.9) Specific S.A. PBBMA before 2.40 19.34 58.20 0.3623 grinding PBBMA in 0.36 1.54 6.62 2.2554 suspension
[0026] In an embodiment of the process of the invention, wherein suspensions of PBBMA and additional compounds—such as fire-retardant synergists, e.g. fire-retardant antimony oxide (AO), the process comprises preparing a suspension of the additional compound in a way similar to the preparation of the PBBMA suspension, and then mixing the two suspensions, preferably by adding the suspension of the additional compound to a slowly stirred suspension of PBBMA, and continuing stirring until a homogeneous, mixed suspension is obtained.
[0027] The suspensions, in particular the aqueous suspensions, of the invention are stable. When stored at room temperature, they are stable for at least two weeks and preferably at least one month. Their stability may be higher, e.g. three months or more. If they have to be stored at high temperature, they should pass the “Tropical Storage Test”, at 54° C., viz. be stable under such Test for at least one week.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0028] The following examples are intended to illustrate the invention, but are not binding or limitative.
EXAMPLE 1
Preparation of a Suspension of PBBMA
[0029] A glass bead wet mill equipped with cooling jacket and continuous feed by a peristaltic pump, was utilized for grinding. PBBMA (750 gr) was mixed with water (240 ml), NP-6 (Nonylphenol ethoxylate) (1 ml) and Darvan#1 (Naphtalenesulfonic acid formaldehyde condensate, sodium salt) (30 gr). The mixture was fed into the grinding beads mill over a period of 25 min. The resulting slurry was stirred gently, mechanical blade stirrer, 40-60 rpm, and 10 ml of 1.5% Rhodopol 23, Xanthan Gum (CAS N° 11138-66-2) in water with preserving agents, 1% Methyl Paraben, methyl-4-hydroxybenzoate, CAS N° 99-76-3 and 0.5% Propyl Paraben, propyl-4-hydroxybenzoate, CAS N° 94-13-3, were added.
EXAMPLE 2
Preparation of a PBBMA-AO Suspension
[0030] A suspension of Antimony Oxide was prepared as follows. To a 3-liter round bottom flask, fitted with a mechanical stirrer, were added water (240 ml), NP-6 (1 ml) (Nonylphenol ethoxylate), and Darvan #1 (Naphtalenesulfonic acid formaldehyde condensate, sodium salt) (30 g). Finely ground antimony oxide, Ultrafine grade with typical average particle size of 0.2 □m-0.4 □m. (AO, 750 g) was slowly added under fast stirring, 400-600 rpm. The stirrer was slowed, 50-150 rpm and a 1.5% solution of Rhodopol 23 Xanthan Gum (CAS N° 11138-66-2) with preserving agents—1% Methyl Paraben, methyl-4-hydroxybenzoate, (CAS N° 99-76-3) and 0.5% Propyl Paraben, propyl-4-hydroxybenzoate, (CAS N° 94-13-3) were added (115 ml).
[0031] The mixed PBBMA-AO suspension was prepared as follows. To a slowly stirred, 40 rpm, suspension of PBBMA (750 ml) at 25° C.-30° C., obtained as described in Example 1, was added the AO suspension (250 ml) as described above. After five minutes, stirring was stopped, yielding a homogeneous mixture.
EXAMPLE 3
Preparation of a PBBMA-Styrene-Butylacrylate Terpolymer Latex
[0032] In a 0.5L 4 necked round bottom flask fitted with mechanical stirrer, reflux condenser, thermometer, dropping funnel and Nitrogen inlet were charged 1.4 gr SDS (Sodium Dodecyl Sulfate) and 100 mL of water. The flask was immersed in an oil bath and heated to 70° C. with continuous stirring, 250 rpm, Nitrogen was introduced under the surface of the liquid. After 1 hr. the nitrogen inlet was raised above the surface of the liquid and 0.15 gr of K 2 S 2 O 8 were added. 5 min. later a solution of 15 gr Styrene and 15 gr Butylacrylate was added dropwise over 30 min. The emulsion pre-polymerization was continued for another 90 min. after which 6 gr of a PBBMA suspension (˜60% solids) were added dropwise over 70 min. The polymerization was continued overnight.
[0033] A stable latex ( stable for more than two month ) was obtained.
[0034] The terpolymer isolated from this emulsion was characterized. The bromine content was 7% and the glass transition temperature was 18.8° C.
EXAMPLE 4
Preparation of a PBBMA-Styrene-Acrylonitrile Terpolymer
[0035] In a 0.5L 4 necked round bottom flask fitted with mechanical stirrer, reflux condenser, thermometer, dropping funnel and Nitrogen inlet were charged 1.4 gr SDS (Sodium Dodecyl Sulfate) and 100 mL of water. The flask was immersed in an oil bath and heated to 70° C. with continous stirring, 250 rpm, Nitrogen was introduced under the surface of the liquid. After 1 hr. the nitrogen inlet was raised above the surface of the liquid and 0.15 gr of K 2 S 2 O 8 were added. 5 min. later a solution of 18.2 gr Styrene and 5.8 gr Acylonitrile was added dropwise over 30 min. The emulsion pre-polymerization was continued for another 20 min. after which 8.5 gr of a PBBMA suspension (˜60% solids) were added dropwise over 40 min. A second portion of 0.15 gr of K 2 S 2 O 8 was added 3 hr. after the addition of the suspension was finished. The polymerization was continued overnight.
[0036] A stable latex (stable for at least one month ) was obtained.
[0037] The terpolymer isolated from this emulsion was characterized. The bromine content was 12.5%, the nitrogen content was 5% and the glass transition temperature was 107° C. The molecular weight depends on the polymerization conditions. In this particular case a Weight Average Molecular Weight, Mw, of 1.2*10 6 and Number Average Molecular Weight, Mn, of 422,000, was determined (in Dimethylformamide solution, calibrated with Polystyrene standards).
[0038] The suspensions of the invention are useful for a number of applications, and the way in which they are used and the resulting products, are also part of the invention.
[0039] Fire Retardants are commonly used in carpet-backings . However, the fire retardants of the prior art are not bound to the carpet, and are susceptible to removal by dry cleaning. According to the invention, the aqueous suspension of PBBMA is applied to the reverse side of the carpets and is polymerized by heating at temperatures above 130° C. This results in a coating of PBBMA polymer which is bound to the carpet.
[0040] In the prior art, fire retardants are used in the textile industry. However, they generally produce light scattering, because they are used in powder form. According to the invention, the aqueous solution of PBBMA, optionally with complementary components, is applied to textile materials and penetrates into the fibers, and then polymerization is effected by heating at temperatures above 130° C., thus polymerizing PBBMA and binding the resulting polymers to the fibers. Addition of free radical initiating catalysts , the conventional polymerization catalysts such as organic peroxides, e.g., benzoylperoxide , or other free radical producing catalysts, e.g.., azobisisobutyronitrile , will shorten polymerization time.
[0041] The PBBMA suspensions of the invention can be used to copolymerize PBBMA with other monomers or grafted to polymers, in order to produce adhesives which are also fire-retardants or other types of surface modifiers and binding promoters.
[0042] Likewise, the suspensions of the invention can be used to copolymerize PBBMA with other (meth)acrylate derivatives, such as butyl acrylate, methyl methacrylate or other monomers, to produce transparent plastics of predetermined refraction indices.
[0043] Double layered particles can also be produced, according to the invention, by adding another monomer, e.g. another (meth)acrylic derivative, to the PBBMA suspensions under polymerization conditions, to produce very stable latexes. An example of such other monomers can be, for instance, aliphatic (meth)acrylates or hydroxyethyl acrylate.
[0044] The novel products obtained according to the invention, and the processes for their production, are also part of the invention.
[0045] While examples of the invention have been described for purposes of illustration, it will be apparent that many modifications, variations and adaptations can be carried out by persons skilled in the art, without exceeding the scope of the claims. | Suspensions of PBBMA, characterized in that they comprise PBBMA in the form of finely ground particles and contain suspending agents chosen from among xanthene gums, anionic or nonionic purified, sodium modified montmorilonite, naphthalene sulfonic acid-formaldehyde condensate sodium salt, sodium or calcium or ammonium salts of sulfonated lignin, acrylic acids/acrylic acids ester copolymer neutralized—sodium polycarboxyl, and wetting agents chosen from among alkyl ether, alkylaryl ether, fatty acid diester and sorbitan monoester types, polyoxyethylene (POE) compounds. | 3 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to an X-ray device which includes an X-ray imaging apparatus and an X-ray generator for powering an X-ray source which co-operates with the X-ray imaging apparatus and also includes a diaphragm unit which is connected to the X-ray source and includes an adjustable diaphragm aperture in order to preset an exposure field on an X-ray image detection device, the diaphragm aperture being adjustable on the one hand by a drive unit which is controlled by a control system and on the other hand by adjusting means for manual adjustment of the diaphragm aperture.
2. Description of the Related Art
X-ray devices of this kind are known for the formation of Bucky images. Such devices utilize image detection devices in the form of film/foil combinations of various formats which are accommodated in suitably dimensioned cassettes. The examiner then selects the cassette format required for the next X-ray exposure and inserts the cassette into the X-ray device. The X-ray device is provided with a measuring device for measuring the cassette format. The control system then adjusts the diaphragm aperture in dependence on the measured cassette format so that the exposure field corresponds to the cassette format or the format of the film present therein. Such X-ray devices require manual adjustment of the exposure field only if the examiner wishes to constrict the exposure field.
Since recently so-called “digital” X-ray detectors are used as the image detection devices; such detectors include a large number of (for example, 2000×2000) detector elements which are arranged in the form of a matrix, are sensitive to light or X-rays and generate electric signals which are dependent on the X-ray intensity and are processed in the X-ray device. The X-ray device may comprise various imaging units, for example a grid exposure table for forming X-ray images of a supine patient and/or a grid wall stand for forming X-ray images of a standing patient; each of these units is provided with only a single digital detector of this kind whose dimensions, therefore, have to correspond to the largest possible exposure format (for example, 43×43 cm). Automatic adjustment of the diaphragm aperture to the format of this image detector, however, would in most cases require a rather substantial manual restriction of the exposure field, thus complicating the use of such an apparatus.
Citation of a reference herein, or throughout this specification, is not to be construed as an admission that such reference is prior art to the Applicants' invention of the invention subsequently claimed.
SUMMARY OF THE INVENTION
It is an object of the present invention to simplify the use of an X-ray device whose imaging unit (units) has (have) an image detector which has each time only a single (maximum) format. On the basis of an X-ray device of the kind set forth this object is achieved in that there is provided a storage device which co-operates with the control system and in which a respective set of exposure parameters is stored for each of a number of organs, that each set contains, in addition to the exposure parameters for the X-ray detector, an adjustment value for adjusting the exposure field, and that, when an organ is selected, the adjustment value is fetched and the exposure field is adjusted, by way of the control system and the drive unit, in conformity with the adjustment value associated with the selected organ.
The use of a storage device in which respective sets of exposure parameters are stored for various organs has since long been known in the X-ray imaging technique. According to such so-called APR (Anatomically Programmed Radiography) methods, essentially exposure parameters for the X-ray generator, for example the voltage to the X-ray tube, the current through the X-ray tube and the exposure duration, are stored in an organ-dependent manner in order to be fetched and adjusted when the relevant organ is selected.
The invention is based on the recognition of the fact that the size of the exposure field is correlated to the organ or to the body region to be imaged by way of the subsequent X-ray exposure. Therefore, for each organ the size of the required exposure field is stored additionally. The stored adjustment value is fetched when the relevant organ is selected and controls, via the control system and the drive unit, the diaphragm unit in such a manner that the preset exposure field is adjusted. After that, the examiner need only slightly change the exposure field, if at all.
During manual adjustment of the exposure field the examiner is present in the vicinity of the patient who is arranged, for example on a patient table. However, the other adjusting operations, for example selection of an organ, triggering of an X-ray exposure etc., are carried out at a control desk or a workstation which is situated in a room other than that in which the patient is present. In the embodiment wherein the control system is programmed in such a manner that, after actuation of the adjusting means, the manual adjustment of the exposure field is carried out or preserved independently of an adjustment value fetched before or after that, it is ensured that the manual adjustment made for the exposure of the relevant organ is not overwritten by an adjustment value stored for this organ so that it is canceled again. The appropriately programmed control system then consists effectively of a diaphragm controller which is arranged to control the drive unit and the diaphragm unit, as well as of the workstation which controls all components of the X-ray device as well as the overall exposure procedure.
The further embodiment wherein the control system is programmed in such a manner that after an X-ray exposure or a change of a patient to be examined an exposure field adjusted by actuation of the adjusting means is adjusted in conformity with the relevant adjustment value fetched, however, enables a change-over to be made from the manual adjustment to the stored adjustment values when an X-ray exposure or change of patient has taken place after the manual adjustment.
Bucky exposures or exposures on the wall stand are generally executed with a given distance between the X-ray source and the image detector, for example 1.15 m. In that case each exposure field corresponds to a given diaphragm aperture. However, it is often desirable to increase or decrease the distance between the X-ray source and the image detector. Therefore, the further embodiment wherein the distance between the X-ray source and the X-ray image detection device is adjustable, further comprising means for measuring this distance, and wherein the control system is programmed in such a manner that in dependence on the measured distance the diaphragm aperture has a value such that the size of the exposure field on the image detection device assumes its preset value, ensures that when said distance is changed, the diaphragm aperture is also readjusted in such a manner that the desired exposure field is obtained in the plane of the image detector.
The invention can be used with an image detector indicating a flat detector with light-sensitive or X-ray sensitive detector elements which are arranged in the form of a matrix. The invention, however, can in principle be used for all imaging units involving only a single format of the image detector.
BRIEF DESCRIPTION OF THE DRAWING
The invention will be described in detail hereinafter with reference to the drawings. Therein:
FIG. 1 shows an X-ray device according to the invention, and
FIGS. 2A-2E show flow charts illustrating the control of the diaphragm unit.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The X-ray device shown in FIG. 1 includes an X-ray source 1 which is controlled by an X-ray generator 2 . The X-ray source is mounted on a stand (not shown) so as to be displaceable at least in the vertical direction. The X-ray device also includes a patient table which is symbolically represented by a table top 3 ; underneath the table there is arranged a digital image detector 4 with a matrix-like array of detector elements. In addition to the patient table, or instead of the table, there may be provided a grid or Bucky wall stand with such an image detector.
The size of the exposure field formed on the image detector 4 by the X-ray source 1 is adjusted by means of a diaphragm unit 5 . The diaphragm aperture, i.e. the angle of aperture of the radiation beam denoted by dashed lines in the plane of drawing, is determined by a first set of collimators 51 which are made of, for example lead and whose edges extend perpendicularly to the plane of drawing of FIG. 1 . There is also provided a second set of collimators which, however, is not shown in FIG. 1; these collimators have edges which extend parallel to the plane of drawing and determine the angle of aperture of the radiation beam 10 in the direction perpendicular to the plane of drawing. The diaphragm aperture can be adjusted by means of a motor 52 which is accommodated in the diaphragm unit 5 (unlike the situation shown in the drawing). The motor 52 is controlled by means of a diaphragm controller 53 which co-operates with a workstation 6 .
The diaphragm aperture can also be adjusted manually by the examiner while using an adjusting member 54 . The actuation of the adjusting member 54 is detected by the diaphragm controller 53 . The examiner can check the size of the adjusted exposure field prior to an exposure by using a light localizer (not shown) which is included in the diaphragm unit 5 and produces a light beam which is bounded by the collimators 51 etc. in the same way as the X-ray beam 10 during the exposure. The distance between the X-ray source and the image detector is measured by a measuring device 55 and the measured value is applied to the diaphragm controller 53 .
The workstation 6 controls inter alia the diaphragm controller 53 and the X-ray generator 2 . To this end it can access a storage device 61 with a data base in which a respective data set is stored for each of a plurality of organs. Each data set contains the optimum exposure parameters for the relevant organ in the normal case; it also includes a value concerning the size of the exposure field to be adjusted. This adjustment value can be applied to the diaphragm controller 53 in order to adjust the exposure field while taking into account the measured distance between the X-ray source and the image detector.
Moreover, the workstation can reconstruct an X-ray image from the signals of the X-ray image detector 4 for display on a monitor 62 . On the other hand, the workstation can also reproduce a patient and exposure list on the monitor, which list contains not only the name of the patient but also the organs or parts of the body to be radiographed. This list can be applied to the workstation 6 , for example via a so-called RIS (Radiology Information System) link. There is also provided an input unit 63 , for example a keyboard and/or a touch screen unit, for communication with the workstation 6 . The patient table 3 (and possibly also the above-mentioned grid wall stand) with the X-ray source 1 and the diaphragm unit 5 are present in a room other than that in which the components 6 , 61 , 62 and 63 are installed. The examiner is active in both rooms for each X-ray exposure: during the adjustment of the exposure parameters by selection of the organ as well as during the initiation of an X-ray exposure the examiner will be present in one room while he or she will be present in the other room during the positioning of the patient and also during manual adjustment of the diaphragm unit, if any.
The FIGS. 2A to 2 E show parts of flow charts which govern the adjustment of the exposure field. In conformity with FIG. 2A, after the selection of an organ or the fetching of APR data, in the step 101 it is checked whether a given flag has been set (M−flag=1) or not (step 102 ). When the flag has not been set, in the step 103 the workstation generates an instruction for the diaphragm controller 53 so as to adjust the size of the exposure field while taking into account the distance between the X-ray source 1 and the image detector 4 in conformity with the adjustment value stored for the relevant organ to be imaged. However, if the flag has been set, the adjustment remains the same. As is shown in the FIGS. 2B . . . 2 E, the flag can be set and reset in dependence on four different events.
In conformity with FIG. 2B, in the case of manual adjustment of the diaphragm aperture by means of the adjusting member 54 (block 110 ) the flag is set in the step 111 (M−flag=1). However, in the case of a change of patient (block 120 ), the flag is reset in the step 121 (M−flag=0, FIG. 2 C). The same takes place in the step 131 as shown in FIG. 2D after the initialization of an X-ray exposure (block 130 ) or in the step 141 upon a (new) start of the system 140 .
The operation of the X-ray unit during the execution of a patient and exposure list, reproduced on the monitor 62 by the examiner, will be described in detail hereinafter. It is assumed that the list successively specifies a first exposure in the form of an exposure of the organ 1 (for example, a lateral chest exposure) of the patient A and a second exposure of a second organ of the patient A, for example lung p.a.(even though the lung is to be imaged in both cases, the p.a. and the lateral exposure of this organ are treated as different organs with a different set of exposure parameters). It is assumed that the patient and exposure list specifies as the third exposure an exposure of the same organ (lung p.a.) of a further patient B.
For the first exposure the examiner positions the patient A on the patient table (or in front of said wall stand) and adjusts the size of the exposure field on the diaphragm unit by means of the adjusting member 54 , thus setting the flag as shown in FIG. 2 B. The examiner subsequently enters the room in which the workstation is located and adjusts the X-ray device for the first exposure, i.e. the exposure of the patient A with the organ 1 is selected, so that an adjustment value for the exposure field is fetched. However, because the flag is set, in conformity with the flow chart shown in FIG. 2A the exposure field is not adjusted to the fetched adjustment value. The examiner then triggers the first X-ray exposure, with the result that (in conformity with FIG. 2D) the flag is reset in conformity with the step 131 .
If desired, the patient table may be constructed so that the X-ray source 1 and the image detector 4 are simultaneously displaceable in opposite directions so that slice images can be formed. In such a slice imaging mode usually a series of images of slices in different positions is formed, so that in this mode a (slice) image may not give rise to the described resetting of the flag.
Therefore, when the examiner selects the second exposure on the workstation, in conformity with FIG. 2A the adjustment value for the second organ (lung p.a.) is fetched and adjustment is performed by the diaphragm controller 53 and the motor 52 so that the manual adjustment concerning the previous exposure is overwritten. The examiner then positions the patient A in such a manner that the second exposure can be made. When the adjusting member 54 is then actuated, the preset of the diaphragm unit is changed accordingly by the adjustment value fetched for lung p.a. from the memory 61 , so that the flag is set again.
When after this second exposure the third exposure (patient B) in the list is selected in the workstation 3 , the flag is reset because of the change of patient (step 121 ), even if the same organ as during the preceding exposure is to be imaged. The manual adjustments carried out for the second exposure are, therefore, overwritten in conformity with the adjustment value preset for the third organ to be imaged (lung p.a.). If necessary, the examiner can change this preset again by means of the adjusting member 54 .
The described routine illustrates that the X-ray device offers the examiner very good economics in combination with high flexibility in respect of adjustment.
All references cited herein are incorporated herein by reference in their entirety and for all purposes to the same extent as if each individual publication or patent or patent application was specifically and individually indicated to be incorporated by reference in its entirety for all purposes. | The invention relates to an X-ray device which operates with only a single image detection device whose format corresponds to the maximum exposure format. In order to facilitate the adjustment of the exposure field for an exposure, a respective set of exposure parameters is stored in a memory for each of the various organs to be imaged; this set includes inter alia an adjustment value for the size of the exposure field for an exposure of the relevant organ. This adjustment value is fetched and the diaphragm unit is automatically controlled in such a manner that the fetched adjustment value is (pre)adjusted. | 6 |
BACKGROUND OF THE INVENTION
The present invention is directed to a socket having gripping means for gripping a tool having a cylindrical shaft, such as a dental tool. The socket includes a sleeve-shaped shaft which is mounted for rotation and accepts a clamping sleeve which holds a tool shaft. The clamping sleeve has at least two longitudinal slots extending inward from a first end of the clamping sleeve which faces away from the tool to form resilient tongues which are movable from a clamping position for engaging the tool shaft to an outward position to allow releasing of the shaft. The socket includes an axially movable ram, which is actuated by a handle for the purpose of moving the tongues from the clamping position to an unclamped position to allow releasing the tool, and the ram has an outside tapering conical surface for engaging the one end of the clamping sleeve which is provided with an inwardly tapering surface.
A rotary socket having a clamping sleeve for gripping a shaft of a tool is disclosed in U.S. Pat. No. 4,089,115. In this arrangement, a ram is threaded into the end of the shaft and is movable by means of a separate tool, such as a polygonal-shaped wrench or the like, from a retracted position withdrawn from engagement with the gripping sleeve to a position causing the gripping sleeve to release the tool. In the clamped position, the tool shaft is held by the clamping tongues of the clamping sleeve with a fricational grip. In a retracted position, the ram is situated at a slight axial distance from the corresponding ends of the sleeve. For removing the tool, the ram is threaded into the shaft until its outside conical end engages inside, conical surfaces of the clamping sleeve to resiliently bias the tongues radially outward to a releasing position to release the tool shaft.
Dependent on the extent on which the ram is screwed into the shaft, a certain pre-adjustment of the clamping tongues can also be achieved with this device. The two cones are in engagement with one another in this pre-adjustment on one hand, but on the other hand, a reliable holding of the tool shaft in the clamped position still is established.
A disadvantage with this clamping device is that an additional tool is required for removing a tool that is gripped in the gripping sleeve. Another significant disadvantage, moreover, is that the clamping tongues are subjected to a torsional stress when the ram is screwed in and, thus, the useful life of the clamping sleeve is reduced.
Another known type of clamping device or socket is disclosed in German OS 34 02 635. As disclosed, a pre-adjustment of the clamping tongues, such as mentioned above, is achieved in that the clamping tongues are spread by a pressure member, which is seated in an axial movable fusion in the head housing. A stop element for one-time adjustment of this pre-adjustment is allocated to this pressure member, and this stop element is positioned in various positions by means of being screwed into the shaft and limiting the movement of the pressure member from the clamping sleeve. Of the two exemplary embodiments shown in this German reference, one, likewise, has the disadvantage that relatively high forces must be exerted in order to bring the clamping sleeve out of the clamping position into an unclamped position to allow removal of the tool. The other embodiment is relatively complicated to manufacture due to the many parts of the arrangement composed of the spreader element and pressure member and, in particular, due to the spreader element with the key surfaces. Another disadvantage is that the spreader element must be integrated positionally dependent on the clamping sleeve and this makes assembly more difficult.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a chuck or socket with a clamping device, which is an improvement over the prior art and which, in particular, is well-suited for push-button actuation. The improved socket has the improved possibilities of integration being established in comparison to known designs and has, insofar as possible, fewer or, respectively, less involved parts. The socket enables removal of the tool with a low exertion of force while holding the tool with high retaining forces. Over and above this, the goals of the improved socket are to be able to assemble the parts, which are positionally independent of one another.
Significant advantages of the invention over the prior art are that the clamping device is composed of a total of only three parts, that the lower number of contacting faces having a higher processing quality are present, and that the assembly can occur proceeding from the tool side. This has the advantage that the adjustment tolerances lie at the side facing away from the pressure cover and, by contrast, extremely narrow tolerances can be observed at the side of the pressure cover.
Other advantages and features of the invention will be readily apparent from the following description of the preferred embodiments, the drawings and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross sectional view, with portions in elevation for purposes of illustration, of a head housing of a dental turbine handpiece having the rotary socket of the present invention;
FIG. 1a is a side view of a tool received in the rotary socket of the present invention;
FIG. 2 is a longitudinal cross sectional view of a socket with the clamping arrangement of the present invention;
FIG. 3 is a longitudinal cross sectional view of the clamping sleeve removed from the socket in accordance with the present invention;
FIG. 4 is a side elevational view, with portions removed for purposes of illustration, of the clamping sleeve of FIG. 3 rotated through approximately 90°;
FIG. 5 is an end view of the clamping sleeve of FIG. 3;
FIG. 6 is a longitudinal cross sectional view similar to FIG. 2 of a modification of the clamping sleeve in accordance with the present invention;
FIG. 7 is a perspective view, with portions broken away for purposes of illustration, of an embodiment of the socket in accordance with the present invention;
FIG. 8 is a perspective view of a ram utilized with the clamping sleeve of FIG. 7;
FIG. 9 is an enlarged perspective view of an end of the clamping sleeve of FIG. 7.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The principles of the present invention are particularly useful when incorporated in a socket or chuck, generally indicated at 100 in FIG. 2. The socket 100 has an outer sleeve 3 which is connected with a rotor 2 (FIG. 1) and the sleeve and rotor are mounted in a head housing 1 of a dental handpiece having a turbine for rotation in a known manner, such as by ball bearings. The socket 100 has a clamping sleeve 4 mounted in the outer sleeve 3 for releasably holding a cylindrical shaft 5a of a tool 5 (FIG. 1a), which may be a drill, a miller or the like. As illustrated in FIG. 1, for the removal of the tool, a pressure cover 6 is arranged on an end of the head housing 1 facing away from the tool, and this pressure cover, when pushed against a compressive spring 7, has a pressure face or projection 8 that presses against a sleeve-shaped ram 9, which is axially displaceable within the outer sleeve 3. When the ram 9 is moved into engagement with a first end of the clamping sleeve 4, it will cause the clamping sleeve to release the tool to allow its removal.
The structure of the socket 100 is best illustrated in FIGS. 2-5. The outer sleeve 3 is fashioned as a sleeve structure with an inwardly extending flange forming a step or shoulder 10 at a first or one end, which is away from a second end 101 in which the tool is inserted. A ram 9 having a shoulder 11 is movable from a position illustrated in FIG. 2, with the shoulder 11 engaging the step 10 axially towards the opposite end 101. At the opposite end 101 of the sleeve 3, which is the tool entry end, the clamping sleeve 4 has its first end inserted into the outer sleeve 3 and the two sleeves are secured together, such as by having threads on the inner sleeve engaged in threads on the outer sleeve to form a screw-type connection 12 adjacent a second end of the sleeves, which is also adjacent the entry end for the tool. A slot 13 is provided on a second end of the sleeve 4 to enable engagement by a separate tool, such as a screwdriver, in order to facilitate this threading of the sleeves together.
The sleeve 4, as best illustrated in FIGS. 3 and 4, has an inside bore or diameter 14, which roughly corresponds to the diameter of the tool shaft 5a of the tool 5, which is to be received in the sleeve. In the first or the upper end facing away from the tool entry end, the inside diameter is slightly smaller than the shaft diameter of the tool to provide contact faces, such as 15, with which the clamping sleeve presses against the tool shaft 5a with a defined clamping force in this region. In order to keep the wear of the contact faces 15 and of the inside bore 14 as low as possible, the clamping sleeve is completely or partially coated with CVD. (Chemical-Vapour-Deposition)
In a known fashion, the clamping sleeve 4 has two slots 16, which extend inward from the first end and are diametrically opposite one another. Each of the slots 16 inward of the first end passes through two circular opening or apertures 17 with the slot ending in the axially spaced innermost aperture. Adjacent the first end, the slot 16 extends into a semicircular recess 18. As a result of the slot 16, the apertures 17 and recesses 18, two resilient tonges 4a and 4b are formed over the circumference of the sleeve 4, as best illustrated in FIGS. 3 and 5. These tongues 4a and 4b will press against the tool shaft 5a with the contact faces 15 when in the clamped position and are spread radially outward to an unclamping position to allow removal of the tool. The recesses 18 are, advantageously, such that the circumferential line from slot to slot decreases towards the free, first end of the tongues, and the resilient tongues become narrower towards their free, first ends, as seen in FIG. 4.
At the first end, which faces away from the second or tool entry end, the clamping sleeve 4 comprises a partial inside cone or inner tapering surface 20, which extends at approximately 18° relative to the axis of the sleeve. The cone 20 corresponds with an outside cone or outer tapering surface 21 of the ram 9. The outside cone 21 extends at approximately 30° angle with the axid and is, thus, flatter than the inside cone of the clamping sleeve. In combination with the aforementioned recess 18, the contacting between the two cones 20 and 21 is practically limited to a light contact, such as the end line 23 of the tongues, and this results in a very low disengagement force being required.
In the clamping position, the two cones 20 and 21 are in engagement with one another; however, with the insertion of the tool 5, by contrast, the two cones 20 and 21 do not contact while in the clamped position of the clamping sleeve. The tool shaft 5a is held in the clamped position via the contact faces 15. The ram is pushed against the step 10 of the shaft 3, given axial introduction of the tool. In order to cancel the retaining force and to be able to remove the tool from the clamping device, a select pressure on a pressure cover 6 is required. Pressure member or projection 8 of the cover will then be pressed against the end face of the ram 9 and further pressure will move this axially downward, as illustrated in FIG. 2, so that as a consequence the conical connection of the ram cone 21 of the ram with the cone 20 of the two clamping tongues 4a and 4b will occur. The two clamping tongues 4a and 4b will then be pressed radially outward and the retaining force on the contact faces 15 will be cancelled. After the pressure cover 6 is released, it will move back to its initial position due to the force of the spring 7. The ram 9 is again pressed against the detent or stop surface 10 due to a consequence of the force components acting parallel to the axis, which occur due to the slanting surfaces of the cone faces.
Since the ram 9 is a rotationally symmetrically turned part, it is very easy to manufacture during an automated manufacturing process. Since the insertion of the ram 9 into the sleeve 3 is positionally independent, an assembly of the ram is very simple. First, the ram 9 is axially introduced into the sleeve 3 from the second end or tool side 101. Subsequently, the clamping sleeve 4 is inserted and threaded to form the thread connection 12 with the depth of the thread connection defining the degree of pre-adjustment for the tongues 4a and 4b relative to the ram 9.
A modification of the arrangement of FIG. 2 is illustrated in FIG. 6. In this modification, clamping sleeve 4' can be pressed into or glued into the outer sleeve 3'. Then, however, an additional part is required, namely a screw ring 22, which provides the required detent or stop in a pre-selected and pre-adjusted position. The positional independence when the parts are assembled is also established in this embodiment, however, it is not as advantageous as the embodiment shown in FIG. 2, because the pre-adjustment in the embodiment of FIG. 2 is established without influencing the gap which exists between the pressure cover 6 and the ram 9.
The recesses 18 can, advantageously, be formed in that the end face at the first end of the clamping sleeve 4 is approached from above with a cylindrical miller having a transverse disposed axis or in that it is milled in a long, slot plane with an arbitrary profile cutter having a rotational axis proceeding transverse relative to the slot plane. A circular shape is not absolutely necessary for the recesses 18, and the only thing critical is that as much material as possible is removed from the clamping sleeve 4 itself in the region of the slots so that only a line contact at the corresponding cooperating cone 20 of the clamping sleeve occurs with the cone 21 of the ram entering into the first end of the clamping sleeve. With only a line contact, the disengagement forces can be reduced to a minimum. This line contact forms only a fraction of the contacting circumference. Instead of being produced by milling and boring, the slot 16, aperture 17 and recess 18 can also be produced in a suitable way with an erosion process.
In comparison to the prior art, the embodiment described above has the advantage that the overall clamping device is constructed of only three parts, namely the outer sleeve 3, the clamping sleeve 4 and the ram 9.
An embodiment of the socket is generally indicated at 100' in FIG. 7. In this embodiment, a clamping sleeve 25 has a collar 26 at a second end which collar 26 has outside threads 29. An outer sleeve 28 at a second end has internal threads 30, and the clamping sleeve 25 is inserted into the second end of the outer sleeve 28 with the threads 29 received in the threads 30. After the clamping sleeve 25 is positioned, it is then secured against rotation. This can occur with one or more gluing or welding spots. For example, one or more access bores 41 are provided in the circumference of the outer sleeve 28 through which a welding or gluing can occur.
As in the first embodiment, the clamping sleeve 25 is provided with longitudinal slots 31 on both sides, and these longitudinal slots 31 end in recesses or apertures, such as 32. Lying diametrically opposite each other and offset by approximately 90° from the slots 31, the clamping sleeve 25 contains two grooves with conical seating surfaces 33, which correspond with the likewise conical or tapered mating surfaces 34 on projections 36 (FIG. 8), which projections extend from a lower end of a sleeve-shaped ram 35. The ram 35 also includes a step 37, with which the ram is axially seated against an inside collar or flange 38 at the first end of the outer sleeve 28. The coaction between the inside collar 38 and the step 37 forms an axial detent that insures that the two continuations or projections 36 of the ram 38 provided with the conical outside surfaces 34 remain engaged in the grooves forming the conical seating surfaces 33. The position of the ram 35 and the clamping sleeve 25 is adjusted only once during assembly of the ram and clamping sleeve, and are aligned relative to one another by insertion into the outer sleeve 28 proceeding from the second or tool side of the outer sleeve. The depth that the clamping sleeve 25 is threaded into the sleeve 28 will determine the degree of pre-adjustment of the tongues of the clamping sleeve. In this embodiment, too, the two cones or, respectively, conical seating surfaces 33 and 34 are designed so that only a line contact is established therebetween, for example at the location 39 in FIG. 9. This line contact remains practically unaltered during the disengagement action.
As illustrated in FIGS. 2 and 7, the opening 17 and 32, in which the longitudinal slots 16 and 31 extent, can have different designs and shapes. The shape as shown in FIG. 6 is especially advantageous. The recess therein is formed by tangential connections of two axially-spaced circles K1 and K2, which have different diameters. A particular advantage of this type of recess lies in the fact that a uniform course of material tension is established for the resilient tabs or tongues.
Although various minor modifications may be suggested by those versed in the art, it should be understood that we wish to embody within the scope of the patent granted hereon all such modifications as reasonably and properly come with the scope of our contribution to the art. | A socket, which receives a tool having a cylindrical shaft and which is mounted for rotation to rotate the tool, has an outer sleeve which receives a clamping sleeve and a ram for engaging a first end of the clamping sleeve. The first end of the clamping sleeve is provided with slots defining resilient tongues which are moved from a clamping position radially outward to a position for releasing the shaft by engagement with the ram. The ram has either an outer conically tapered surface or partially conically outer tapered surfaces on projections which engage inner tapered surfaces of each of the tongues or fingers. Preferably, the tapers of the ram and fingers are selected so that only substantially a line contact is formed therebetween to reduce the force necessary to move the fingers or tongues radially outward to the declamping or disengaging position. | 8 |
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part applicaton of application Ser. No. 08/335,040 filed Nov. 7, 1994, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a novel flux washing agent used in the production of printed circuit boards and the like. More particularly, the present invention relates to a flux washing agent having the property to suppress etching of solder on printed circuit boards.
2. Description of the Related Arts
Generally in conventional production processes of printed circuits and printed circuit boards, flux is coated on a printed circuit or a printed circuit board for the purpose of fixing solder firmly to the board. The flux is generally removed by washing with a flux washing agent after the soldering is finished because, when the flux is left remaining on the printed circuit or the board, the residual flux causes a decrease in electric resistance of the board and the breaking of the circuit by corrosion.
As the flux washing agent, chlorofluorohydrocarbon solvents, such as 1,1,2-trichloro-1,2,2-trifluoroethane (Flon 113), trichloroethylene, 1,1,1-trichloroethane and the like, have heretofore been widely used because of the excellent washing ability and the absence of inflammability. However, the chlorofiuorohydrocarbon solvents cause social and environmental problems, such as ozonosphere destruction, underground water pollution, and air pollution, and total prohibition of use and production of these materials are in progress.
As flux washing agents other than the chlorofiuorohydrocarbons, various kinds of flux washing agents, such as alcohols, glycols, glycol ethers, hydrocarbons including terpenes, and agents containing these solvents and surfactants, have been proposed. However, the proposed solvents are dangerous because of infiammabiIity and are not preferable for maintaining working safety.
As safe flux washing agents using aqueous systems, inorganic alkaline washing agents are widely used. However, the alkaline washing agents have drawbacks in that the washing ability is inferior to the chlorofluorohydrocarbons and that reliability of the printed circuits and printed circuit boards are decreased because the inorganic alkaline washing agents have a greater tendency to remain on the boards and the circuits. The inorganic alkaline washing agents have also another drawback in that etching of solder components such as lead and tin by the agents occurs vigorously and various kinds of trouble are caused.
JP 01-14924 (Mitsubishi) concerns a semiconductor surface cleaning composition containing 0.01 to 30 weight % quaternary ammonium hydroxide, 0.01 to 30 weight % hydrazine and 0.01 to 5 weight % nonionic surfactant. The nonionic surfactant results in a difficulty in that the nonionic surfactant causes a decrease in the solubility of rosin flux.
As described above, no solder flux washing agents have heretofore been known which are superior to the chlorofluorohydrocarbons in view of the washing ability and the safety. In other words, no solder flux washing agent which can replace chlorofiuorohydrocarbon has heretofore been found.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a high performance solder flux washing agent having a washing ability which is comparable with those of Flon 113 and trichloroethylene, but which are safe and do not cause environmental pollution and exhibiting an excellent rinsing property.
As the result of extensive studies by the present inventors to develop a flux washing agent which can replace Flon 113 and trichloroethylene, it was discovered that an alkaline aqueous solution containing a quaternary ammonium salt and hydrazinc has an excellent washing property and provides a safe washing agent. The present invention has been completed on the basis of the discovery.
Thus, the present invention provides a flux washing agent which comprises an aqueous solution containing a quaternary ammonium salt represented by the general formula (R 1 ) 3 N-R)! + .X- wherein R indicates an alkyl group having 1 to 4 carbon atoms or a hydroxy-substituted alkyl group having 1 to 4 carbon atoms, R 1 indicates an aIkyl group having 1 to 4 carbon atoms, and X indicates OH group, HCO 3 group or CO 3 group, and hydrazinc.
Other and further objects, features and advantages of the invention will appear more fully from the following description.
DESCRIPTION OF PREFERRED EMBODIMENTS
The quaternary ammonium salt in the present invention is represented by the general formula (R 1 ) 3 N-R)! + .X - , wherein R indicates an alkyl group having 1 to 4 carbon atoms or a hydroxy-substituted alkyl group having 1 to 4 carbon atoms, R 1 indicates an alkyl group having 1 to 4 carbon atoms, and X indicates OH group, HCO 3 group or CO 3 group. Examples of the quaternary ammonium salts include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethyl-2-hydroxyethylammonium hydroxide, triethyl-2-hydroxyethyl-ammonium hydroxide, tripropyl-2-hydroxyethylammonium hydroxide, tributyl-2-hydroxyethylammonium hydroxide, tetramethylammonium carbonate, tetraethylammonium carbonate, tetrapropylammonium carbonate, tetrabutylammonium carbonate, trimethyl-2-hydroxyethylammonium carbonate, triethyl-2-hydroxyethylammonium carbonate, tripropyl-2-hydroxyethylammonium carbonate, tributyl-2-hydroxyethylammonium carbonate, tetramethylammonium hydrogen carbonate, tetraethylammonium hydrogen carbonate, tetrapropylammonium hydrogen carbonate, tetrabutylammonium hydrogen carbonate, trimethyl-2-hydroxyethylammonium hydrogen carbonate, triethyl-2-hydroxyethylammonium hydrogen carbonate, tripropyl-2-hydroxyethylammonium hydrogen carbonate, and tributyl-2-hydroxyethylammonium hydrogen carbonate. The quaternary ammonium salt may be used singly or as a combination of two or more kinds.
In the flux washing agent of the present invention, concentration of the quaternary ammonium salt described above is not particularly limited, but is generally 0.01 to 30% by weight, preferably 0.1 to 10% by weight. Concentration of hydrazine is 0.5 to 15% by weight, preferably 1 to 10% by weight. When the concentration of the quaternary ammonium salt or hydrazine is lower than the specified range for the respective compound, sufficient washing ability cannot be obtained. When the concentration of the quaternary ammonium salt or hydrazine is higher than the specified range for the respective compound, almost no increase in the washing ability is found and the concentration is economically disadvantageous. Thus, concentrations of these compounds out of the specified ranges are not preferable.
In the present invention, the quaternary ammonium salt and hydrazinc can be used in various combinations as desired depending on the material and the form of the article for washing and the kind of the flux. However, the washing ability is significantly decreased when either one of the indispensable components which are the quaternary ammonium salt and hydrazinc is absent. In other words, the practical flux washing agent showing safety to the environment and having excellent washing ability and rinsing property can be obtained only by the combination of the two indispensable components.
The flux washing agent of the present invention is used at a temperature in the range of ordinary temperature to 90° C. The temperature can be selected suitably depending on the material and the form of the article for washing and the kind of the flux.
The flux washing agent of the present inention does not contain surfactants.
The flux washing agent of the present invention can be used as a washing agent for dogreusing instruments and electronic parts as well as a flux washing agent.
To summarize the advantages obtained by the invention, the flux washing agent of the present invention has excellent washing ability, is highly safe, and exhibits property to sufficiently suppress dissolution of solder. The flux washing agent of the present invention also has an excellent rinsing property because it is an aqueous solution. Therefore, the flux washing agent has the excellent properties practically to replace chlorofluorohydrocarbon solvents, such as Flon 113 and trichloroethylene.
The invention will be understood more readily with reference to the fallowing examples; however, these examples are intended to illustrate the invention and are not to be construed to limit the scope of the invention.
EXAMPLE 1 TO 9 AND COMPARATIVE EXAMPLES 1 TO 5
On the whole surface of a printed circuit board (a copper-plated laminate board), a rosin flux (a product of Sanwa Kagaku Co., Ltd.; a trade name, SF-270) was coated and dried at 140° C. for 2 minutes. The board was treated with a solder flow at 250° C. for 5 seconds to prepare a sample board. The sample board was treated for testing with various kinds of washing agent having various compositions at various washing temperatures for various washing times and evaluated on the washing ability.
For the test, the sample board was dipped into a washing solution. Degree of removal of the flux was visually observed and the washing ability was evaluated according to the following criterion:
⊚ The flux is removed completely.
◯ Most of the flux is removed.
Δ Some amount of the flux is remaining.
X A considerable amount of the flux is remaining.
Results of the evaluation is shown in Table 1.
TABLE 1__________________________________________________________________________quaternary ammonium salt concen- concen- tration of washing washing tration hydrazine temperature timekind % by wt. % by wt. °C. minute evaluation__________________________________________________________________________Example 1 tetramethylammonium 0.7 3.0 60 5 ⊚ hydroxideExample 2 the same as Example 1 3.7 3.0 60 5 ⊚Example 3 the same as Example 1 1.5 3.0 40 10 ⊚Example 4 the same as Example 1 3.7 1.0 60 5 ∘Example 5 trimethyl-2-hydroxy- 1.0 5.0 70 5 ⊚ ethylammonium hydroxideExample 6 the same as Example 5 4.0 0.5 60 5 ⊚Example 7 tetraethylammonium 5.0 1.5 50 5 ∘ hydroxideExample 8 tetramethylammonium 8.0 2.0 70 10 ∘ carbonateExample 9 tetramethylammonium 4.0 3.0 60 5 ⊚ hydroxide tetramethylammonium 1.0 hydrogen carbonateComparative tetramethylammonium 3.7 -- 60 5 ΔExample 1 hydroxideComparative tetramethylammonium 0.7 -- 60 5 xExample 2 hydroxideComparative tetramethylammonium 8.0 -- 70 10 x˜ΔExample 3 carbonateComparative tetramethylammonium 0.7 -- 80 5 ΔExample 4 hydroxideComparative none -- 5.0 60 5 xExample 5__________________________________________________________________________
EXAMPLES 10 to 12 and Comparative Examples 6 to 8
Etching rates of lead and tin at 60° C. were measured with a printed circuit board prepared by using a conventional solder (lead/tin: 6/4). Results are shown in Table 2.
TABLE 2______________________________________quaternary ammonium salt concen- etching etching concen- tration of rate of rate of tration hydrazine lead tinkind % by wt. % by wt. Å/min. Å/min.______________________________________Example 10 tetramethyl- 3.7 3.0 5 10 ammonium hydroxideExample 11 trimethyl-2- 1.0 5.0 1 or less 5 hydroxyethyl- ammonium hydroxideExample 12 tetramethyl- 8.0 2.0 1 or less 5 ammonium carbonateComparative tetraethyl- 3.7 -- 100 950Example 6 ammonium hydroxideComparative trimethyl-2- 1.0 -- 65 700Example 7 hydroxyethyl- ammonium hydroxideComparative tetramethyl- 8.0 -- 35 300Example 8 ammonium carbonate______________________________________
EXAMPLE 13
A sample board prepared as in the Examples hereinabove was dipped in a washing agent consisting of 0.7% by weight of tetramethylammonium hydroxide (TMAH) and 3.0% by weight of hydrazine, at a temperature of 60° C. for 5 minutes, and the amount of the dissolved rosin flux was determined. The result is shown in Table 3.
Comparative Examples 9 to 12
The sample board (prepared as described in the Example 13 hereinabove) was dipped in a washing agent consisting of 0.7% by weight of tetramethylammonium hydroxide (TMAH), 3.0% by weight of hydrazine, and a prescribed amount of nonionic surfactant (EP-130A™ produced by Dai-ichi Kogyo Seiyaku Co., Ltd. of Japan) at a temperature of 60° C for 5 minutes, and the amount of the dissolved rosin flux was determined. The results are shown in Table 3.
TABLE 3______________________________________ amount of concentration (% by weight) rosin flux nonionic dissolved TMAH hydrazine surfactant (mg/ml)______________________________________Example 13 0.7 3.0 -- 3.4Comparative Example 9 0.7 3.0 0.02 3.1Comparative Example 10 0.7 3.0 0.2 2.8Comparative Example 11 0.7 3.0 0.6 2.8Comparative Example 12 0.7 3.0 1.2 2.8______________________________________
As Table 3 shows, when a nonionic surfactant is added to the washing agent of the present invention, the solubility of the rosin flux becomes substantially lowered, which is contrary to the object of the present invention.
As clearly shown in the examples, the flux washing agent of the present invention has an excellent washing ability and shows very small etching rates of lead and tin. | A flux washing agent which comprises an aqueous solution containing a quaternary ammonium salt and hydrazine is disclosed. The flux washing agent is used in the production of printed circuit boards and the like. The flux washing agent has a washing ability, and a property to suppress etching of solder which are comparable with those of Flon 113 and trichloroethylene heretofore used as flux washing agents. Furthermore, the flux washing agent is safe, does not cause environmental pollution and has an excellent rinsing property. | 2 |
FIELD OF THE INVENTION
[0001] The present invention relates to an intestine-targeted pharmaceutical composition comprising a Phenanthrenequinone-based compound. More specifically, the present invention relates to an oral pharmaceutical composition with formulation of an intestinal delivery system of a certain Phenanthrenequinone-based compound or a pharmaceutically acceptable salt, prodrug, solvate or isomer thereof, as an active ingredient.
BACKGROUND OF THE INVENTION
[0002] With recent study of the present applicant, it was revealed that, as compounds of similar series to phenanthrenequinone-based compound in accordance with the present invention, naphthoquinone-based compound such as β-lapachone {7,8-dihydro-2,2-dimethyl-2H-naphtho(2,3-b)dihydropyran-7,8-dione}, dunnione {2,3,3-tirmethyl-2,3,4,5-tetrahydro-naphtho(2,3-b) dihydrofuran-6,7-dione}, α-dunnione {2,3,3-tirmethyl-2,3,4,5-tetrahydro-naphtho(2,3-b)dihydrofuran-6,7-dione}, nocardinone A, nocardinone B, lantalucratin A, lantalucratin B, lantalucratin C and the like is effective for prevention or treatment of obesity, diabetic, metabolic diseases, degenerative diseases, and mitochondrial dysfunction-related diseases (Korean Patent Application Nos. 2004-0116339 and 2006-14541).
[0003] However, the aforesaid naphthoquinone-based compound is a sparingly-soluble material which is soluble at a low degree of about 2 to 10% only in high-solubility solvents, such as CH 2 Cl 2 , CHCl 3 , CH 2 ClCH 2 Cl, CH 3 CCl 3 , Monoglyme, and Diglyme, but is poorly soluble in other ordinary polar or nonpolar solvents. For this reason, the aforesaid naphthoquinone-based compound suffers from various difficulties associated with formulation of preparations for in vivo administration, in spite of excellent pharmacological effects.
[0004] Under current circumstances, the aforementioned highly-insoluble naphthoquinone-based compound has a disadvantage of a significant limit in formulation of the compound into desired pharmaceutical preparations. Even though physiological activity of the naphthoquinone-based compound is elucidated by the present applicant, a dosage form of the naphthoquinone-based compound is limited to a formulation for in vivo administration via intravenous injection.
[0005] However, when the naphthoquinone-based compound which is a sparingly-soluble drug is administered by itself or in the form of a conventional simple formulation via an oral route, there is substantially no absorption of the compound into the body, that is, the bioavailability of the drug is very low, so it is impossible to exert the intrinsic efficacy of the drug.
[0006] Meanwhile, the present applicant has proposed a novel phenanthrenequinone-based compound having the structure of the naphthoquinone-based compound (Korean Patent Application Nos. 2007-0040673). However, the phenanthrenequinone-based compound has also sparingly-soluble problems.
[0007] The drugs can exert therapeutic effects only when an active ingredient is absorbed into the body in an amount exceeding a certain concentration; however, a variety of factors are implicated in bioavailability, the degree to which a drug or other substance becomes available to the target tissue after administration. Low bioavailability of the drug or substance raises serious problems in development of drug compositions.
[0008] Therefore, in order to sufficiently and satisfactorily exploit inherent pharmacological properties of the phenanthrenequinone-based compounds, there is an urgent need for development and introduction of a method which is capable of maximizing the bioavailability of these drugs.
SUMMARY OF THE INVENTION
[0009] Therefore, the present invention has been made to solve the above problems and other technical problems that have yet to be resolved.
[0010] As a result of a variety of extensive and intensive studies and experiments to solve the problems as described above, the inventors of the present invention have discovered that when a sparingly-soluble phenanthrenequinone-based compound is formulated into an intestine-targeted pharmaceutical composition, it is possible to minimize inactivation of the active ingredient which may occur due to internal bodily environment such as stomach, it is possible to solve a problem of low bioavailability suffered by conventional oral administration, and finally it is possible to significantly improve pharmacokinetic properties of the phenanthrenequinone-based compound. The present invention has been completed based on these findings.
[0011] In accordance with an aspect of the present invention, the above and other objects can be accomplished by the provision of an oral pharmaceutical composition wherein a phenanthrenequinone-based compound represented by Formula 1 below, or a pharmaceutically acceptable salt, prodrug, solvate or isomer thereof, as an active ingredient, is prepared into an intestine-targeted formulation:
[0000]
[0000] wherein
[0012] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently hydrogen, halogen, hydroxyl or C 1 -C 6 alkyl, alkene or alkoxy, C 4 -C 10 cycloalkyl, heterocycloallcyl, aryl or heteroaryl, or two substituents thereof may be taken together to form a cyclic structure or form a double bond;
[0013] X is selected from the group consisting of C(R)(R′), N(R″), O and S, wherein R, R′ and R″ are each independently hydrogen or C 1 -C 6 lower alkyl; and
[0014] m and n each independently are 0 or 1, with proviso that when morn is 0, carbon atoms adjacent to morn form a cyclic structure via a direct bond.
[0015] As used in the present specification, the term “pharmaceutically acceptable salt” means a formulation of a compound that does not cause significant irritation to an organism to which it is administered and does not abrogate the biological activity and properties of the compound. Examples of the pharmaceutical salt may include acid addition salts of the compound (I) with acids capable of forming a non-toxic acid addition salt containing pharmaceutically acceptable anions, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrobromic acid and hydroiodic acid; organic carbonic acids such as tartaric acid, formic acid, citric acid, acetic acid, trichloroacetic acid, trifluoroacetic acid, gluconic acid, benzoic acid, lactic acid, fumaric acid, maleic acid and salicylic acid; or sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid. Specifically, examples of pharmaceutically acceptable carboxylic acid salts include salts with alkali metals or alkaline earth metals such as lithium, sodium, potassium, calcium and magnesium, salts with amino acids such as arginine, lysine and guanidine, salts with organic bases such as dicyclohexylamine, N-methyl-D-glucamine, tris(hydroxymethyl)methylamine, diethanolamine, choline and triethylamine. The compound in accordance with the present invention may be converted into salts thereof, by conventional methods well-known in the art.
[0016] As used herein, the term “prodrug” means an agent that is converted into the parent drug in vivo. Prodrugs are often useful because, in some situations, they may be easier to administer than the parent drug. They may, for instance, be bioavailable by oral administration, whereas the parent may be not. The prodrugs may also have improved solubility in pharmaceutical compositions over the parent drug. An example of a prodrug, without limitation, would be a compound of the present invention which is administered as an ester (“prodrug”) to facilitate transport across a cell membrane where water-solubility is detrimental to mobility, but which then is metabolically hydrolyzed to the carboxylic acid, the active entity, once inside the cell where water solubility is beneficial. A further example of the prodrug might be a short peptide (polyamino acid) bonded to an acidic group, where the peptide is metabolized to reveal the active moiety.
[0017] As an example of such prodrug, the pharmaceutical compounds in accordance with the present invention can include a prodrug represented by Formula Ia below as an active material:
[0000]
[0000] wherein,
[0018] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , m, n and X are as defined in Formula 1.
[0019] R 17 and R 18 are each independently —SO 3 —Na + or substituent represented by Formula 2 below or a salt thereof,
[0000]
[0020] wherein,
R 19 and R 20 are each independently hydrogen or substituted or unsubstituted C 1 ˜C 20 linear alkyl or C 1 ˜C 20 branched alkyl R 21 is selected from the group consisting of substituents i) to viii) below: i) hydrogen; ii) substituted or unsubstituted C 1 ˜C 20 linear alkyl or C 1 ˜C 20 branched alkyl; iii) substituted or unsubstituted amine; iv) substituted or unsubstituted C 3 ˜C 10 cycloalkyl or C 3 ˜C 10 heterocycloalkyl; v) substituted or unsubstituted C 4 ˜C 10 aryl or C 4 ˜C 10 heteroaryl; vi) —(CRR′—NR″CO) 1 —R 22 , wherein R, R′ and R″ are each independently hydrogen or substituted or unsubstituted C 1 ˜C 20 linear alkyl or C 1 ˜C 20 branched alkyl, R 14 is selected from the group consisting of hydrogen, substituted or unsubstituted amine, cycloalkyl, heterocycloalkyl, aryl and heteroaryl, 1 is selected from the 1˜5; vii) substituted or unsubstituted carboxyl; viii) —OSO 3 —Na + ; k is selected from the 0˜20, with proviso that when k is 0, R 19 and R 20 are not anything, and R 21 is directly bond to a carbonyl group.
[0032] As used herein, the term “solvate” means a compound of the present invention or a salt thereof, which further includes a stoichiometric or non-stoichiometric amount of a solvent bound thereto by non-covalent intermolecular forces. Preferred solvents are volatile, non-toxic, and/or acceptable for administration to humans. Where the solvent is water, the solvate refers to a hydrate.
[0033] As used herein, the term “isomer” means a compound of the present invention or a salt thereof, that has the same chemical formula or molecular formula but is optically or sterically different therefrom. D type optical isomer and L type optical isomer can be present in the Formula 1, depending on the R 1 ˜R 16 types of substituents selected.
[0034] Unless otherwise specified, the term “phenanthrenequinone-based compound” is intended to encompass a compound per se, and a pharmaceutically acceptable salt, prodrug, solvate and isomer thereof.
[0035] As used herein, the term “alkyl” refers to an aliphatic hydrocarbon group. The alkyl moiety may be a “saturated alkyl” group, which means that it does not contain any alkene or alkyne moieties. Alternatively, the alkyl moiety may also be an “unsaturated alkyl” moiety, which means that it contains at least one alkene or alkyne moiety. The term “alkene” moiety refers to a group in which at least two carbon atoms form at least one carbon-carbon double bond, and an “alkyne” moiety refers to a group in which at least two carbon atoms form at least one carbon-carbon triple bond. The alkyl moiety, regardless of whether it is substituted or unsubstituted, may be branched, linear or cyclic.
[0036] As used herein, the term “heterocycloalkyl” means a carbocyclic group in which one or more ring carbon atoms are substituted with oxygen, nitrogen or sulfur and which includes, for example, but is not limited to furan, thiophene, pyrrole, pyrroline, pyrrolidine, oxazole, thiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, pyrazolidine, isothiazole, triazole, thiadiazole, pyran, pyridine, piperidine, morpholine, thiomorpholine, pyridazine, pyrimidine, pyrazine, piperazine and triazine.
[0037] As used herein, the term “aryl” refers to an aromatic substituent group which has at least one ring having a conjugated pi (π) electron system and includes both carbocyclic aryl (for example, phenyl) and heterocyclic aryl (for example, pyridine) groups. This term includes monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) groups.
[0038] As used herein, the term “heteroaryl” refers to an aromatic group that contains at least one heterocyclic ring.
[0039] Examples of aryl or heteroaryl include, but are not limited to, phenyl, furan, pyran, pyrimidyl and triazyl.
[0040] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 in Formula 1 in accordance with the present invention may be optionally substituted. When substituted, the substituent group(s) is(are) one or more group(s) individually and independently selected from cycloalkyl, aryl, heteroaryl, heteroalicyclic, hydroxy, alkoxy, aryloxy, mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamyl, N carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amido, N-amido, S-sulfonamido, N-sulfonamido, C-carboxy, O-carboxy, isocyanato, thiocyanato, isothiocyanato, nitro, silyl, trihalomethanesulfonyl, and amino including mono and di substituted amino, and protected derivatives thereof. Further, in Formula 2, where R 19 , R 20 and R 20 are substituted, they may be substituted by the above substituents.
[0041] Among compounds of Formula 1 in accordance with the present invention, preferred are compounds of Formulas 3 and 6 below.
[0042] Compounds of Formula 3 below are compounds wherein m is 1, n is 0 and adjacent carbon atoms form a cyclic structure (furan ring) via a direct bond therebetween and are often referred to as ‘furanotetrahydrophenanthrene compounds’ or ‘furanotetrahydro-3,4-phenanthrenequinone’ hereinafter.
[0000]
[0043] Compounds of formula 4 below are compounds wherein m and n is respectively 1 and are often referred to as ‘pyranotetrahydrophenanthrene compounds’ or ‘pyranotetrahydro-3,4-phenanthrenequinone’ hereinafter.
[0000]
[0044] In the aforesaid pyranotetrahydrophenanthrene compounds and pyranotetrahydro-3,4-phenanthrenequinone, it is also possible that R 2 and R 4 and/or R 6 and R 8 form a chemical bond. In this regard, when m and n are respectively 0 and 1, the compounds are classified into two types of formula 5 and formula 6 below.
[0045] That is, compounds of Formula 5, wherein m is 1, n is 0 and adjacent carbon atoms form a cyclic structure (furan ring) via a direct bond therebetween, are often referred to as ‘furanophenanthrene compounds’ or ‘furan-3,4-phenanthrenequinone’ hereinafter.
[0000]
[0046] Compounds of Formula 6, wherein m and n are respectively 1, are often referred to as ‘pyranophenanthrene compounds’ or ‘pyrano-3,4-phenanthrenequinone’ hereinafter.
[0000]
[0047] The term “pharmaceutical composition” as used herein means a mixture of a compound of Formula 1 as an active material and other components which are required for an intestine-targeted formulation.
Preparation of Active Materials
[0048] In the pharmaceutical composition in accordance with the present invention, compounds of Formula 1 which are active materials, as will be illustrated hereinafter, can be prepared. The preparation processes described below are only exemplary ones and other processes can also be employed. As such, the scope of the instant invention is not limited to the following processes.
[0049] In general, tricyclic naphthoquinone (pyrano-o-naphthoquinone and furano-o-naphthoquinone) derivatives can be synthesized mainly by two methods. One is to derive cyclization reaction using 3-allyl-2-hydroxy-1,4-naphthoquinone in acid catalyst condition, like in the following β-lapachone synthesis method. In the present invention, when a compound in which R 11 and R 12 are not hydrogen simultaneously, most of compounds of formula 1 were synthesized on the basis of that method.
[0000]
[0050] That is, 3-allyloxy-1,4-phenanthrenequinone can be obtained by deriving Diels-Alder reaction between 2-allyloxy-1,4-benzoquinone and styrene or 1-vinylcyclohexane derivatives and dehydrating the resulting intermediates using oxygen present in the air or oxidants such as NaIO 4 and DDQ. By further re-heating the above compound, 2-allyl-3-hydroxy-1,4-phenanthrenequinone of Lapachole form can be synthesized via Claisen rearrangement.
[0000]
[0051] When the thus obtained 2-allyl-3-hydroxy-1,4-phenanthrenequinone is ultimately subject to cyclization in an acid catalyst condition, various 3,4-phenanthrenequinone-based or 5,6,7,8-tetrahydro-3,4-phenanthrenequinone-based compounds can be synthesized. In this case, 5 or 6-cyclic cyclization occurs depending on the types of substituents (R 21 , R 22 , R 23 in the above formula) represented in the above formula, and also they are converted to the corresponding, adequate substituents (R 11 , R 12 , R 13 , R 14 , R 15 , R 16 ).
[0000]
[0052] Further, 3-allyloxy-1,4-phenanthrenequinone is hydrolyzed to 3-oxy-1,4-phenanthrenequinone, in the condition of acid or alkali (OH) catalyst, which is then reacted with various allyl halides to synthesize 2-allyl-3-hydroxy-1,4-phenanthrenequinone by C-alkylation. The thus obtained 2-allyl-3-hydroxy-1,4-phenanthrenequinone derivatives are subject to cyclization in the condition of acid catalyst to synthesize various 3,4-phenanthrenequinone-based or 5,6,7,8-tetrahydro-3,4-naphthoquinone-based compounds. In this case, 5 or 6-cyclic cyclization occurs depending on the types of substituents (R 21 , R 22 , R 23 , R 24 in the above formula) represented in the above formula, and also they are converted to the corresponding, adequate substituents (R 11 , R 12 , R 13 , R 14 , R 15 , R 16 ).
[0000]
[0053] However, compounds in which substituents R 11 and R 12 are hydrogen simultaneously cannot be obtained by cyclization in the condition of acid catalyst. These compound were obtained on the basis of the method reported by J. K. Snyder (Tetrahedron Letters, 28, 3427˜3430, 1987; Journal of Organic Chemistry, 55, 4995˜5008, 1990), more specifically, by first obtaining furanobenzoquinone, to which a furan ring is introduced, by cyclization, and then obtaining tricyclic phenanthroquinone by cyclization with 1-vinylcyclohexene derivative, followed by reduction via hydrogen addition. The above synthesis process can be summarized as follows.
[0000]
[0054] Based on the above-mentioned preparation methods, various derivatives may be synthesized using relevant synthesis methods, depending upon kinds of substituents.
[0055] Among compounds of Formula 1 in accordance with the present invention, particularly preferred are exemplified in Table 1 below, but are not limited to, Specific preparation methods will be described in the following Examples.
[0000]
TABLE 1
Molecular
No.
Chemical structure
Formula
weight
1
C 17 H 16 O 3
268.31
2
C 19 H 20 O 3
296.36
3
C 19 H 20 O 3
296.36
4
C 21 H 24 O 3
324.41
5
C 21 H 24 O 3
324.41
6
C 19 H 20 O 3
296.36
7
C 17 H 12 O 3
264.28
8
C 19 H 16 O 3
292.33
9
C 18 H 14 O 3
278.30
10
C 20 H 18 O 3
306.36
11
C 21 H 20 O 3
320.38
12
C 23 H 24 O 3
348.43
13
C 17 H 11 ClO 3
298.72
14
C 18 H 14 O 3
278.30
15
C 18 H 14 O 4
294.30
16
C 20 H 18 O 3
306.36
17
C 18 H 18 O 3
282.33
18
C 18 H 16 O 3
280.33
19
C 18 H 14 O 3
278.33
20
C 18 H 12 O 3
276.33
[0056] Generally, an oral pharmaceutical composition passes through the stomach upon oral administration, is largely absorbed by the small intestine and then diffused into all the tissues of the body, thereby exerting therapeutic effects on the target tissues.
[0057] In this connection, the oral pharmaceutical composition according to the present invention enhances bioabsorption and bioavailability of a certain phenanthrenequinone-based compound active ingredient via intestine-targeted formulation of the active ingredient. More specifically, when the active ingredient in the pharmaceutical composition according to the present invention is primarily absorbed in the stomach, and upper parts of the small intestine, the active ingredient absorbed into the body directly undergoes liver metabolism which is then accompanied by substantial degradation of the active ingredient, so it is impossible to exert a desired level of therapeutic effects. On the other hand, it is expected that when the active ingredient is largely absorbed around and downstream of the lower small intestine, the absorbed active ingredient migrates via lymph vessels to the target tissues to thereby exert high therapeutic effects.
[0058] Further, as it is constructed in such a way that the pharmaceutical composition according to the present invention targets up to the colon which is a final destination of the digestion process, it is possible to increase the in vivo retention time of the drug and it is also possible to minimize decomposition of the drug which may take place due to the body metabolism upon administration of the drug into the body. As a result, it is possible to improve pharmacokinetic properties of the drug, to significantly lower a critical effective dose of the active ingredient necessary for the treatment of the disease, and to obtain desired therapeutic effects even with administration of a trace amount of the active ingredient. Further, in the oral pharmaceutical composition, it is also possible to minimize the absorption variation of the drug by reducing the between- and within-individual variation of the bioavailability which may result from intragastric pH changes and dietary uptake patterns.
[0059] Therefore, the intestine-targeted formulation according to the present invention is configured such that the active ingredient is largely absorbed in the small and large intestines, more preferably in the jejunum, and the ileum and colon corresponding to the lower small intestine, particularly preferably in the ileum or colon.
[0060] The intestine-targeted formulation may be designed by taking advantage of numerous physiological parameters of the digestive tract, through a variety of methods. In one preferred embodiment of the present invention, the intestine-targeted formulation may be prepared by (1) a formulation method based on a pH-sensitive polymer, (2) a formulation method based on a biodegradable polymer which is decomposable by an intestine-specific bacterial enzyme, (3) a formulation method based on a biodegradable matrix which is decomposable by an intestine-specific bacterial enzyme, or (4) a formulation method which allows release of a drug after a given lag time, and any combination thereof.
[0061] Specifically, the intestine-targeted formulation (1) using the pH-sensitive polymer is a drug delivery system which is based on pH changes of the digestive tract. The pH of the stomach is in a range of 1 to 3, whereas the pH of the small and large intestines has a value of 7 or higher, as compared to that of the stomach. Based on this fact, the pH-sensitive polymer may be used in order to ensure that the pharmaceutical composition reaches the lower intestinal parts without being affected by pH fluctuations of the digestive tact. Examples of the pH-sensitive polymer may include, but are not limited to, at least one selected from the group consisting of methacrylic acid-ethyl acrylate copolymer (Eudragit: Registered Trademark of Rohm Pharma GmbH), hydroxypropylmethyl cellulose phthalate (HPMCP) and a mixture thereof.
[0062] Preferably, the pH-sensitive polymer may be added by a coating process. For example, addition of the polymer may be carried out by mixing the polymer in a solvent to form an aqueous coating suspension, spraying the resulting coating suspension to form a film coating, and drying the film coating.
[0063] The intestine-targeted formulation (2) using the biodegradable polymer which is decomposable by the intestine-specific bacterial enzyme is based on the utilization of a degradative ability of a specific enzyme that can be produced by enteric bacteria. Examples of the specific enzyme may include azoreductase, bacterial hydrolase glycosidase, esterase, polysaccharidase, and the like.
[0064] When it is desired to design the intestine-targeted formulation using azoreductase as a target, the biodegradable polymer may be a polymer containing an azoaromatic linkage, for example, a copolymer of styrene and hydroxyethylmethacrylate (HEMA). When the polymer is added to the formulation containing the active ingredient, the active ingredient may be liberated into the intestine by reduction of an azo group of the polymer via the action of the azoreductase which is specifically secreted by enteric bacteria, for example, Bacteroides fragilis and Eubacterium limosum.
[0065] When it is desired to design the intestine-targeted formulation using glycosidase, esterase, or polysaccharidase as a target, the biodegradable polymer may be a naturally-occurring polysaccharide or a substituted derivative thereof. For example, the biodegradable polymer may be at least one selected from the group consisting of dextran ester, pectin, amylase, ethyl cellulose and a pharmaceutically acceptable salt thereof. When the polymer is added to the active ingredient, the active ingredient may be liberated into the intestine by hydrolysis of the polymer via the action of each enzyme which is specifically secreted by enteric bacteria, for example, Bifidobacteria and Bacteroides spp. These polymers are natural materials, and have an advantage of low risk of in vivo toxicity.
[0066] The intestine-targeted formulation (3) using the biodegradable matrix which is decomposable by an intestine-specific bacterial enzyme may be a form in which the biodegradable polymers are cross-linked to each other and are added to the active ingredient or the active ingredient-containing formulation. Examples of the biodegradable polymer may include naturally-occurring polymers such as chondroitin sulfate, guar gum, chitosan, pectin, and the like. The degree of drug release may vary depending upon the degree of cross-linking of the matrix-constituting polymer.
[0067] In addition to the naturally-occurring polymers, the biodegradable matrix may be a synthetic hydrogel based on N-substituted acrylamide. For example, there may be used a hydrogel synthesized by cross-linking of N-tert-butylacryl amide with acrylic acid or copolymerization of 2-hydroxyethyl methacrylate and 4-methacryloyloxyazobenzene, as the matrix. The cross-linking may be, for example an azo linkage as mentioned above, and the formulation may be a form where the density of cross-linking is maintained to provide the optimal conditions for intestinal drug delivery and the linkage is degraded to interact with the intestinal mucous membrane when the drug is delivered to the intestine.
[0068] Further, the intestine-targeted formulation (4) with time-course release of the drug after a lag time is a drug delivery system utilizing a mechanism that is allowed to release the active ingredient after a predetermined time irrespective of pH changes. In order to achieve enteric release of the active drug, the formulation should be resistant to the gastric pH environment, and should be in a silent phase for 5 to 6 hours corresponding to a time period taken for delivery of the drug from the body to the intestine, prior to release of the active ingredient into the intestine. The time-specific delayed-release formulation may be prepared by addition of the hydrogel prepared from copolymerization of polyethylene oxide with polyurethane.
[0069] Specifically, the delayed-release formulation may have a configuration in which the formulation absorbs water and then swells while it stays within the stomach and the upper digestive tract of the small intestine, upon addition of a hydrogel having the above-mentioned composition after applying the drug to an insoluble polymer, and then migrates to the lower part of the small intestine which is the lower digestive tract and liberates the drug, and the lag time of drug is determined depending upon a length of the hydrogel.
[0070] As another example of the polymer, ethyl cellulose (EC) may be used in the delayed-release dosage formulation. EC is an insoluble polymer, and may serve as a factor to delay a drug release time, in response to swelling of a swelling medium due to water penetration or changes in the internal pressure of the intestines due to a peristaltic motion. The lag time may be controlled by the thickness of EC. As an additional example, hydroxypropylmethyl cellulose (HPMC) may also be used as a retarding agent that allows drug release after a given period of time by thickness control of the polymer, and may have a lag time of 5 to 10 hours.
[0071] In the oral pharmaceutical composition according to the present invention, the active ingredient may have a crystalline structure with a high degree of crystallinity, or a crystalline structure with a low degree of crystallinity.
[0072] As used herein, the term “degree of crystallinity” is defined as the weight fraction of the crystalline portion of the total compound and may be determined by a conventional method known in the art. For example, measurement of the degree of crystallinity may be carried out by a density method or precipitation method which calculates the crystallinity degree by previous assumption of a preset value obtained by addition and/or reduction of appropriate values to/from each density of the crystalline portion and the amorphous portion, a method involving measurement of the heat of fusion, an X-ray method in which the crystallinity degree is calculated by separation of the crystalline diffraction fraction and the noncrystalline diffraction fraction from X-ray diffraction intensity distribution upon X-ray diffraction analysis, or an infrared method which calculates the crystallinity degree from a peak of the width between crystalline bands of the infrared absorption spectrum.
[0073] In the oral pharmaceutical composition according to the present invention, the crystallinity degree of the active ingredient is preferably 50% or less. More preferably, the active ingredient may have an amorphous structure from which the intrinsic crystallinity of the material was completely lost. The amorphous phenanthrenequinone-based compound exhibits a relatively high solubility, as compared to the crystalline phenanthrenequinone-based compound, and can significantly improve a dissolution rate and in vivo absorption rate of the drug.
[0074] In one preferred embodiment of the present invention, the amorphous structure may be formed during preparation of the active ingredient into microparticles or fine particles (micronization of the active ingredient). The microparticles may be prepared, for example by spray drying of active ingredients, melting methods involving formation of melts of active ingredients with polymers, co-precipitation involving formation of co-precipitates of active ingredients with polymers after dissolution of active ingredients in solvents, inclusion body formation, solvent volatilization, and the like. Preferred is spray drying. Even when the active ingredient is not of an amorphous structure, that is has a crystalline structure or semi-crystalline structure, micronization of the active ingredient into fine particles via mechanical milling contributes to improvement of solubility, due to a large specific surface area of the particles, consequently resulting in improved dissolution rate and bioabsorption rate of the active drug.
[0075] The spray drying is a method of making fine particles by dissolving the active ingredient in a certain solvent and the spray-drying the resulting solution. During the spray-drying process, a high percent of the crystallinity of the phenanthrenequinone-based compound is lost to thereby result in an amorphous state, and therefore the spray-dried product in the form of a fine powder is obtained.
[0076] The mechanical milling is a method of grinding the active ingredient into fine particles by applying strong physical force to active ingredient particles. The mechanical milling may be carried out by using a variety of milling processes such as jet milling, ball milling, vibration milling, hammer milling, and the like. Particularly preferred is jet milling which can be carried out using an air pressure, at a temperature of less than 40° C.
[0077] Meanwhile, irrespective of the crystalline structure, a decreasing particle diameter of the particulate active ingredient leads to an increasing specific surface area, thereby increasing the dissolution rate and solubility. However, an excessively small particle diameter makes it difficult to prepare fine particles having such a size and also brings about agglomeration or aggregation of particles which may result in deterioration of the solubility. Therefore, in one preferred embodiment, the particle diameter of the active ingredient may be in a range of 5 nm to 500 μm. In this range, the particle agglomeration or aggregation can be maximally inhibited, and the dissolution rate and solubility can be maximized due to a high specific surface area of the particles.
[0078] Preferably, a surfactant may be additionally added to prevent the particle agglomeration or aggregation which may occur during formation of the fine particles, and/or an antistatic agent may be additionally added to prevent the occurrence of static electricity.
[0079] If necessary, a moisture-absorbent material may be further added during the milling process. The phenanthrenequinone-based compound of Formula 1 has a tendency to be crystallized by water, so incorporation of the moisture-absorbent material inhibits recrystallization of the phenanthrenequinone-based compound over time and enables maintenance of increased solubility of compound particles due to micronization. Further, the moisture-absorbent material serves to suppress coagulation and aggregation of the pharmaceutical composition while not adversely affecting therapeutic effects of the active ingredient.
[0080] Examples of the surfactant may include, but are not limited to, anionc surfactants such as docusate sodium and sodium lauryl sulfate; cationic surfactants such as benzalkonium chloride, benzethonium chloride and cetrimide; nonionic surfactants such as glyceryl monooleate, polyoxyethylene sorbitan fatty acid ester, and sorbitan ester; amphiphilic polymers such as polyethylene-polypropylene polymer and polyoxyethylene-polyoxypropylene polymer (Poloxamer), and Gelucire™ series (Gattefosse Corporation, USA); propylene glycol monocaprylate, oleoyl macrogol-6-glyceride, linoleoyl macrogol-6-glyceride, caprylocaproyl macrogol-8-glyceride, propylene glycol monolaurate, and polyglyceryl-6-dioleate. These materials may be used alone or in any combination thereof.
[0081] Examples of the moisture-absorbent material may include, but are not limited to, colloidal silica, light anhydrous silicic acid, heavy anhydrous silicic acid, sodium chloride, calcium silicate, potassium aluminosilicate, calcium aluminosilicate, and the like. These materials may be used alone or in any combination thereof.
[0082] Some of the above-mentioned moisture absorbents may also be used as the antistatic agent.
[0083] The surfactant, antistatic agent, and moisture absorbent are added in a certain amount that is capable of achieving the above-mentioned effects, and such an amount may be appropriately adjusted depending upon micronization conditions. Preferably, the additives may be used in a range of 0.05 to 20% by weight, based on the total weight of the active ingredient.
[0084] In one preferred embodiment, during formulation of the pharmaceutical composition according to the present invention into preparations for oral administration, water-soluble polymers, solubilizers and disintegration-promoting agents may be further added. Preferably, formulation of the composition into a desired dosage form may be made by mixing the additives and the particulate active ingredient in a solvent and spray-drying the mixture.
[0085] The water-soluble polymer is of help to prevent aggregation of the particulate active ingredients, by rendering surroundings of phenanthrenequinone-based compound molecules or particles hydrophilic to consequently enhance water solubility, and preferably to maintain the amorphous state of the active ingredient phenanthrenequinone-based compound.
[0086] Preferably, the water-soluble polymer is a pH-independent polymer, and can bring about crystallinity loss and enhanced hydrophilicity of the active ingredient, even under the between- and within-individual variation of the gastrointestinal pH.
[0087] Preferred examples of the water-soluble polymers may include at least one selected from the group consisting of cellulose derivatives such as methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, ethyl cellulose, hydroxyethylmethyl cellulose, carboxymethyl cellulose, hydroxypropylmethyl cellulose, hydroxypropylmethyl cellulose phthalate, sodium carboxymethyl cellulose, and carboxymethylethyl cellulose; polyvinyl alcohols; polyvinyl acetate, polyvinyl acetate phthalate, polyvinylpyrrolidone (PVP), and polymers containing the same; polyalkene oxide or polyalkene glycol, and polymers containing the same. Preferred is hydroxypropylmethyl cellulose.
[0088] In the pharmaceutical composition of the present invention, an excessive content of the water-soluble polymer which is higher than a given level provides no further increased solubility, but disadvantageously brings about various problems such as overall increases in the hardness of the formulation, and non-penetration of an eluent into the formulation, by formation of films around the formulation due to excessive swelling of water-soluble polymers upon exposure to the eluent. Accordingly, the solubilizer is preferably added to maximize the solubility of the formulation by modifying physical properties of the phenanthrenequinone-based compound.
[0089] In this respect, the solubilizer serves to enhance solubilization and wettability of the sparingly-soluble phenanthrenequinone-based compound, and can significantly reduce the bioavailability variation of the phenanthrenequinone-based compound originating from diets and the time difference of drug administration after dietary uptake. The solubilizer may be selected from conventionally widely used surfactants or amphiphiles, and specific examples of the solubilizer may refer to the surfactants as defined above.
[0090] The disintegration-promoting agent serves to improve the drug release rate, and enables rapid release of the drug at the target site to thereby increase bioavailability of the drug.
[0091] Preferred examples of the disintegration-promoting agent may include, but are not limited to, at least one selected from the group consisting of Croscarmellose sodium, Crospovidone, calcium carboxymethylcellulose, starch glycolate sodium and lower substituted hydroxypropyl cellulose. Preferred is Croscarmellose sodium.
[0092] Upon taking into consideration various factors as described above, it is preferred to add 10 to 1000 parts by weight of the water-soluble polymer, 1 to 30 parts by weight of the disintegration-promoting agent and 0.1 to 20 parts by weight of the solubilizer, based on 100 parts by weight of the active ingredient.
[0093] In addition to the above-mentioned ingredients, other materials known in the art in connection with formulation may be optionally added, if necessary.
[0094] The solvent for spray drying is a material exhibiting a high solubility without modification of physical properties thereof and easy volatility during the spray drying process. Preferred examples of such a solvent may include, but are not limited to, dichloromethane, chloroform, methanol, and ethanol. These materials may be used alone or in any combination thereof. Preferably, a content of solids in the spray solution is in a range of 5 to 50% by weight, based on the total weight of the spray solution.
[0095] The above-mentioned intestine-targeted formulation process may be preferably carried out for formulation particles prepared as above.
[0096] In one preferred embodiment, the oral pharmaceutical composition according to the present invention may be formulated by a process comprising the following steps:
[0097] (a) adding a phenanthrenequinone-based compound of Formula 1 alone or in combination with a surfactant and a moisture-absorbent material, and grinding the phenanthrenequinone-based compound of Formula 1 with a jet mill to prepare active ingredient microparticles;
[0098] (b) dissolving the active ingredient microparticles in conjunction with a water-soluble polymer, a solubilizer and a disintegration-promoting agent in a solvent and spray-drying the resulting solution to prepare formulation particles; and
[0099] (c) dissolving the formulation particles in conjunction with a pH-sensitive polymer and a plasticizer in a solvent and spray-drying the resulting solution to carry out intestine-targeted coating on the formulation particles.
[0100] The surfactant, moisture-absorbent material, water-soluble polymer, solubilizer and disintegration-promoting agent are as defined above. The plasticizer is an additive added to prevent hardening of the coating, and may include, for example polymers such as polyethylene glycol.
[0101] Alternatively, formulation of the active ingredient may be carried out by sequential or concurrent spraying of vehicles of Step (b) and intestine-targeted coating materials of Step (c) onto jet-milled active ingredient particles of Step (a) as a seed.
[0102] The oral pharmaceutical composition suitable for use in the present invention contains the active ingredient in an amount effective to achieve its intended purpose, that is therapeutic purpose. More specifically, a therapeutically effective amount refers to an amount of the compound effective to prevent, alleviate or ameliorate symptoms of disease. Determination of the therapeutically effective amount is well within the capability of those skilled in the art, especially in light of the detailed disclosure provided herein.
[0103] Further, the oral pharmaceutical composition according to the present invention is particularly effective for the treatment and/or prevention of metabolic diseases, degenerative diseases, and mitochondrial dysfunction-related diseases. Examples of the metabolic diseases may include, but are not limited to, obesity, obesity complications, liver diseases, arteriosclerosis, cerebral apoplexy, myocardial infarction, cardiovascular diseases, ischemic diseases, diabetes, diabetes-related complications and inflammatory diseases.
[0104] Complications caused from obesity include, for example hypertension, myocardiac infarction, varicosis, pulmonary embolism, coronary artery diseases, cerebral hemorrhage, senile dementia, Parkinson's disease, type 2 diabetes, hyperlipidemia, cerebral apoplexy, various cancers (such as uterine cancer, breast cancer, prostate cancer, colon cancer and the like), heart diseases, gall bladder diseases, sleep apnea syndrome, arthritis, infertility, venous ulcer, sudden death, fatty liver, hypertrophic cardiomyopathy (HCM), thromboembolism, esophagitis, abdominal wall hernia (Ventral Hernia), urinary incontinence, cardiovascular diseases, endocrine diseases and the like.
[0105] Diabetic complications include, for example hyperlipidemia, hypertension, retinopathy, renal insufficiency, and the like.
[0106] Examples of the degenerative diseases may include Alzheimer's disease, Parkinson's disease and Huntington's disease.
[0107] Diseases arising from mitochondrial dysfunction may include for example, multiple sclerosis, encephalomyelitis, cerebral radiculitis, peripheral neuropathy, Reye's syndrome, Friedrich's ataxia, Alpers syndrome, MELAS, migraine, psychosis, depression, seizure and dementia, paralytic episode, optic atrophy, optic neuropathy, retinitis pigmentosa, cataract, hyperaldosteronemia, hypoparathyroidism, myopathy, amyotrophy, myoglobinuria, muscular hypotonia, myalgia, reduced exercise tolerance, renal tubulopathy, renal failure, hepatic failure, hepatic dysfunction, hepatomegaly, sideroblastic anemia (iron-deficiency anemia), neutropenia, thrombocytopenia, diarrhea, villous atrophy, multiple vomiting, dysphagia, constipation, sensorineural hearing loss (SNHL), mental retardation, epilepsy, and the like.
[0108] As used herein, the term “treatment” refers to stopping or delaying of the disease progress, when the drug is used in the subject exhibiting symptoms of disease onset. The term “prevention” refers to stopping or delaying of symptoms of disease onset, when the drug is used in the subject exhibiting no symptoms of disease onset but having high risk of disease onset.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0109] Now, the present invention will be described in more detail with reference to the following Examples. These examples are provided only for illustrating the present invention and should not be construed as limiting the scope and spirit of the present invention.
Example 1
Micronization of Active Ingredient Using Jet Mill
[0110] Micronizing of an active ingredient was carried out using a Jet mill (SJ-100, Nisshin, Japan). Operation was run at a supply pressure of 0.65 Mpa, and a feed rate of 16 to 20 g/hr 0.2 g of sodium lauryl sulfate (sodium lauryl sulfate) and 10 g of cryptotanshinone as a phenanthrenequinone-based compound were add to 100 ml of water and then ground for 10 hours. Micronized particles were recovered and a particle size was determined by zeta potential measurement. An average particle diameter was 1500 nm.
Example 2
Preparation of Spray-Drying Product
[0111] Cryptotanshinone per se or cryptotanshinone which was micronized in Example 1 was added to methanol. Then, a salt such as sodium chloride, a saccharide such as white sugar or lactose, or a vehicle such as microcrystalline cellulose, monobasic calcium phosphate, starch or mannitol, a lubricant such as magnesium stearate, talc or glyceryl behenate, and a solubilizer such as Poloxamer were added thereto, followed by homogeneous dispersion to prepare a spray-drying solution which will be used for subsequent spray-drying.
Experimental Example 1
Dissolution of Spray-Dried Formulation
[0112] To the spray-dried product of Example 2 were added approximately an equal amount of a water-soluble polymer (hydroxypropylmethyl cellulose) relative to an active ingredient, and vehicles such as Croscaimellose sodium and light anhydrous silicic acid, and the mixture was formulated without causing interference of disintegration. A drug dissolution test was carried out in a buffer (pH 6.8). All the compositions exhibited drug dissolution of 90% or higher after 6 hours.
Experimental Example 2
Evaluation of Relative Bioavailability of Spray-Dried Formulations in which the Phenanthrenequinone-Based Compound is Contained
[0113] 10 male Sprague-Dawley rats were fasted, and the relative bioavailability in animals was evaluated for various formulations. Specifically, evaluation of the relative bioavailability was made for a preparation where a cryptotanshinone was roughly ground and was added in conjunction with 2% by weight of sodium lauryl sulfate (SLS) to an aqueous solution (preparation prior to grinding of an active ingredient), a preparation where a cryptotanshinone was ground into microparticles with a Jet mill, and was added in conjunction with 2% by weight of SLS to an aqueous solution (preparation after grinding of an active ingredient), a preparation where a formulation composed of the spray-dried product of Example 2 and the vehicle of Experimental Example 1 was added to an aqueous solution (spray-dried preparation), and a preparation where a cryptotanshinone was ground into microparticles with a Jet mill, formulated using the vehicle of Experimental Example 1 and added to an aqueous solution (solid-dispersed preparation).
[0000]
TABLE 2
Blood conc. (ng/mL): Fasted
Preparation
Preparation
before
after
Spray-dried
Solid-dispersed
Time (hour)
grinding
grinding
preparation
preparation
0
0.00
0.00
0.00
0.00
0.5
176.92
150.55
368.54
373.49
1
96.38
169.12
458.65
475.19
2
154.91
205.35
246.42
241.38
3
256.63
222.51
272.35
281.39
6
135.81
421.16
880.82
889.66
12
77.30
141.15
252.94
256.04
24
65.90
137.98
166.90
166.10
Avg. Cmax
256.63
421.16
880.82
889.66
Avg. AUC
2491.82
4695.78
8132.44
8215.08
(last)
[0114] As can be seen from the results of Table 2, the spray-dried formulation and the solid-dispersed formulation, which were added to an aqueous solution, exhibited an about 3-fold increase of the bioavailability in a fasted state, as compared to the comparative formulation containing the same amount of the active ingredient, particularly the formulation prior to grinding of the active ingredient.
Example 3
Preparation of Intestine-Targeted Formulation
[0115] The spray-dried formulation prepared in Experimental Example 1 was added to an ethanol solution containing about 20% by weight of Eudragit S-100 as a pH-sensitive polymer and about 2% by weight of PEG #6,000 as a plasticizer, and the mixture was then spray-dried to prepare an intestine-targeted formulation.
Experimental Example 3
Acid Resistance of Intestine-Targeted Formulation
[0116] The intestine-targeted formulation prepared in Example 3 was exposed to pH 1.2 and pH 6.8, respectively. After 6 hours, the intestine-targeted formulation was removed and washed, and a content of an active ingredient was analyzed by HPLC. An effective amount of the active ingredient was assessed as a measure of the acid resistance. The acid resistance exhibited a very excellent result of 90 to 100%, thus suggesting that the intestine-targeted formulation is chemically stable in the stomach or small intestine.
Experimental Example 4
Measurement of Drug-Dissolution Profiles
[0117] After the intestine-targeted formulation was exposed to acidic environment of pH 1.2, as in Experimental Example 3, the acidity was changed to a value of pH 6.8 under artificial environment. A residual amount of the dissolved active ingredient was measured by HPLC. The results thus obtained are given in Table 3 below.
[0000]
TABLE 3
Time (min.)
Dissolution (%) at pH 6.8
0
0.00
10
68.48
30
82.99
45
88.48
60
88.62
120
91.20
180
91.43
240
94.18
Experimental Example 5
Therapeutic Efficacy of Intestine-Targeted Formulation
[0118] 400 mg/kg of an intestine-targeted formulation in terms of active ingredient content was administered to ob/ob mice once a day, and changes in the body weight (BW) of animals were examined.
[0119] 10-week-old ob/ob male mice (Jackson Lab) as an obese mouse model of type 2 diabetes were purchased from Orient Co. (Kyungki-do, Korea) and were allowed to acclimate to a new environment of the breeding room for 10 days prior to experiments. Animals were fed a solid feed (P5053, Labdiet) as a laboratory animal feed. The ob/ob male mice were housed and allowed to acclimate to a new environment for 10 days, in a breeding room maintained at a temperature of 22±2° C., humidity of 55±5%, and a 12-h light/dark (L/D) cycle (light from 8:00 a.m. to 8:00 p.m.). According to a randomized blocks design, the thus-acclimated animals were randomly divided into four groups, each consisting of 7 animals: a control group with administration of sodium lauryl sulfate (10 mg/kg), a group with administration of simply finely-divided powder of a cryptotanshinone (400 mg/kg), a group with administration of a jet-milled cryptotanshinone, and a group with administration of an intestine-targeted formulation of a ground cryptotanshinone. Each group of animals was given perorally (PO) 400 mg/kg of samples. Animals were fed solid feed pellets and water ad libitum. The changes in the body weight of animals in each group were measured.
[0120] As an experimental result, it was confirmed that the control group with administration of sodium lauryl sulfate and the group with administration of simply finely-divided powder of a cryptotanshinone were increased in body weight, whereas the group with administration of a jet-milled cryptotanshinone and the group with administration of an intestine-targeted formulation decreased in body weight. Particularly, the group with administration of an intestine-targeted formulation exhibited more than two times loss of body weight as compared to the group with administration of cryptotanshinone. Accordingly, the group with administration of the intestine-targeted formulation exhibited the highest loss (%) of body weight, thus confirming that excellent bioavailability is obtained.
INDUSTRIAL APPLICABILITY
[0121] As apparent from the above description, an oral pharmaceutical composition according to the present invention increases a bioabsorption rate and an in vivo retention time of an active ingredient to thereby improve pharmacokinetic properties of the drug. As a result, it is possible to achieve desired therapeutic effects by increasing the bioavailability of a certain phenanthrenequinone-based compound as the active ingredient.
[0122] Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. | Provided is an oral pharmaceutical composition with improved bioavailability and pharmacokinetic properties of a drug, by increasing a bioabsorption rate and an in vivo retention time of an active ingredient via intestine-targeted formulation of a particular phenanthrenequinone-based compound, or a pharmaceutically acceptable salt, prodrug, solvate or isomer thereof, as an active ingredient. | 0 |
This application is a continuation, of application Ser. No. 320,087, filed Nov. 10, 1981 now abandoned.
FIELD OF THE INVENTION
The present invention relates to the discovery that a certain component of normal blood serum is selectively toxic to certain tumor cells and is not present in the sera of patients afflicted with such tumors, and, more particularly, the present invention relates to pharmaceutical compositions including such compounds and the method of treating tumors against which such compounds are effective, with such compounds.
BACKGROUND OF THE INVENTION
It has been hypothesized that there might be a component of normal individual blood serum which prevents the invasion of certain cancer cells in a healthy individual. Reference to comparative studies of components of normal healthy individual blood sera as compared with cancer patient sera, particularly with respect to organic solvent extracts, could not be found in the literature.
In order to test this hypothesis, a large number of samples of blood from normal individuals and from individuals suffering from various malignancies were taken and the sera were extracted with the following organic solvents:
methylene chloride
benzene
petroleum ether
toluene
diethyl ether.
The sera of both normal individuals and cancer patients were acidified, shaken with the above solvents, separated and evaporated to dryness. In those cases where any discernible residues were found, the only time that there was a difference between the results of the tests with normal individual sera as opposed to cancer patient sera, was found with the diethyl ether extraction. There was a white precipitate in the diethyl ether extracts of all normal individual's sera, although to different extents, but no precipitate from the diethyl ether extracts of cancer patients' sera.
This extract was tested and was found to be extremely toxic to cancer cells while totally non-toxic to normal cells.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a novel composition which is selectively toxic to certain cancer cells.
It is another object of the present invention to provide a method for the treatment of malignancies against which the compounds of the present invention are active by administration of such compounds.
An analysis of the extract left after diethyl ether extraction of normal patient serum showed this material to be octacosanedioic acid. This compound is a saturated fatty dicarboxylic acid having the formula of HOOC-(CH 2 ) 26 -COOH.
The cancer patients' sera tested were from individuals having the following malignancies:
1. breast carcinoma
2. carcinoma of the colon
3. bronchogenic carcinoma.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
In order to test for anti-cancer activity of this compound, the disodium salt of octacosanedioic acid was synthesized and then introduced in different concentrations to cancer cell suspensions of the above mentioned neoplasms in saline solutions, as well as to suspensions of normal cells of the same origin. This treatment resulted in lysis of the cancer cells starting within 20 minutes at a concentration of 0.0001%. No damage occurred to the normal cells except for the slight damage that occurred to these cells while making the suspension, which damage was equal in both groups of the cells.
In order to determine whether this property was unique to this particular dicarboxylic acid, similar tests were conducted with homologs of this material which are available commercially. The results are indicated in Table 1.
TABLE 1______________________________________Formula Common Name Effect______________________________________1. HOOC --CH.sub.2 --COOH malonic no lytic effect2. HOOC--(CH.sub.2).sub.2 --COOH succinic slight lytic effect at concentration of 0.1%3. HOOC--(CH.sub.2).sub.3 --COOH glutaric no lytic effect4. HOOC--(CH.sub.2).sub.4 --COOH adipic no lytic effect5. HOOC--(CH.sub.2).sub.5 --COOH pimelic no lytic effect6. HOOC--(CH.sub.2).sub.6 --COOH suberic a lytic effect at concentration of 0.001%7. HOOC--(CH.sub.2).sub.7 --COOH azelaic no lytic effect8. HOOC--(CH.sub.2).sub.8 --COOH sebacic no lytic effect9. HOOC--(CH.sub.2).sub.9 --COOH no lytic effect10. HOOC--(CH.sub.2).sub.10 --COOH a lytic effect at at concentration of 0.005%11. HOOC(CH.sub.2).sub.14 --COOH thapsic a lytic effect at concentration of 0.0005%______________________________________
Acids 1-10 of the above table were obtained from Sigma Chemical Company and acid No. 11 (thapsic acid) was obtained from Aldrich Chemical Company.
In all of the tests listed in Table 1, the disodium salt of the dicarboxylic acid was used in order to increase the solubility. The concentrations that were used were far lower than those necessary to affect the osmolarity. Thus, no lysis could be contributed to osmotic pressure. For each of the tests in Table 1 it was further noted that normal cells of the same origin were not affected.
A study of this table shows that lysis of cancer cells occurs when the number of --C 2 H 4 -- groups in the compound is odd. In other words, when the total carbon atom count of the compounds is divisible by 4, the desired effect is observed. Furthermore, it is evidenced that the longer the chain, the stronger the lytic effect.
The present invention comprehends the use of any straight-chain saturated aliphatic dicarboxylic acid or pharmaceutically acceptable salt thereof whose total number of carbon atoms is divisible by 4 for the treatment of various malignancies against which such compounds are effective in vitro. More particularly, such dicarboxylic acids having a total number of 8, 12, 16, 20, 24 or 28 carbon atoms are preferred compounds for use in the present invention.
While the tests discussed hereinabove relate only to breast carcinoma, carcinoma of the colon, and bronchogenic carcinoma, it will be readily apparent to those skilled in the art that by routine experimentation it can be determined whether the compounds of the present invention would also be effective against any other given neoplasm. This test would simply involve the preparation of a suspension of the cancer cells of the neoplasm in question in saline solution, and treatment in vitro with one of the compounds of the present invention to determine whether lysis of the cancer cells results. If no lysis results, then it is clear that the compounds of the present invention are ineffective against this particular type of neoplasm. If lysis results, then it would be expected that the compounds of the present invention would indeed be effective against these tumors in vivo.
Succinic acid has been reported to have a low order of toxicity in animals and has been used as an acidulant in foods. Subaric acid also has low toxicity. The higher dibasic acids (C 8 and higher) are reported to have lower internal toxicity. As pointed out hereinabove, octacosanedioic acid is a component of normal human blood serum.
The compounds in accordance with the present invention are preferably administered in the form of their sodium salt in order to increase their solubility, although other pharmaceutically acceptable salts may also be used for this purpose. They are preferably administered orally and they may be in the form of a composition with the usual pharmaceutically acceptable carriers and/or excipients. The precise dosage must be determined empirically and will differ depending upon the condition of the patient. Relatively small amounts of the compound of the present invention can be administered at first with steadily increasing daily dosages if no adverse effects are noted. A dosage of 15 g/day, for example, may be found to be preferred. Of course, the maximum safe toxicity dosage as determined in routine animal toxicity tests should never be exceeded. Furthermore, the dosage should be monitored to avoid any side effects due to the release of toxins caused by the dying cancer cells.
Anti-ammonia intoxication treatment, such as that used for treatment of cirrhosis of the liver, should be used to avoid such side effects.
Besides oral administration, the dicarboxylic acids in accordance with the present invention may be administered by any means of parenteral administration.
The theory behind the effectiveness of the compounds of the present invention is not fully understood. It is known, however, that many dicarboxylic acids are inhibitors of tyrosinase and that tyrosinase activity is caused by many malignant tumors. In view of the possibility that the action of these compounds on tyrosinase has something to do with their effectiveness, it may also be worthwhile to administer concurrently other inhibitors of tyrosinase, such as chemicals that can chelate or complex copper ions. Such inhibitors include D-penicillamine, p-aminobenzylic acid, BAL (dimercaprol), thioproline, etc.
Octacosanedioic acid may be prepared in accordance with classical methods of production of higher dicarboxylic acids. It is not believed that this compound has ever been prepared in pure form prior to the present invention, although those of ordinary skill in the art would find no difficulty in arriving at methods for the preparation of this compound, once the desirability of making it was known.
It will be obvious to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification. | Saturated aliphatic straight chain dicarboxylic acids having a total number of carbon atoms which are divisible by four, are selectively toxic to certain tumor cells while non-toxic to normal cells of the same origin. Octacosanedioic acid is particularly preferred as it is a component of normal blood serum. Compositions containing these compounds may be used in the treatment of certain malignancies. | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser. No. 11/321,322, which was filed on Dec. 28, 2005, and which is incorporated by reference in its entirety for all purposes.
FIELD OF THE INVENTION
[0002] This present invention relates generally to memory systems, components, and methods, and more particularly to fully buffered memory controllers that efficiently retire entries in a replay queue.
BACKGROUND OF THE INVENTION
[0003] Conventional computer memory subsystems are often implemented using memory modules. A computer circuit board is assembled with a processor having an integrated memory controller, or coupled to a separate memory controller. The processor having the integrated memory controller or the separate memory controller is connected by a memory bus to one or more memory module electrical connectors (the bus may also connect to additional memory permanently mounted on the circuit board). System memory is configured according to the number of and storage capacity of the memory modules inserted in the electrical connectors.
[0004] As processor speeds have increased, memory bus speeds have been pressured to the point that the multi-point (often referred to as “multi-drop”) memory bus model no longer remains viable. Referring to FIG. 1 , one current solution uses a “point-to-point” memory bus model employing buffered memory modules. In FIG. 1 , a computer system 100 comprises a host processor 105 communicating across a front-side bus 108 with a memory controller 110 that couples the host processor to various peripherals (not shown except for system memory). Memory controller 110 communicates with a first buffered memory module 0 across a high-speed point-to-point bus 112 . A second buffered memory module 1 , when included in system 100 , shares a second high-speed point-to-point bus 122 with first memory module 0 . Additional high-speed point-to-point buses and buffered memory modules can be chained behind memory module 1 to further increase the system memory capacity.
[0005] Buffered memory module 0 is typical of the memory modules. A memory module buffer (MMB) 146 connects module 0 to a host-side memory channel 112 and a downstream memory channel 122 . A plurality of memory devices (Dynamic Random Access Memory Devices, or “DRAMs” like DRAM 144 , are shown) connect to memory module buffer 146 through a memory device bus (not shown in FIG. 1 ) to provide addressable read/write memory for system 100 .
[0006] As an exemplary memory transfer, consider a case in which processor 105 needs to access a memory address corresponding to physical memory located on memory module 1 . A memory request issues to memory controller 110 , which then sends a memory command, addressed to memory module 1 , out on host memory channel 112 . Memory controller 110 also designates an entry 115 corresponding to the memory command into replay queue 111 . Prior entries corresponding to prior memory commands may be ahead of entry 115 in queue 111 .
[0007] For tractability reasons, entry 115 may be retired from the queue 111 only after two conditions are met. First, memory controller 110 only retires an entry after a corresponding non-error response is received. Second, memory controller 110 only retires an entry if all prior entries have been retired.
[0008] The MMB 146 of buffered memory module 0 receives the command, resynchronizes it, if necessary, and resends it on memory channel 122 to the MMB 148 of buffered memory module 1 . MMB 146 detects that the command is directed to it, decodes it, and transmits a DRAM command and signaling to the DRAMs controlled by that buffer. If the memory transfer was successful, MMB 148 sends a non-error response through memory module 0 back to memory controller 110 . Memory controller 110 retires entry 115 from replay queue 111 after the non-error response is received, but only if all prior entries have also been retired.
[0009] Due to economies, the size of the replay queue 111 is limited. Therefore, entries need to be retired as quickly as possible. Due to northbound bandwidth limitations of high-speed point-to-point bus 112 , receipt of non-error responses such as write acknowledges may be delayed. Delayed receipt of such a write acknowledgement may in turn delay the retirement of subsequent entries that were entered into replay queue 111 after entry 115 . The delayed retirement of an entry and subsequent entries limits the amount of space available in replay queue 111 for new entries.
[0010] Because of the forgoing limitations, the amount of free space in replay queues of memory controllers is limited. The disclosure that follows solves this and other problems.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a diagram showing a conventional memory controller.
[0012] FIG. 2 is a diagram of a memory controller that retires two entries from a replay queue in response to a single non-error response.
[0013] FIG. 3 is a flowchart showing how the memory controller of FIG. 2 retires the entries.
[0014] FIG. 4A is a timing diagram showing the operation illustrated in FIG. 2 .
[0015] FIG. 4B is a timing diagram showing an alternative operation of the memory controller of FIG. 2 .
DETAILED DESCRIPTION
[0016] FIG. 2 shows one example of a memory controller 200 that retires two replay queue entries according to a single non-error response. The memory controller 200 includes an issue engine 201 , a memory 202 and a replay queue 203 . The issue engine 201 performs the functions described in the flowcharts of FIG. 3 . The timing of the signals shown in FIG. 2 is depicted in the timing diagram in FIG. 4 a.
[0017] Memory controller 200 sends memory command 204 a to memory module 1 . In this example memory command 204 a is a burst length eight read command including a starting address for a multicycle read operation. In other examples memory command is any type of read command. An entry 204 b corresponding to memory command 204 a is created in replay queue 203 . Upon receiving memory command 204 a , memory module 1 starts reading data beginning with the start address. As memory module 1 is reading data, it sends back the read data in non-error memory response 204 c.
[0018] Next memory controller 200 sends memory command 205 a to memory module 0 that is north of memory module 1 . In this example memory command 205 a is a burst length four write command that provides write data to memory module 0 during four successive strobes. In other examples memory command 205 a is any type of write command. An entry 205 b corresponding to memory command 205 a is created in replay queue 203 . Entry 205 b is a consecutive entry with respect to entry 204 b . Upon receiving memory command 205 a , memory module 0 begins writing the data provided with memory command 205 a . Memory module 0 begins writing data concurrently with memory module 1 reading data according to memory command 204 b.
[0019] Memory controller 200 sends memory command 206 a to memory module 1 that is south of memory module 0 . Memory command 206 a is a burst read command similar to memory command 204 a . An entry 206 b corresponding to memory command 206 a is created in replay queue 203 .
[0020] Memory module 0 finishes writing data according to the burst length four write command 205 a . However, since memory module 1 is still sending read data via Memory Module Buffer (MMB) 245 of memory module 0 there is no bandwidth available for memory module 0 to send a non-error response 205 c . The non-error response 204 c including the read data consumes all of the bandwidth in the northbound direction. Accordingly, the memory controller 200 does not observe a non-error response including a write acknowledgement at this time.
[0021] After data is read according to memory command 204 a , memory module 1 begins reading data according to memory command 204 c . As memory module 1 is reading data, it sends back the read data in non-error memory response 206 c . Non-error response 206 c consumes all of the bandwidth in the northbound direction and is sent immediately after non-error responses 204 c . According to conventional FBD protocol, memory controller 200 must continue to wait to observe non-error response 205 c until bandwidth is available. As used within the specification, the FBD protocol refers to, for example, any revision of the FBD specification on the JEDEC website. Non-error response 205 c may include explicit signals such as idle patterns or write acknowledgements.
[0022] Memory controller 200 receives non-error response 204 c . Entry 204 b is retired from the replay queue 203 because there are no prior entries pending. Although memory controller 200 has not received an explicit non-error response 205 c corresponding to entry 205 b , memory controller 200 may also retire entry 205 b in response to non-corresponding non-error response 204 c . This is in contrast to conventional FBD protocol where memory controller 200 must continue to wait for non-error response 205 c . Thus two entries may be retired in response to a single non-error response 204 c.
[0023] Entry 205 b may be retired upon receipt of non-corresponding non-error response 204 c because of the following occurrences. First, entry 205 b corresponds to a write to a memory module that is north of a memory module that was read. Second, the write occurs concurrently with the read from the southern memory module. Third, an alert corresponding to memory command 205 a was not received. An alert corresponding to memory command 205 a would have taken priority over non-error response 204 c . Accordingly, the receipt of non-error response 204 c implicitly signals memory controller 200 that an alert was not issued and that memory command 205 a must have been successful. Thus, entry 205 b may be advantageously retired early before a corresponding non-error response 205 c is received.
[0024] Next non-error response 206 c is received. Entry 206 b may advantageously be retired immediately because there are no prior entries in memory queue 203 . Had memory controller 200 waited for a corresponding non-error response 205 c before retiring entry 205 b , prior entry 205 b would exist causing a delay in retiring 206 b . Thus memory controller 200 retires entries 205 b and 206 b early compared to a conventional memory controller.
[0025] Finally, non-error response 205 c including a write acknowledgement may be received. Since memory controller 200 has already been signaled that memory command 205 a was successful, memory controller 200 may forgo observation of explicit non-error response 205 c . Optionally forgoing explicit write acknowledgement 205 c due to the presence of the aforementioned occurrences advantageously increases southbound occupancy. The increase in southbound occupancy increases maximum bandwidth by as much as 50% over conventional systems with similar replay queue limitations.
[0026] The above process is illustrated in a flowchart in FIG. 3 . Referring to FIG. 3 , the memory controller 200 issues a read command to cause a first memory module to be read in block 300 . In block 301 , a write command is issued to cause a second memory module that is farther north than the first memory module to be concurrently written. Next the memory controller 200 creates a first entry corresponding to the read command in a replay queue 203 in block 302 . In block 303 a second entry is created corresponding to the write command.
[0027] Next, in block 304 the memory controller 200 waits for a non-error response corresponding to the read command. If the non-error response is received in block 305 , the memory controller 200 retires both entries in block 306 A. If the non-error response is not received, in block 306 B memory controller 200 resets the branch and then replays the contents of replay queue 203 .
[0028] FIG. 4A shows a timing diagram for the system illustrated in FIG. 2 . DIMM 1 receives a read command 204 a from memory controller 200 and begins reading data at T 6 . DIMM 0 receives a write command 205 a and begins writing data at T 7 concurrently with DIMM 1 reading data. As DIMM 1 is reading data a transmission 204 c from DIMM 1 begins at T 7 . Transmission 204 c continues up to T 10 , thereby preventing the memory controller 200 from immediately observing an explicit write acknowledge 205 c.
[0029] Meanwhile, DIMM 1 receives a read command 206 a from memory controller 200 at T 9 and begins reading. Immediately after DIMM 1 completes transmission 204 c , transmission 206 c begins at T 11 . Memory controller 200 is still unable to observe an explicit write acknowledgement 205 c because transmissions 204 c and 206 c consume all of the northbound bandwidth.
[0030] Meanwhile, memory controller 200 starts receiving the read data transmission 204 c from DIMM 1 at T 8 . When the transmission is completed at T 11 , memory controller 200 retires entry 204 b from the replay queue 203 . Memory controller 200 also retires entry 205 b from the replay queue 203 in response to receiving non-corresponding non-error response 204 c . Non-corresponding non-error response 204 c was not sent in response to memory command 205 a and does not correspond to entry 205 b . Nonetheless, entry 205 b is retired. Finally, at T 15 memory controller 200 receives non-error response 206 c and retires entry 206 b.
[0031] It is not necessary for memory controller 200 to observe write acknowledge 205 c at a first opening T 15 . Bandwidth may be saved for other transmissions by forgoing explicit observation of write acknowledge 205 c.
[0000] FIG. 4B shows a timing diagram according to a different series of transmissions than illustrated in FIG. 2 . The memory controller 200 causes DIMM 1 to start a first read T 6 and DIMM 0 to start writing data at T 7 . The memory controller 200 also causes DIMM 0 to start a second read at T 10 .
[0032] Memory controller 200 begins receiving a non-error response corresponding to the first read at T 8 . When the complete non-error response corresponding to the first read is received at T 11 , entries associated with the first read and the write are both retired. In other words, the entry associated with the write is retired in response to a non-corresponding non-error response. Finally, the memory controller 200 retires an entry associated with the second read at T 15 .
[0033] The system described above can use dedicated processor systems, micro controllers, programmable logic devices, or microprocessors that perform some or all of the operations. Some of the operations described above may be implemented in software and other operations may be implemented in hardware.
[0034] For the sake of convenience, the operations are described as various interconnected functional blocks or distinct software modules. This is not necessary, however, and there may be cases where these functional blocks or modules are equivalently aggregated into a single logic device, program or operation with unclear boundaries. In any event, the functional blocks and software modules or features of the flexible interface can be implemented by themselves, or in combination with other operations in either hardware or software.
[0035] Having described and illustrated the principles of the invention in a preferred embodiment thereof, it should be apparent that the invention may be modified in arrangement and detail without departing from such principles. I claim all modifications and variation coming within the spirit and scope of the following claims. | A memory controller uses a scheme to retire two entries from a replay queue due to a single non-error response. Advantageously, entries in a replay queue may be retired earlier than conventional systems, minimizing the size of the replay queue. | 6 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application claims priority to and incorporates by reference the entire contents of Japanese Patent Application No. 2015-255087, filed in Japan on Dec. 25, 2015.
BACKGROUND
[0002] 1. Related Technical Fields
[0003] Related technical fields include network devices, methods, and programs that identify similar users based on physiological characteristics to predict expense trends.
[0004] 2. Related Art
[0005] Services are present that analyze information about users in relation to the user's asset management so as to introduce asset management methods suitable for the users.
[0006] As an example of techniques relating to such services, a technique about a system is known that can efficiently perform simulation to support making a financial plan using the Internet. A conventional technique is described in Japanese Patent Application Laid-open No. 2002-41808, for example.
SUMMARY
[0007] It is, however, difficult for the conventional technique to provide a user with appropriate information about the user's future plan. For example, the conventional technique only provides the user with a result of the simulation about the asset at various stages in the user's life. The user, thus, obtains only a plan for managing income and expense under a specific situation. As a result, the user does not always obtain appropriate information about asset formation based on a comprehensive viewpoint such as whether a current tendency in expense is appropriate in the user's future life plan, for example.
[0008] Exemplary embodiments of the broad inventive principles described herein at least partially solve the problems in the conventional technology.
[0009] Network devices, methods, and programs according to exemplary embodiments access a memory that stores expense information for each of a plurality of subjects, the expense information for each of the plurality of subjects being associated with a stored subject profile that identifies physiological characteristics of a corresponding one of the subjects. The devices, methods, and programs receive a user profile from a user terminal via a network interface, the user profile identifying physiological characteristics of the user and an age of the user, and compare the physiological characteristics of the received user profile with the physiological characteristics in each stored profile to identify one of the plurality of subjects having similar physiological characteristics to the user. The devices, methods, and programs analyze the stored expense information that is associated with the identified subject in the memory to determine a trend of the expense of the identified subject, and generate a proposal including a predicted future expense trend for the user based on the determined trend and the user's age. The devices, methods, and programs then transmit the generated proposal to the user terminal via the network interface.
[0010] The above and other objects, features, advantages and technical and industrial significance will be better understood by reading the following detailed description of exemplary embodiments, when considered in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a schematic diagram illustrating an example of generation processing according to an embodiment;
[0012] FIG. 2 is a schematic diagram illustrating an exemplary structure of a generation device according to the embodiment;
[0013] FIG. 3 is a schematic diagram illustrating an example of a genetic test result table according to the embodiment;
[0014] FIG. 4 is a schematic diagram illustrating an example of a settlement information storage unit according to the embodiment;
[0015] FIG. 5 is a flowchart illustrating a processing procedure according to the embodiment;
[0016] FIG. 6 is a schematic diagram illustrating an example of generation processing according to a modification;
[0017] FIG. 7 is a schematic diagram illustrating an exemplary structure of the generation device according to the modification;
[0018] FIG. 8 is a schematic diagram illustrating an example of an attribute information table according to another modification; and
[0019] FIG. 9 is a hardware structural diagram illustrating an example of a computer that achieves the functions of the generation device.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
[0020] The following describes an embodiment of a generation device, a generation method, and a program stored on a computer-readable storage medium in detail with reference to the accompanying drawings. (As used herein the term “storage medium” is not intended to encompass transitory signals.) The following embodiments do not necessarily limit the broader inventive principles for which protection is sought. In the following respective embodiments, the same components are denoted by the same reference numerals and duplicated explanations thereof are omitted.
1. Example of Generation Processing
[0021] The following describes an example of generation processing according to the embodiment with reference to FIG. 1 . FIG. 1 is a schematic diagram illustrating an example of the generation processing according to the embodiment. With reference to FIG. 1 , an aspect of the generation processing according to the embodiment is described using a generation system 1 as an example. Specifically, with reference to FIG. 1 , an example of the generation processing is described in which a generation device 100 , which is a server, included in the generation system 1 identifies a similar user who is a user similar to a user serving as the processing object, and generates information indicating a trend of income or expense of the identified similar user.
[0022] As illustrated in FIG. 1 , the generation system 1 includes a user terminal 10 and the generation device 100 . The devices (the user terminal 10 and the generation device 100 ) included in the generation system 1 are coupled to each other via a communication network such as the Internet (not illustrated) in a communicable manner. The number of each of the devices included in the generation system 1 is not limited to that illustrated in FIG. 1 . For example, the generation system 1 may include a plurality of user terminals 10 .
[0023] The user terminal 10 is an information processing device used by a user. Specifically, the user terminal 10 is used for transmitting certain information to the generation device 100 or receiving information transmitted from the generation device 100 . The user terminal 10 is achieved by a mobile terminal such as a smartphone, a tablet terminal, or a personal digital assistant (PDA), a desktop personal computer (PC), or a notebook PC. In the example illustrated in FIG. 1 , the user terminal 10 is a smartphone used by a user U 01 . In the following explanation, the user terminal 10 is described as the user U 01 in some cases. The user U 01 , thus, can be replaced with the user terminal 10 in the following explanation.
[0024] The generation device 100 is a server that provides certain information to the user terminal 10 . Specifically, the generation device 100 identifies the similar user who is a user similar to the user U 01 under a certain condition on the basis of information received from the user terminal 10 . The generation device 100 acquires information about income or expense of the user U 01 and the similar user. The generation device 100 generates information that indicates a trend of income or expense of the similar user on the basis of the acquired information. Specifically, the generation device 100 generates comparison information that indicates a comparison of the trend of income or expense between the user U 01 and the similar user, and provides the generated comparison information to the user U 01 . The information about income or expense is a concept widely including information such as an amount of income, an amount of expense, a breakdown of income or expense, information about an income-expense balance, a difference between income and expense, and an amount of savings derived from balance information. The information about income or expense is described as “asset information” in the present specification in some cases.
[0025] The generation device 100 may generate a proposal (recommendation) to the user U 01 together with the comparison information. For example, the generation device 100 generates a proposal relating to actions that the user U 01 could perform in the future. The actions are derived from the comparison of the trend of the asset information about the user U 01 and the trend of the asset information about the similar user. For an exemplary proposal, the generation device 100 indicates an amount of expense the user U 01 is assumed to need for payments in the future and proposes actions relating to the asset management that the user could perform in the future for covering the assumed amount of expense. The generation device 100 generates the proposal relating to the asset formation of the user U 01 on the basis of the trend of the asset information about the similar user, thereby giving certain guidance to the user U 01 for preparing future assets. The following describes a flow of the generation processing performed by the generation device 100 with reference to FIG. 1 . FIG. 1 illustrates medical expense as an example of the amount of expense the user U 01 is assumed to need for payments in the future.
[0026] The generation device 100 requests the user U 01 to provide information about the user U 01 as information used for identifying the user who is similar to the user U 01 . For example, the generation device 100 requests the information about health of the user U 01 . The generation device 100 analyzes the information about the health of the user U 01 ' and information about health of another user, determines similarity between the users, and identifies the user who is similar to the user U 01 .
[0027] In the embodiment, the generation device 100 requests, as the information about the health of the user U 01 , a result of a genetic test the user U 01 already underwent. The user U 01 transmits the result of the genetic test that the user U 01 already underwent to the generation device 100 via the user terminal 10 (step S 11 ).
[0028] The result of the genetic test that the user U 01 underwent includes types of diseases the user U 01 tends to develop and risk values that are values indicating possibilities of developing diseases. In the example illustrated in FIG. 1 , the genetic test result of the user U 01 includes the risk value of developing diabetes is “1.7” while the risk value of developing “high blood pressure” is “2.9.” In the result of the genetic test that the user U 01 underwent, when the risk value corresponding to a type of disease exceeds “2.0,” the possibility (a degree of risk) of developing the disease is determined to be “high.” The determination means that the risk of developing the disease is high, i.e., the possibility of developing the disease is high. When the risk value is between “1.5” and “2.0” in the genetic test result, the possibility of developing the disease is determined to be “medium.” The determination means that the risk of developing the disease is medium, i.e., the possibility of developing the disease is not high enough to be that of the disease determined to be a “high” risk but the possibility of developing the diseases is relatively high.
[0029] The generation device 100 receives the genetic test result transmitted from the user terminal 10 and stores the received genetic test result in a genetic test result table 122 . The generation device 100 stores, in the genetic test result table 122 , not only the genetic test result of the user U 01 but also the respective genetic test results transmitted from other users.
[0030] When receiving the genetic test result of the user U 01 , the generation device 100 performs processing that identifies a user who is similar to the user U 01 (step S 12 ). Specifically, the generation device 100 compares the types of diseases and the risk values of the respective diseases between the user U 01 and other users. For example, the generation device 100 extracts the genetic test result for each of the other users when the types of diseases included in the genetic test result of the user are same as those included in the genetic test result of the user U 01 , and the percentage of the same disease types is a certain percentage (e.g., 80% or more). The generation device 100 further extracts the genetic test result out of the extracted genetic test results when the degrees of the risks, which are indicated with the risk values of the respective diseases, in the extracted genetic test result are the same as those included in the genetic test result of the user U 01 , and the percentage of the same degrees of risks is a certain rate. The generation device 100 identifies the users corresponding to the extracted genetic test results as the users who are similar to the user U 01 .
[0031] In the example illustrated in FIG. 1 , the generation device 100 identifies a user U 02 as the user who is similar to the user U 01 . The user U 02 is a user who underwent the genetic test in which risks of many same diseases as the genetic test that the user U 01 underwent are tested, and many items in whose genetic test result match those in the genetic test result of the user U 01 . For example, the user U 02 was diagnosed that a degree of risk of diabetes is “medium” and a degree of risk of high blood pressure is “high” in the genetic test result.
[0032] The user U 01 provides information about assets of the user U 01 to the generation device 100 after transmitting the genetic test result. For example, the user U 01 periodically provides, to the generation device 100 , information about an amount of monthly expense and a breakdown of the amount of expense. In this case, the user U 01 may transmit the information about the assets of the user U 01 by itself or provide information (asset information) about income and expense by providing, to the generation device 100 , an authority allowing access to data indicating the breakdown of the expense (e.g., a use history of a credit card or logs of interaction with financial institutions). The asset information provided by the user U 01 is not limited to the information after the transmission of the genetic test result. The user U 01 may provide asset information before the transmission of the genetic test result. The generation device 100 successively stores the asset information provided from the user U 01 in a settlement information storage unit 125 .
[0033] The user U 02 periodically provides the asset information about the user U 02 to the generation device 100 because the user U 02 is also a user serving as the processing object of the generation device 100 besides the user U 01 . The user U 02 is older than the user U 01 and has provided asset information to the generation device 100 for a longer period of time than the user U 01 . The past information at the time when the user U 02 was of the same age as the user U 01 now, is thus, stored in the settlement information storage unit 125 as the asset information about the user U 02 .
[0034] The generation device 100 generates information to be presented to the user U 01 on the basis of the acquired asset information (step S 13 ). Specifically, the generation device 100 generates the comparison information that indicates a comparison of a trend of the asset information about the user U 01 and a trend of the asset information about the user U 02 , who is a similar user. In the example illustrated in FIG. 1 , the generation device 100 generates the comparison information using the information about medical expense, which is an example of the asset information, in the expense of the users U 01 and U 02 .
[0035] For example, the generation device 100 generates comparison information 30 illustrated in FIG. 1 . As illustrated in FIG. 1 , the comparison information 30 includes a graph 32 that indicates a comparison of the trend of the asset information between the users U 01 and U 02 . In the graph 32 , the age of the user U 01 and the amount of medical expense paid at each age are indicated with the broken line titled “your (user U 01 's) medical expense.” In the graph 32 , the age of the user U 02 and the amount of medical expense paid at each age are indicated with the broken line titled “similar user's (user U 02 's) medical expense.” The ordinate axis of the graph 32 represents the amount of medical expense in unit of ten thousand yen. The generation device 100 generates the comparison information 30 that indicates transition in the amounts of medical expense of the user U 01 and the user U 02 who is similar to the user U 01 as the information to be presented to the user U 01 .
[0036] Furthermore, the generation device 100 may generate a proposal to the user U 01 as information included in the comparison information 30 . For example, the generation device 100 compares a trend of the amount of medical expense of the user U 01 from the past to the present and a tendency of the amount of medical expense of the user U 02 when the user U 02 was of the same age as the user U 01 . The generation device 100 obtains information that the user U 01 is predicted to need to pay a larger amount of medical expense than the current amount a few years later as a result of referring to the tendency of the medical expense of the user U 02 . For example, the generation device 100 refers to an amount of savings of the user U 01 in the asset information acquired from the user U 01 and calculates a difference between the amount of savings of the user U 01 and the amount of medical expense when the user U 02 was of the same age as the user U 01 for each of the age of the user U 01 in the future. As a result, the generation device 100 obtains information how much amount of money the user U 01 should save for another few more years. Using the information, the generation device 100 generates, as a proposal to the user U 01 , information about actions such as saving money corresponding to the difference calculated from the amount of medical expense paid by the user U 02 or take out insurance that covers high risk diseases. The generation device 100 may include the generated proposal in the comparison information 30 as the information displayed together with the graph 32 .
[0037] The generation device 100 transmits the information such as the generated comparison information 30 to the user terminal 10 to notify the user U 01 of the generated information (step S 14 ). The user U 01 refers to the comparison information 30 displayed in the user terminal 10 , thereby making it possible to obtain information about such as the trend of the amount of medical expense for each age of the user U 02 who underwent the genetic test result similar to that of the user U 01 . When the comparison information 30 includes the proposal generated by the generation device 100 , the user U 01 can grasp the amount of medical expense predicted to be needed for payments in the future or know actions that should be taken in preparation for the future.
[0038] As described above, the generation device 100 according to the embodiment identifies the user U 02 who is a user having similarity to the user U 01 who is the processing object under a certain condition. The generation device 100 acquires the asset information about the user U 01 and the identified user U 02 . The generation device 100 generates the comparison information that indicates the comparison of the trend of the acquired asset information about the user U 01 and the trend of the acquired asset information about user U 02 .
[0039] Specifically, the generation device 100 according to the embodiment identifies the user U 02 who is the similar user using the similarity to the genetic test result acquired from the user U 01 as the certain condition. The generation device 100 can generate the comparison information 30 that indicates an amount of medical expense assumed to be paid by the user U 01 in the future on the basis of the asset information acquired from the users U 01 and U 02 . The generation device 100 notifies the user U 01 of the generated information, thereby making it possible to transmit, to the user U 01 , the trend of the amount of medical expense of the user U 02 who has the genetic test result similar to that of the user U 01 . As a result, the user U 01 can obtain certain guidance with regard to expenses containing many uncertain factors in the future such as medical expense. The generation device 100 can provide the user U 01 with appropriate information about the future plan.
[0040] In the example illustrated in FIG. 1 , the user U 02 is the user who is similar to the user U 01 . The generation device 100 may extract not only the user U 02 but also a plurality of similar users as the users who are similar to the user U 01 . The generation device 100 may present the trend of the asset information statistically obtained from the multiple similar users as the object compared with the trend of the asset information about the user U 01 . The generation device 100 , thus, can generate the information that compares the trend of the averaged asset information obtained from a number of samples with the trend of the asset information about the user U 01 , thereby making it possible to provide comparison information having high reliability to the user U 01 . In the example illustrated in FIG. 1 , the trend of the asset information about the user U 01 and the trend of the asset information about the similar user are displayed together in the graph 32 included in the comparison information 30 . The display manner is, however, not limited to this example. The generation device 100 may generate the information that indicates only the trend of the asset information about the user U 02 instead of the information about the comparison between the users U 01 and U 02 . This information also enables the user U 01 to know the trend of the asset information about the user U 02 who is a similar user, thereby making it possible for the user U 01 to obtain useful information about the future plan of the user U 01 .
2. Structure of Generation Device
[0041] The following describes a structure of the generation device 100 according to the embodiment with reference to FIG. 2 . FIG. 2 is a schematic diagram illustrating an exemplary structure of the generation device 100 according to the embodiment. As illustrated in FIG. 2 , the generation device 100 includes a communication unit 110 , a storage unit 120 , and a control unit 130 . The generation device 100 may include an input unit (e.g., a keyboard or a mouse) that receives various types of operation from an administrator, for example, who uses the generation device 100 , and an output unit (e.g., a liquid crystal display) that outputs various types of information.
[0042] The communication unit 110 is achieved by a network interface card (NIC), for example. The communication unit 110 is connected to a communication network in a wired or wireless manner, and exchanges information between itself and the user terminal 10 via the communication network.
[0043] The storage unit 120 is achieved by a semiconductor memory element such as a random access memory (RAM) or a flash memory, or a storage device such as a hard disk drive or an optical disc drive. The storage unit 120 according to the embodiment includes a user information storage unit 121 and the settlement information storage unit 125 . The following describes the respective storage units one by one.
[0044] The user information storage unit 121 stores therein user information that indicates risks relating to the users. In the embodiment, the user information storage unit 121 includes the genetic test result table 122 as one of the data tables that store therein the user information.
[0045] The genetic test result table 122 stores therein the information about the genetic test results. FIG. 3 illustrates an example of the genetic test result table 122 according to the embodiment. As illustrated in FIG. 3 , the genetic test result table 122 includes items such as “user ID,” “analysis item,” “risk value,” and “degree of risk.”
[0046] The “user ID” indicates identification information to identify the user. In the embodiment, the user ID is in common with the reference sign used in the description. For example, a user having a user ID of “U 01 ” is the “user U 01 .”
[0047] The “analysis item” indicates the item analyzed in the genetic test. The analysis item is represented using the name of a disease, for example. The “risk value” indicates a value obtained by quantifying the risk of developing a disease corresponding to the analysis item.
[0048] The “degree of risk” indicates a result obtained by determining the risk of developing a disease on the basis of the risk value. In the embodiment, the analysis item having a risk value lower than “1.5” is determined to be “low” in the degree of risk. This determination indicates that a risk of a user developing the disease corresponding to the analysis item is lower than the disease corresponding to the analysis item having “high” or “medium” in the degree of risk. The analysis item having a risk value higher than “2.0” is determined to be “high” in the degree of risk. This determination indicates that a risk of a user developing the disease corresponding to the analysis item is extremely high. The analysis item having a risk value from “1.5” to “2.0” is determined to be “medium” in the degree of risk. This determination indicates that a risk of a user developing the disease corresponding to the analysis item is higher than the disease corresponding to the analysis item having “low” in degree of risk and lower than the disease corresponding to the analysis item having “high” in degree of risk.
[0049] FIG. 3 illustrates the genetic test result that the user U 01 identified by the user ID “U 01 ” underwent as an example. The genetic test result shows that the analysis items in the test are “diabetes,” “high blood pressure,” “hay fever,” and “gout,” for example, and the risk values are “1.7,” “2.9,” “1.6,” and “1.2,” respectively, and the degrees of risks are “medium,” “high,” “medium” and “low,” respectively.
[0050] As for the degrees of risks illustrated in FIG. 3 , the generation device 100 may employ the standard represented by a company conducting the genetic test or the standard determined uniquely by the generation device 100 on the basis of the risk values of the genetic test results. For example, the generation device 100 may acquire the risk values of the genetic test results and statistical information about the number of users who actually developed the diseases, learn a relation therebetween, and uniquely determine the degrees of risks.
[0051] The settlement information storage unit 125 stores therein information (settlement logs) about settlement. FIG. 4 illustrates an example of the settlement information storage unit 125 according to the embodiment. As illustrated in FIG. 4 , the settlement information storage unit 125 includes items such as “user ID,” “age,” “collection time,” “expense item,” and “amount.”
[0052] The “user ID” corresponds to the same item illustrated in FIG. 3 . The “age” indicates the age of the user. FIG. 4 illustrates the ages as “AA,” “XX,” and so on in a conceptual manner. Practically, the age of the user when the settlement log is stored, is stored in the item of “age.”
[0053] The “collection time” indicates the time when the user performs the expenditure. The “expense item” indicates the breakdown of the expense. The “amount” indicates the amount of expense for each expense item.
[0054] FIG. 4 illustrates information stored in the settlement information storage unit 125 as the settlement log relating to the user U 01 . The information indicates that the amount of the “medical expense” is “ 30 , 000 ” yen and the amount of the “food expense” is “30,000” yen out of the expense items collected on November 2015 when the user U 01 was “AA” years old.
[0055] In the example illustrated in FIG. 4 , the amount of expense is collected on a monthly basis. The collection manner of the amount of expense to be stored is, however, not limited to the example. For example, an amount of annual expense or a cumulative amount of expenses may be stored for each user in the settlement information storage unit 125 .
[0056] The control unit 130 is achieved by various programs (corresponding to an example of a generation program) stored in an internal storage device of the generation device 100 , the various programs being executed by a central processing unit (CPU) or a micro processing unit (MPU) using a RAM as a working area, for example. The control unit 130 is achieved by an integrated circuit such as an application specific integrated circuit (ASIC) or a field programmable gate array (FPGA).
[0057] As illustrated in FIG. 2 , the control unit 130 according to the embodiment includes an acquisition unit 131 , an identification unit 132 , a generation unit 133 , and a notification unit 134 , and achieves or generates functions and operation of the information processing described below. The internal structure of the control unit 130 is not limited to that illustrated in FIG. 2 and may be any other structure that performs the information processing described below. The connection relation among the respective processing units included in the control unit 130 is not limited to that illustrated in FIG. 2 and may be another connection relation.
[0058] The acquisition unit 131 acquires various types of information. The acquisition unit 131 acquires the user information about the user as the information used for identifying the user who has similarity to the user serving as the processing object under a certain condition, for example. The acquisition unit 131 acquires information about the health of the user as an example of the user information. Specifically, the acquisition unit 131 acquires, as the user information, a result of the genetic test the user already underwent.
[0059] The acquisition unit 131 acquires, from the user serving as the processing object, the information (asset information) about the income or expense of the user. Specifically, the acquisition unit 131 acquires, as the asset information, the settlement information about such as an amount of expense paid by the user or the breakdown of the expense. The acquisition unit 131 may acquire, as the asset information, an amount of the user's income or an amount of the user's savings, for example.
[0060] The acquisition unit 131 may acquire various types of information used for the generation processing, which is described later. For example, when recommending the user to take out insurance covering diseases as the information proposed to the user, the acquisition unit 131 acquires information about the insurance. The acquisition unit 131 may acquire the information by receiving input from the administrator of the generation device 100 or by receiving the information from a company providing the insurance. The acquisition unit 131 may acquire information about a definition used for the processing, such as how the similarity is determined under which condition in the genetic test results of a plurality of users or what kind of proposal is generated.
[0061] The acquisition unit 131 stores the acquired information in the respective storage units. For example, the acquisition unit 131 stores the acquired user information in the user information storage unit 121 . For another example, the acquisition unit 131 stores the acquired asset information in the settlement information storage unit 125 . The acquisition unit 131 does not necessary store the acquired information in the storage unit 120 but may send the acquired information directly to the respective processing units used for the processing.
[0062] The identification unit 132 identifies the similar user who is a user having similarity to the user serving as the processing object under a certain condition. For example, the identification unit 132 identifies the similar user by determining similarity in the user information acquired from the user.
[0063] When the acquisition unit 131 acquires the genetic test result from the user, the identification unit 132 identifies, as the similar user, a certain user who satisfies a condition of the genetic test result being similar to that of the user. For example, the identification unit 132 determines whether the genetic test result of a certain user has similarity to the genetic test result of the user serving as the processing object using a matching percentage of the items (types of diseases) analyzed in the genetic test result and a matching percentage of the degrees of risks of the analyzed items in the genetic test result of the certain user. Specifically, the identification unit 132 determines the genetic test result having similarity on the basis of that the matching percentage of the items analyzed in the genetic test result is 80% or more and the matching percentage of the degrees of risks of the analyzed items is 80% or more. The identification unit 132 , thus, can identify, as the similar users, the users who probably develop the same disease on the basis of the genetic test results. The value of the matching percentage can be changed to any value. For example, the identification unit 132 may perform the identification processing on a plurality of users, perform certain learning processing after the identification processing, and determine an appropriate value for the matching percentage.
[0064] The generation unit 133 generates information that indicates a trend of the income or expense of the similar user on the basis of the information acquired by the acquisition unit 131 . The generation unit 133 generates the comparison information that indicates a comparison of the trend of income or expense between the user and the similar user, for example. When the acquisition unit 131 acquires, as the information about income or expense, information about the amount of expense with a classification in which the breakdown of the expense is classified into certain items, the generation unit 133 generates the comparison information about the trend of the amount of expense for each certain item. Practically, the generation unit 133 generates the comparison information 30 that indicates the comparison of the amount of medical expense between the user and the similar user as illustrated in FIG. 1 .
[0065] When the acquisition unit 131 acquires the information (asset information) about the income or expense of a plurality of similar users, the generation unit 133 may generate the comparison information about the trend of the asset information about the user and the trend of the asset information statistically obtained from the multiple similar users.
[0066] The generation unit 133 may generate a proposal to the user together with the comparison information notified to the user. For example, the generation unit 133 calculates an assumed amount of medical expense of the user in the future, and generates, as the proposal, the information about actions to secure money for the medical expense in the future. Specifically, the generation unit 133 generates the proposal that indicates actions (e.g., save money or make an investment) relating to the asset formation performed by the user and insurance the user should take out, for example. The generation unit 133 may generate a proposal that indicates a specific amount such as a proposal of how much amount of expense the user should reduce or a proposal of a slight increase in an amount of expense being acceptable.
[0067] When generating a proposal to the user, the generation unit 133 may use definition information that indicates contents of proposed actions. The definition information is generated by the administrator of the generation device 100 and held in the generation device 100 , for example. The definition information includes a definition used for the processing such as a definition in which an action proposed to the user is “to save money” when a certain difference is present between an amount of expense of the user serving as the processing object and an amount of the expense of the similar user when the similar user was of the same age as the user. The generation device 100 can generate an appropriate proposal to the user in accordance with the definition information. The definition information may be appropriately amended or changed by the administrator, for example, of the generation device 100 or by the generation device 100 . Information about types of insurance (insurance covering diseases) proposed to the user or an appropriate investment destination based on an assumed amount of medical expense may be stored as the definition information.
[0068] The notification unit 134 makes notification of various types of information. For example, the notification unit 134 transmits the information generated by the generation unit 133 to the user terminal 10 to notify the user of the trend of the asset information about the similar user. Specifically, the notification unit 134 transmits the comparison information generated by the generation unit 133 to the user terminal 10 to notify the user of the information that indicates the comparison of the asset information between the user and the similar user.
[0069] The notification unit 134 notifies the user of the information that indicates the comparison of the trend of the asset information between the users U 01 and U 02 as represented by the graph 32 in the comparison information 30 illustrated in FIG. 1 , for example. When the information generated by the generation unit 133 includes a proposal to the user, the notification unit 134 notifies the user of the generated proposal. For example, the notification unit 134 notifies the user of a proposal that encourages the user to save more money on the basis of the comparison of current asset information about the user and the asset information about the similar user when the similar user was of the same age as the user. The user can obtain guidance for actions that the user could perform by referring to the information via the user terminal 10 .
3. Processing Procedure
[0070] The following describes a procedure of the processing performed by the generation device 100 according to the embodiment with reference to FIG. 5 . FIG. 5 is a flowchart illustrating a processing procedure performed by the generation device 100 according to the embodiment.
[0071] As illustrated in FIG. 5 , the acquisition unit 131 of the generation device 100 determines whether a genetic test result is received from a user as the user information (step S 101 ). If no genetic test result is received (No at step S 101 ), the acquisition unit 131 stands-by until the reception of the genetic test result.
[0072] If the acquisition unit 131 receives the genetic test result (Yes at S 101 ), the identification unit 132 identifies a user whose genetic test result is similar to that of the user (step S 102 ).
[0073] The generation unit 133 generates the comparison information about the comparison of the user serving as the processing object and the user identified by the identification unit 132 (step S 103 ). The generation unit 133 generates a proposal to the user (step S 104 ). The notification unit 134 transmits the information generated by the generation unit 133 to the user, thereby notifying the user of the information (step S 105 ).
[0074] The generation unit 133 does not have to generate a proposal to the user in case of notifying the user only of the comparison information about the comparison of the trend of the asset information. In this case, the processing at step S 104 is skipped.
4. Modifications
[0075] The generation device 100 according to the embodiment may be implemented in various forms besides the embodiment. The following describes other embodiments of the generation device 100 .
4-1. Attribute Information
[0076] In the embodiment described above, the generation device 100 generates the comparison information on the basis of the genetic test result acquired from the user. The generation device 100 may further acquire detailed information about the user as the user information to generate the comparison information. The following describes the generation processing with reference to FIG. 6 .
[0077] FIG. 6 is a schematic diagram illustrating an example of the generation processing according to a modification. In the example illustrated in FIG. 6 , the user U 01 who uses the user terminal 10 further provides detailed information about the user U 01 to the generation device 100 together with the genetic test result. The generation device 100 generates the comparison information on the basis of the information provided from the user U 01 .
[0078] As illustrated in FIG. 6 , the user terminal 10 transmits the user information serving as the information about the user U 01 (step S 21 ). The user information transmitted from the use terminal 10 is attribute information that indicates attributes of the user U 01 , for example. The attribute information about the user U 01 is the information that indicates a family structure, an academic history, an annual income, an occupation, or a residential area, for example.
[0079] The generation device 100 acquires the attribute information about the user U 01 transmitted from the user terminal 10 . The generation device 100 stores the acquired attribute information in an attribute information table 123 . The generation device 100 specifies a similar user on the basis of the attribute information about the user U 01 (step S 22 ).
[0080] For example, the generation device 100 extracts other users having attribute information including the same items as the attribute information about the user U 01 . Examples of the items include the family structure, the academic history, the annual income, the occupation, and the residential area. The generation device 100 identifies a user as the similar user when the certain number or more of items in the attribute information of the user are the same as those of the attribute information about the user U 01 , for example. The generation device 100 may further identify a user who has the attribute information more similar to that of the user U 01 out of the extracted users who are similar to the user U 01 and are extracted on the basis of the genetic test results illustrated in FIG. 1 .
[0081] The generation device 100 generates, as the information to be presented to the user U 01 , comparison information 34 about the comparison of the user U 01 and the similar user identified at step S 22 (step S 23 ).
[0082] In FIG. 6 , the comparison information 34 generated by the generation device 100 includes a graph 36 . As illustrated in FIG. 6 , the graph 36 includes an amount of income of the similar user in addition to the amount of your (user U 01 's) expense and an amount of expense of the similar user. In this way, the generation device 100 acquires the attribute information from the user serving as the processing object, thereby generating the comparison information 34 including more information than that of the comparison information 30 illustrated in FIG. 1 .
[0083] The generation device 100 transmits the information such as the generated comparison information 34 to the user terminal 10 to notify the user U 01 of the generated information (step S 24 ). As a result, the user U 01 can browse the comparison information including not only the amount of expense but also the comparison of the attribute information between the user U 01 and the other user.
[0084] When the generation device 100 according to the modification acquires the information about the attributes of a user, and the information about the acquired attributes of the user and the information about the attributes of another user have similarity, the generation device 100 may perform processing in such a mariner that the other user is identified as the similar user.
[0085] The generation device 100 acquires, as the user information, not only the genetic test result but also the attribute information about the user U 01 , thereby making it possible to identify the user who is similar to the user U 01 on the basis of the acquired information. For example, a difference occurs, in some cases, in the trend of an amount of income or expense of a user who is similar to the user U 01 in the genetic test result depending on whether the residential area of the user who is similar to the user U 01 in the genetic test result is a city or a countryside. The generation device 100 according to the modification identifies the user using further the attribute information about the user U 01 , thereby making it possible to accurately identify the user who is similar to the user U 01 . As a result, the user U 01 can obtain the comparison information about the comparison with an appropriate similar user as a further reference to the asset formation of the user U 01 in the future.
[0086] The following describes a structure of the generation device 100 according to the modification. FIG. 7 is a schematic diagram illustrating an exemplary structure of the generation device 100 according to the modification. As illustrated in FIG. 7 , the generation device 100 according to the modification further includes the attribute information table 123 in addition to the structure of the generation device 100 illustrated in FIG. 1 .
[0087] The attribute information table 123 is one of the data tables included in the user information storage unit 121 . The attribute information table 123 stores therein the information about the attribute information about the user. FIG. 8 illustrates an example of the attribute information table 123 according to the modification. As illustrated in FIG. 8 , the attribute information table 123 includes items such as “user ID,” “attribute,” and “content.”
[0088] The “user ID” corresponds to the same item illustrated in FIG. 3 . The “attribute” indicates the type of attribute information about the user. The “content” indicates the content of each type of the attribute information.
[0089] FIG. 8 illustrates the attribute information about the user U 01 as an example of the information stored in the attribute information table 123 . In the example, types of attribute information such as “gender,” “age,” “family structure,” “academic history,” “annual income,” “occupation,” and “residential area” are stored. The contents of the respective types of attribute information about the user U 01 indicate that the gender is “male,” the age is “AA,” the family structure is “single,” the academic history is “graduate of BBB university,” the annual income is “5,000,000” yen, the occupation is “CCC,” and the residential area is “DDD.”
[0090] The generation device 100 according to the modification can determine similarity between users or generate the comparison information about the attribute information using the attribute information about the respective users stored in the attribute information table 123 .
4-2. Condition Setting
[0091] In the embodiment described above, the generation device 100 identifies the similar user of the user serving as the processing object on the basis of conditions such as similarity to the genetic test result and similarity to the attribute information. The generation device 100 may preliminarily receive a condition from the user serving as the processing object and identify the similar user serving as the comparison object.
[0092] For example, the user transmits, to the generation device 100 , a condition of a user (hereinafter described as a “designated user”) who is the target person, i.e., a person the user wants to compare with. Specifically, the user sets a similar user who has an amount of savings more than “10,000,000” yen at the age of “50 years old” among the similar users as a condition of the designated user who will be the comparison object of the user, and transmits the condition to the generation device 100 . The generation device 100 receives the condition from the user, and extracts the designated user who matches the condition out of the similar users. The generation device 100 generates the comparison information about comparison of the asset information between the designated user and the user serving as the processing object.
[0093] In this case, the user can know the trend of the asset information about the designated user who has an amount of savings more than 10,000,000 yen at 50 years old as the generated information. The user, thus, can check how the designated user, who achieves the target set by the user, formed the asset that the user aims to build up in addition to the similarity with regard to the genetic test result. As a result, the user can obtain the information that is more useful for the user's future plan.
4-3. User Information
[0094] In the embodiment described above, the generation device 100 acquires, as the user information, the genetic test result and information about the attribute information. The user information acquired by the generation device 100 is, however, not limited to the examples. For example, the generation device 100 may use various types of information as the user information as long as the various types of information include the information capable of identifying a similar user. For example, the generation device 100 may use a result of a medical examination that the user U 01 underwent as the user information instead of the genetic test result.
4-4. Display of Risk
[0095] In the embodiment described above, a risk of the user developing a certain disease is indicated by the risk value or the degree of risk evaluated in three stages such as “high,” “medium,” and “low.” The generation device 100 , however, does not have to use such displays when determining or evaluating the risk. For example, the generation device 100 may indicate whether the possibility of the user U 01 developing a certain disease is higher or lower than those of other general users with a percentage or rate.
5. Others
[0096] In the processes described in the embodiment, all or a part of the processes described to be automatically performed can also be manually performed. Alternatively, all or a part of the processes described to be manually performed can also be automatically performed by known methods. In addition, the processing procedures, the specific names, and information including various types of data and parameters described in the above description and drawings can be changed as required unless otherwise specified.
[0097] Furthermore, the components of the devices illustrated in the drawings are functionally conceptual ones, and are not always required to be physically configured as illustrated in the drawings. That is, specific forms of distributions and integrations of the devices are not limited to those illustrated in the drawings. All or a part of the devices can be configured to be functionally or physically distributed or integrated in arbitrary units in accordance with various loads, the usage states, and the like.
[0098] For example, the user information storage unit 121 and the settlement information storage unit 125 , which are illustrated in FIG. 2 , do not have to be included in the generation device 100 but may be included in an external storage server. In this case, the generation device 100 accesses the storage server to acquire the user information and the settlement information.
[0099] The generation device 100 may be separated into a front-end server side that primarily executes processing relating to external devices such as receiving the user information from the user terminal 10 , and a back-end server side that executes internal processing such as generating the comparison information, for example.
6. Hardware Structure
[0100] The generation device 100 according to the embodiment is achieved by a computer 1000 having the structure illustrated in FIG. 9 , for example. FIG. 9 is a hardware structural diagram illustrating an example of the computer 1000 that achieves the functions of the generation device 100 . The computer 1000 includes a CPU 1100 , a RAM 1200 , a read only memory (ROM) 1300 , a hard disk drive (HDD) 1400 , a communication interface (I/F) 1500 , an input-output interface (I/F) 1600 , and a media interface (I/F) 1700 .
[0101] The CPU 1100 operates on the basis of a program stored in the ROM 1300 or the HDD 1400 , and controls the respective components. The ROM 1300 stores therein a boot program executed by the CPU 1100 when the computer 1000 is booted, and programs dependent on the hardware of the computer 1000 , for example.
[0102] The HDD 1400 stores therein programs executed by the CPU 1100 and data used by the programs, for example. The communication I/F 1500 receives data from other apparatuses via a communication network 500 and sends the data to the CPU 1100 . The communication I/F 1500 transmits data generated by the CPU 1100 to other apparatuses via the communication network 500 .
[0103] The CPU 1100 controls an output device such as a display or a printer and an input device such as a keyboard or a mouse via the input-output I/F 1600 . The CPU 1100 acquires data from the input device via the input-output I/F 1600 . The CPU 1100 outputs generated data to the output device via the input-output I/F 1600 .
[0104] The media I/F 1700 reads a program or data stored in a recording medium 1800 and provides it to the CPU 1100 via the RAM 1200 . The CPU 1100 loads the program in the RAM 1200 from the recording medium 1800 via the media I/F 1700 and executes the loaded program. The recording medium 1800 is an optical recording medium such as a digital versatile disc (DVD) or a phase change rewritable disc (PD), a magneto-optical recording medium such as a magneto-optical disc (MO), a tape medium, a magnetic recording medium, or a semiconductor memory.
[0105] For example, when the computer 1000 functions as the generation device 100 , the CPU 1100 of the computer 1000 executes the generation program loaded in the RAM 1200 to achieve the functions of the control unit 130 . The HDD 1400 stores therein the various types of data in the storage unit 120 . The CPU 1100 of the computer 1000 , which reads the programs from the recording medium 1800 and executes them, may acquire the programs from another device via the communication network 500 .
7. Advantages
[0106] As described above, the generation device 100 according to the embodiment includes the identification unit 132 , the acquisition unit 131 , and the generation unit 133 . The identification unit 132 identifies the similar user who is a user having similarity to the user serving as the processing object under a certain condition. The acquisition unit 131 acquires the information about income or expense of the similar user identified by the identification unit 132 . The generation unit 133 generates the information that indicates a trend of the income or expense of the similar user on the basis of the information acquired by the acquisition unit 131 .
[0107] The generation device 100 according to the embodiment identifies the similar user who is similar to the user and generates the information that indicates a trend of income or expense of the identified similar user. The generation device 100 , thus, can give certain guidance to the user for concerns including many items the user hardly foresees such as the asset formation in the future. As a result, the generation device 100 can provide the user with appropriate information about the user's future plan.
[0108] The acquisition unit 131 acquires the information about income or expense of the user. The generation unit 133 generates the comparison information that indicates a comparison of the trend of income or expense between the user and the similar user.
[0109] The generation device 100 according to the embodiment generates the information about the comparison of the similar user and the user when generating the information about the income or expense of the similar user. The user, thus, receives the information that allows the user to check at a glance the comparison of the settlement information and the trend of the assets between the user and the similar user. As a result, the user can more clearly obtain the information about the asset formation. The generation device 100 can provide the user with appropriate information about the user's future plan.
[0110] The acquisition unit 131 acquires the information about the health of the user. When the information about the health of the user acquired by the acquisition unit 131 and the information about the health of another user have similarity, as a certain condition, the identification unit 132 identifies the other user as the similar user.
[0111] The generation device 100 according to the embodiment uses the information about the health of the users, when determining similarity between the users. The generation device 100 , thus, can provide the user with appropriate information about the trend of medical expense, which contains many uncertain factors, out of the expense of the user in the future.
[0112] The acquisition unit 131 acquires the genetic test result of the user. When the genetic test result of the user acquired by the acquisition unit 131 and the genetic test result of another user have similarity, as a certain condition, the identification unit 132 identifies the other user as the similar user.
[0113] The generation device 100 according to the embodiment acquires the genetic test result as a specific example of the user information. The genetic test highly accurately detects characteristics relating to the health of the user, such as a constitution that easily develops diseases. The generation device 100 uses the genetic test result, thereby making it possible to determine similarity with extremely high accuracy. The generation device 100 , thus, can generate the comparison information about the comparison of the user and the similar user who is assumed to tend to be more similar to the user, thereby making it possible to more appropriately provide the user with guidance for the user's asset formation in the future.
[0114] The acquisition unit 131 acquires the genetic test result in which the degrees of the risks are indicated for the respective types of diseases. The identification unit 132 identifies another user as the similar user on the basis of the matching percentages of the types of diseases and the degrees of the risks corresponding to the types of diseases that are included in the genetic test results of the user and the other user. In other words, the identification unit 132 determines the similarity between the genetic test result of the user and the genetic test result of the other user on the basis of the matching percentages of the types of diseases and the degrees of the risks corresponding to the types of diseases that are included in the genetic test results.
[0115] The generation device 100 according to the embodiment determines the similar user on the basis of the types of diseases the analysis results of which are indicated and the degrees of the risks corresponding to the types of diseases in the genetic test result. As a result, the generation device 100 can accurately identify a similar user.
[0116] The acquisition unit 131 acquires, as the information about income or expense, the information about the amounts of expense of the user and the similar user. The generation unit 133 generates the comparison information that indicates a comparison of the trend of the amount of expense between the user and the similar user.
[0117] The generation device 100 according to the embodiment can generate, on the basis of the actual result of the similar user, the information capable of serving as certain guidance for the expense in the future, which is uncertain information for the user. As a result, the generation device 100 can provide the user with appropriate information about the user's future plan.
[0118] The acquisition unit 131 acquires the information about the amount of expense the breakdown of which is classified into certain items. The generation unit 133 generates the comparison information that indicates a comparison of the trend of the amount of expense for each certain item between the user and the similar user in the information about the amounts of expense of the user and the similar user.
[0119] As a result, the generation device 100 can provide the user with the more detailed information about the expense indicated for respective expense items. The generation device 100 , thus, can provide the user with useful information about the user's future plan.
[0120] The acquisition unit 131 acquires the information about income or expense of a plurality of similar users. The generation unit 133 generates the comparison information that indicates a comparison of the trend of income or expense of the user and the trend of income or expense statistically obtained from the multiple similar users.
[0121] The generation device 100 according to the embodiment generates the comparison information about the trend of income or expense from not only data of a specific person but also data statistically obtained from a plurality of samples. As a result, the generation device 100 can provide the user with appropriate comparison information suppressing inclinations.
[0122] The generation unit 133 generates, as the information included in the comparison information, a proposal for the user's actions on the basis of the comparison of the trend of income or expense between the user and the similar user.
[0123] The generation device 100 according to the embodiment can generate a proposal to the user in addition to the comparison information. As a result, the generation device 100 can provide the user with appropriate information about the user's asset formation.
[0124] The generation unit 133 generates, as the proposal for the user's actions, the proposal for the asset management performed by the user or the proposal for insurance the user should take out.
[0125] The generation device 100 according to the embodiment can provide the user with information useful for the user's future such as a proposal that can be used as a factor to determine whether the user should save money or make an investment, and a proposal for an insurance according to the types of diseases.
[0126] The acquisition unit 131 acquires the information about the attributes of the user. When the information about the attributes of the user acquired by the acquisition unit 131 and the information about the attributes of another user have similarity, as a certain condition, the identification unit 132 identifies the other user as the similar user.
[0127] The generation device 100 according to the embodiment may identify the similar user on the basis of not only the information about the health such as the genetic test result but also the information about the attributes of the user. As a result, the generation device 100 can increase the accuracy in identifying the similar user. As a result, the generation device 100 can provide the user with the comparison information about the comparison with the similar user assumed to be more similar to the user.
[0128] The identification unit 132 identifies the designated user who is a user matching a condition designated by the user out of similar users. The acquisition unit 131 acquires the information about income or expense of the designated user identified by the identification unit 132 and the information about income or expense of the user. The generation unit 133 generates the comparison information that indicates a comparison of the trend of the income or expense between the user and the designated user on the basis of the information acquired by the acquisition unit 131 .
[0129] The generation device 100 according to the embodiment may receive any condition from the user, and identify, as the designated user, a user who matches the condition. The generation device 100 , thus, can generate the comparison information that allows the user to refer to the information about income or expense of the other user who achieves the condition that the user aims for, for example. As a result, the generation device 100 enables the user to obtain the information more useful for the future plan.
[0130] The embodiments are described in detail with reference to the accompanying drawings as a way of example. The broad inventive principles can be implemented in other embodiments changed or modified on the basis of the knowledge of the persons skilled in the art besides the embodiments described herein.
[0131] The generation device 100 may be achieved by a plurality of server computers. The structure thereof can be changed flexibly. For example, some functions are achieved by calling external platforms using an application programming interface (API) or a network computing system.
[0132] The above-described embodiments have an advantage of providing the user with appropriate information about the user's future plan.
[0133] Although the inventive principles have been presented in the context of specific exemplary embodiments for a complete and clear disclosure, the appended claims need not be limited by those examples and should be construed as embodying all modifications and alternative constructions that may occur to one skilled in the art that fairly fall within the basic teaching herein set forth. | Network devices, methods, and programs identify similar subjects based on physiological characteristics to predict income and expense trends. The devices, methods, and programs receive a user profile from a user terminal via a network interface, the user profile identifying physiological characteristics of the user and an age of the user, and compare the physiological characteristics of the received user profile with physiological characteristics in stored subject profiles to identify a subject having similar physiological characteristics to the user. The devices, methods, and programs analyze expense information that is associated with the identified subject to determine a trend of the expense of the identified subject, and generate a proposal including a predicted future expense trend for the user based on the determined trend and the user's age. The devices, methods, and programs then transmit the generated proposal to the user terminal via the network interface. | 6 |
REFERENCE TO RELATED APPLICATION
This application is a corresponding non-provisional application and claims priority of provisional application Ser. No. 61/246,954, filed Sep. 29, 2009, the contents of which are incorporated herein by reference.
FIELD OF THE INVENTION
A vehicle restraint system is provided, which is comprised of an easily installable and transportable base having a deployable vehicle retention means contained therein. In particular, a rigid base over which vehicles may drive is provided, having a deployable vehicle retention means, such as a net or flexible panel, disposed in the base. In addition, deployable plates and tire puncturing devices are disposed in the base, to prevent movement of the vehicle.
BACKGROUND OF THE INVENTION
For many years, a small number of companies have sold vehicle crash barriers primarily designed to thwart deliberate vehicle-based attacks of buildings. These barriers are generally heavy steel structures imbedded in concrete or concrete structures in a road surface that physically obstruct the roadway. These heavy steel structure devices are designed so that a barrier device (usually a steel plate) can be raised or lowered to control the ability of a vehicle to pass through or over the barrier and, thus, gain access to the building being secured. These devices differ from the barriers commonly encountered in parking garages and other public venues, in that they have very high stopping power, for example, preventing a 15,000-pound explosive laden truck traveling at 50 mph from passing beyond the vehicle barrier.
Barriers come in numerous designs, but they can generally be categorized in three conventional types: plate, beam, and bollard. The plate barrier can be oriented to lay relatively flat on the surface of the roadway and be selectively actuated to be angled upwardly upon a perceived threat to form a wedge that restricts passage of a vehicle. The plate barrier is considered to be a permanently installed device as the plate is supported on a concrete encased frame that is buried into the surface of the roadway. A variation of the plate barrier has been introduced recently into the marketplace as a portable barrier. Another variation is to fasten the plate barrier to the roadway, such as with bolts. This barrier device is essentially a plate type barrier that is not imbedded in concrete, but instead can be moved to different locations to accommodate the need for temporary or changing security needs. Since the portable plate barrier is not imbedded in concrete, stopping power is relatively limited.
The beam barrier incorporates a vertically movable beam that is typically pivotally supported at one end of the beam by a steel support that is imbedded in concrete to provide a relatively immovable object and at the opposing end by a similar steel support at the opposing side of the roadway. The beam barrier serves as a movable gate that can be raised vertically (or swung horizontally) to allow vehicles to pass or lowered into engagement with the steel supports at either end of the beam to provide a substantial resistance to the passage of any vehicle. As with the conventional plate barrier, the beam barrier provides a permanent installation and relatively high stopping power. Some beam barriers use bands of nylon or similar material that are contained within the hollow beam and wrapped around the pivot structure for the beam to increase the resistance of the steel beam.
The bollards are typically permanently installed steel or concrete barriers that are typically not selectively movable, although vertical movement could be provided to permit the structure to rise into a passage restrictive position above the surface of the roadway, or be retracted into the ground to permit the passage of vehicles. Generally, bollards are a permanent structure that cannot be made portable without loss of substantial stopping power capabilities.
Conventional barriers generally have a disadvantage inherent in their designs in that each barrier design requires active mechanical movement of very heavy structures. Heavy steel plates (plate barriers) or heavy cylinders (bollard barriers) have to be raised against gravity in order to stop vehicles. Further, current vehicle barriers require approximately two seconds for emergency activation from an open position in which the vehicle can pass by the barrier to a deployed position in which a vehicle is prevented from passing by or over the barrier. Activation times for conventional beam barriers and sliding gate barriers are even longer, averaging about ten seconds for barriers that are one traffic lane wide and substantially longer for larger two lane barriers.
A vehicle traveling 50 mph covers 73 feet per second. Even if the barrier activation time is only two seconds, the facility needs to have almost 150 feet of standoff distance between the barrier close signal, such as from a guard or automated system, and the physical location of the barrier itself. Many facilities simply do not have the necessary space to accommodate this type of operation. This means that many existing barriers are seldom used in an “activate only when needed” mode. Thus, the barrier is always up and must be lowered for every authorized vehicle.
In addition, this constant raising and lowering of the vehicle barrier to allow authorized vehicle passage, over the course of its operating lifetime, requires a vehicle barrier to be cycled open and closed hundreds of thousands or even millions of times. Requiring constant movement from highly massive structures presents substantial challenges with respect to the maintenance and repair of vehicle barriers. Simply reducing the weight of the vehicle barrier is not a satisfactory resolution to these maintenance challenges as the stopping power of the vehicle barrier must be maintained.
With regards to the prevention of terrorist attack in ever-changing locations, such as roadblocks or military field installations, conventional barrier systems are generally impractical, as they require extensive installation procedures. In addition, such conventional barrier systems are often unable to stop a large terrorist vehicle, such as a 25,000-pound explosive laden trash truck, as has been employed in Lebanon, in a sufficient distance to prevent tremendous damage to the terrorist's intended target.
In view of the above mentioned disadvantages of conventional vehicle barrier systems, it is an object of the present invention to provide an improved vehicle restraint system that is highly portable, manufacturable at a lower cost than conventional systems, easily controllable, requires a low level of maintenance, yet is a highly effective barrier for security purposes.
SUMMARY OF THE INVENTION
In order to achieve the objects of the invention as described above, the present inventor earnestly endeavored to develop a vehicle restraint system capable of overcoming the disadvantages of the conventional vehicle barrier systems and vehicle restraint systems. Accordingly, a portable vehicle restraint system was developed, over which vehicles may pass freely until the system is actuated so as to deploy retention means therefrom, thereby securing the passing vehicle to the system and allowing the forward kinetic energy of the vehicle to be dissipated by sliding of the system relative to the ground.
In particular, the vehicle retention system of the present invention is comprised generally of a portable base, having a quickly deployable vehicle retention means movable disposed therein. To enable greater portability, the base may be provided in sections, which are then attached together on site. The vehicle retention means, such as netting, flexible polymer or fabric panels, etc., is attached to the base via quickly raisable retention means supports. These retention means supports may be a rigid or flexible column, spring, etc. In addition to retention means supports, which entrap the vehicle, lockable rollers are employed in the base, which may be unlocked and therefore allowed to rotate freely, preventing the vehicles tires from gripping a surface.
Moreover, exit prevention plates are movably disposed on the base, which prevent the vehicles tires from rolling forward or backward, thereby preventing exit of the vehicle from the system. And, as an optional embodiment, tire puncturing devices, such as deployable, tire piercing spikes, may be disposed on or embedded in the base and/or rollers, so as to allow an operator to deploy the spikes and puncture the tires of the intended vehicle.
As mentioned above, the system is highly portable, as the base may be loaded on a flatbed truck and simply laid on any desired surface. Thus, importantly, no extensive installation procedures are needed. Further, the system may be directly controlled via a wired or direct mechanical actuation means or, alternatively, a user may wirelessly control the deployment of the vehicle retention means via a wireless operator control unit (OCU) in wireless communication with the system. Therefore, an operator may stay at a safe distance from the system, while still maintaining a secure perimeter using the system of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective top view of the vehicle restraint system of the present invention, illustrating the orientation of the components of the system after deployment of the vehicle retention means and raising of the first and second exit prevention plates, wherein the vehicle retention means is flexible netting.
FIG. 2 is a side view of the vehicle restraint system of the present invention, illustrating a vehicle being restrained by the system.
FIG. 3 is a perspective top view of the vehicle restraint system of the present invention in a non-deployed state, i.e., wherein the vehicle retention means, exit prevention plates, and tire puncturing devices have not been raised relative to the base. In this state, vehicles may pass over the base without incident.
FIG. 4 is a perspective bottom view, partially cut away, of the vehicle restraint system of the present invention, illustrating the friction generating means that may be removably disposed on the bottom surface of the base, so as to increase friction between the base and surface upon which it rests, as well as the locking means utilized to lock the rollers in place.
FIG. 5 is a perspective top view of the vehicle restraint system of the present invention, in which the vehicle retention means is comprised of a polymeric material having perforations therethrough.
FIG. 6 is perspective top view of the vehicle restraint system of the present invention, in which the vehicle retention means is comprised of a flexible panel of polymeric, plastic or rubber material.
FIG. 7 is a perspective view of the operator control unit (OCU) by which an operator may wirelessly control the system of the present invention, via communication with the actuation control interface means.
FIG. 8 is a partial side view, cut away, of the vehicle restraint system of the present invention, illustrating the connectivity of the vehicle retention means with the first exit prevention plate, the connectivity of the first exit prevention plate with the ratcheted slide rails, the locking means operable to prevent rotation of the rollers, the tire puncturing devices integrated into the rollers, and the communication of the OCU (shown in FIG. 7 ) with the pressure sensor plate.
FIG. 9 is a top perspective view of the vehicle restraint system of the present invention, illustrating the multi-sectional embodiment of the base.
DETAILED DESCRIPTION OF THE INVENTION
As illustrated in FIG. 1 , the present invention provides a vehicle restraint system 1 comprised, generally of a base 3 , retention means supports 17 movably attached to the base at the bottom portion 19 of the supports 17 , and vehicle retention means 23 attached to the supports 17 and base 3 . In particular, a base 3 is provided, having a top surface 5 , a bottom surface 7 (as illustrated in FIG. 4 ), a first end 9 , a second end 11 , opposing sides 13 , and slots 15 formed therein. The base 3 is preferably simply laid upon the installation surface, such as a roadway, and requires no further mounting procedures. To increase portability, as illustrated in FIG. 9 , the base 3 may be formed in a plurality of sections 3 a , 3 b , 3 c , which are then attached together via conventional means on site. Further, to ease handling, handles 4 may be attached to or formed integrally therewith.
The retention means supports 17 , each having a bottom portion 19 and a top portion 21 , are disposed in or adjacent to each of the slots 15 , adjacent the second end 11 of the base 3 . The supports 17 are disposed in movable engagement with the base 3 , so as to allow the supports 17 to be retracted into the base 3 , below the top surface 5 thereof. For example, the supports 17 may be attached via a simple hinge mechanism, or alternatively be comprised of one or more springs stored within the base in a compressed manner which, upon actuation, are freed to spring upwards and project above the top surface 5 of the base 3 .
The retention means supports 17 may be comprised of a rigid material, so as to retain their integrity during vehicle impact, as illustrated in FIG. 2 . Alternatively, in a preferred embodiment, the supports 17 are comprised of one or more semi-rigid or flexible materials, such as plastics, polymers, rubbers, or a combination thereof, such that the retention means supports 17 may support the retention means 23 in an elevated manner, but flex when a vehicle impacts with the vehicle retention means 23 .
As illustrated in FIGS. 1 and 2 , the vehicle retention means 23 is comprised of one or more of a cable, mesh, or netting. Such cable, mesh, or netting is formed of a plastic or polymer, Kevlar, nylon, a metal, or a combination of same. In an alternative embodiment, as illustrated in FIGS. 5 and 6 , the vehicle retention means 23 may be formed of a perforated or solid panel of material, such as a flexible plastic or polymer sheet. In either event, preferably, the vehicle retention means 23 is formed of a material which is flexible in nature, but which is high breaking/tearing strength. Importantly, the material is to be chosen such that it can withstand the vehicle impact, while retaining the vehicle until the inertia thereof is dissipated by the friction between the base and the surface upon which is rests.
An actuation means (now shown) is provided in communication with the retention means supports 17 , such that the actuation means are capable of controlling movement of the retention means supports relative to the base. The actuation means may be one or more of a mechanical actuation device, an electromechanical device, a propellant-charged device, or a combination of same. Importantly, the actuation means is capable of quickly propelling the supports 17 upwards relative to the base, so as to retain the vehicle retention means 23 in an orientation capable of retaining a vehicle, as illustrated in FIG. 2 .
The actuation means may be actuated by a user via an actuation control interface means 47 , as illustrated in FIG. 1 . Such interface 47 may be a simple conventional mechanical interface, wherein a user switches a switch, pulls a cord, etc., so as to actuate the actuation means. Alternatively, the interface means 47 may be comprised of a simply logic device or computer processor in communication with the actuation means, and a wireless communication means, so as to allow a user to control the actuation means 25 remotely, via a wireless capable operator control unit 35 , as illustrated in FIG. 7 . Such remote wireless capability enables users of the system 1 to maintain a safe operating distance from the system 1 , providing a high degree of operational safety.
As illustrated in FIGS. 1 , 3 , 5 , 6 , 8 and 9 , in an preferred embodiment, a plurality of rollers 27 are disposed on or in the base, level with or slightly below the top surface 5 of the base 3 , and in rotatable connection therewith. Although there is no limitation as to where the rollers 27 are disposed, preferably, the rollers 27 are disposed adjacent the first end 9 and second end 11 of the base 3 , such that the tires of passing vehicles may be in alignment therewith. As illustrated in FIG. 8 , to prevent rolling of the rollers 27 during operation, locking means 29 may be disposed in communication with the rollers 27 .
By locking the rollers 27 , vehicle may pass unimpeded over the base 3 . However, when a threatening vehicle is detected, and the supports 17 raised, the locking means 29 may be unlocked into a rollable state either automatically through connection with the actuation means 25 , supports 17 , vehicle retention means 23 , or via a command received directly or indirectly from the OCU 35 . In this rollable state, vehicle tires spin freely without traction when resting upon the rollers, thereby impeding movement of the vehicle relative to the base 3 . As a further means of preventing a vehicle from moving relative to the base 3 , as illustrated in FIGS. 1 and 2 , a first exit prevention plate 31 is provided in hinged connection with the base 3 adjacent the first end 9 thereof. As illustrated in FIG. 3 , during normal operation wherein vehicle are permitted to freely pass over the system 1 , the first exit prevention plate 31 is retracted into a downward orientation, so as to be flush with the top surface 5 of the base 3 . However, as illustrated in FIG. 2 , when a threat is detected, the first exit prevention plate 31 may be raised relative to the top surface of the base 3 , thereby preventing or resisting exit of a vehicle 41 from the system 1 by obstruction of the tires thereof.
In a preferred embodiment, as illustrated FIG. 8 , the first exit prevention plate 31 may be in mechanical communication with the vehicle retention means 23 , such that when the retention means supports 17 are actuated, resulting in the raising of the vehicle retention means 23 relative to the base 3 , and the vehicle impacts with the retention means 23 , the vehicle retention means exert a forward pulling force on the first exit prevention plate 31 . This forward pulling force is translated via a pulley or geared system into a force operable to elevate the plate 31 into an obstructive position.
In a further preferred embodiment, as illustrated in FIGS. 2 and 8 , the first exit prevention plate 31 is in slidable communication with the base 3 via one or more ratcheted slide rails 43 . As illustrated in operation in FIG. 2 , by providing ratchets integral with, on or in communication with the sliding rails, the plate 31 is permitting to slide forward, from adjacent the first end 9 of the base towards the second end 11 , until the plate 31 rests against the tires of vehicle 41 . However, the one-way ratchets prevent the plate 31 from moving back towards the first end 9 , thereby preventing the vehicle from backing up and off of the base 3 .
Alternatively, the first exit prevention plate 31 may be disposed in communication with the actuation means, such that the actuation means is operable to raise the first exit prevention plate relative to the base. In such an alternative embodiment, the plate 31 is in communication with actuation means is operable to directly raise the plate 31 . However, a second actuation means, such as an electric, hydraulic or pneumatic motor, may be provided solely for the raising and lowering of the plate 31 . Such second actuation means is preferably in communication with the interface means 47 and/or the OCU 35 .
In addition to the first exit prevention plate 31 , as illustrated in FIGS. 1 and 3 , a second exit prevention plate 33 is provided in hinged connection with the base 3 adjacent the second end 11 thereof. Like the first exit prevention plate 31 , this second exit prevention plate 33 may be raised relative to the top surface of the base, thereby preventing or resisting exit of a vehicle from the system adjacent the second end 11 thereof. Further, like the first exit prevention plate 31 , the second exit prevention plate 33 may be in communication with the retention means supports, the actuation means, the interface means 47 , and/or the OCU 35 , etc., so as to raise same automatically or upon command.
In an optional embodiment, as illustrated in FIGS. 1 , 3 and 8 , a pressure sensor 45 may be disposed at or adjacent to the first end 9 of the base 3 , and in communication with the actuation means and/or the actuation control interface means 47 . In particular, the pressure sensor 45 may be disposed so as to sense contact of a vehicle with the base 3 . When sensing contact of a vehicle, the pressure sensor 45 may be configured to cause the supports 17 to be raised, the exit prevention plates 31 , 33 to be locked in a timed fashion, the rollers 27 to be unlocked, etc. Further, the pressure sensor may be directly activated/deactivated by a user, or remotely activated/deactivated via the OCU 35 , as illustrated in FIG. 8 .
As mentioned above, the system 1 may be simply laid upon the desired surface, such as roadway, checkpoint, building entrance, military base entrance, etc., and thus desirably requires no technical installation procedures. When a threatening vehicle is retained in the retention means 23 , as illustrated in FIG. 2 , the kinetic energy/inertia of the vehicle is dissipated by frictional interaction of the base 3 with the surface upon which is rests. Therefore, the base 3 is permitted to slide relative to the ground, so as to stop the vehicle 41 in a controlled manner. In order to increase the friction between the base 3 and the support surface, as illustrated in FIG. 4 , one or more friction generating structures 37 may be disposed on or integral with the bottom surface 7 of the base 3 . These friction generating structures 37 may be comprised of metal, polymer, rubber, or a combination thereof, but any material that is suitable to create friction between the surface upon which the system 1 shall be placed is acceptable. Preferably, the friction generating structures 37 are removably connected to the base, so as to allow replacement thereof when they are worn down through use, or are to be replaced with another device structure/material more suitable to the intended application.
As illustrated in FIG. 8 , in a preferred embodiment, a further vehicle impediment is provided, namely tire puncturing devices 55 . In particular, one or more tire-puncturing devices 55 may movably disposed on or within the base 3 and/or rollers 27 , and in communication with one or more of the actuation means, pressure sensor 45 , interface means 47 , and OCU 35 . These tire-puncturing devices, when deployed into an orientation protruding above the top surface 5 of the base 3 , are capable of puncturing a tire of a vehicle upon impact therewith. These tire-puncturing devices 55 may take many forms, but preferably are one or more of mechanically-deployed spikes, hydraulically deployed spikes, pneumatically-deployed spikes, or pyrotechnically deployed spikes.
Although specific embodiments of the present invention have been disclosed herein, those having ordinary skill in the art will understand that changes can be made to the specific embodiments without departing from the spirit and scope of the invention. The scope of the invention is not to be restricted, therefore, to the specific embodiments. Furthermore, it is intended that the appended claims cover any and all such applications, modifications, and embodiments within the scope of the present invention.
List of Drawing Elements:
1 : vehicle restraint system
3 : base
5 : base top surface
7 : base bottom surface
9 : base first end
11 : base second end
13 : base sides
15 : base slots
17 : retention means supports
19 : retention means support bottom portion
21 : retention means support top portion
23 : vehicle retention means
27 : rollers
29 : locking means
31 : first exit prevention plate
33 : second exit prevention plate
35 : operator control unit (OCU)
37 : friction generating structures
41 : vehicle
43 : ratcheted slide rails
45 : pressure sensor
47 : actuation control interface means
55 : tire puncturing devices | A vehicle restraint system is provided, comprised of an easily installable and transportable base having a deployable vehicle retention means contained therein. In particular, a rigid base over which vehicles may drive is provided, having a deployable vehicle retention means, such as a net or flexible panel, disposed in the base. In addition, lockable rollers, deployable plates and tire puncturing devices are disposed in the base, to prevent or resist movement of the vehicle relative to the base. The base is merely laid upon a surface, and requires no mounting thereto. Upon impact with a vehicle, the vehicle is retained on the base, and the forward motion/inertia of the vehicle is depleted via frictional engagement (sliding) of the base over the mounting surface, wherein the base and vehicle come to a controlled stop within a short distance. | 4 |
The present invention relates to a reciprocating piston machine, such as an air-conditioning compressor for motor vehicles, having a pivot ring and a guide sleeve which is disposed axially slidably on a drive shaft and has radially projecting bearing sleeves, the pivot ring and the guide sleeve being interconnected by pins which are supported, on the one hand, in bores of the pivot ring and, on the other hand, in bores of the bearing sleeves of the guide sleeve in such a way that they are rotatable relative to each other, but are axially “fixed” to each other.
BACKGROUND
Reciprocating piston machines of this kind are generally known. However, there are some disadvantages associated therewith. For example, the related-art reciprocating piston machines have a one-piece guide sleeve which is manufactured as a lathe-cut part and thus requires a considerable amount of machining. In addition, during operation, these guide sleeves produce traces of wear on the drive shaft of the machine.
Moreover, between the bearing sleeves of the guide sleeve and the pivot ring, the known machines have a spherical-segment shaped contact surface, which is expensive to manufacture, but is necessitated by the annular inner circumferential wall of the pivot ring, in order to allow an unhindered motion of the pivot ring relative to the bearing sleeves.
Also, in the known machines, the press-fit connection between the pins and the bearing sleeves is disadvantageously configured in the guide sleeve, which can lead to associated tolerance problems. Thus, narrow tolerances are required between the pins and the bearing sleeves due to the coaxiality of the fixed cylinder-pin location holes, and, on the other hand, substantial play is created by the rotatable cylinder-pin location holes in the pivot ring, which can lead to associated noise and vibration problems.
SUMMARY OF THE INVENTION
It is, therefore, an object of the present invention to devise a reciprocating piston machine which will overcome these disadvantages.
The present invention provides a reciprocating piston machine, such as an air-conditioning compressor for motor vehicles, having a pivot ring and a guide sleeve which is disposed axially slidably on a drive shaft and has radially projecting bearing sleeves, the pivot ring and the guide sleeve being interconnected by pins which are supported, on the one hand, in bores of the pivot ring and, on the other hand, in bores of the bearing sleeves of the guide sleeve in such a way that they are rotatable relative to each other, but are axially “fixed” to each other, the guide sleeve having a pot-shaped part, in particular of deep-drawn sheet metal, in which the radially projecting bearing sleeves are inserted in radial bores. Here the advantage is derived that virtually no or only relatively little machining is required to manufacture the guide sleeve. It is thus possible to reduce the cost of component parts.
A reciprocating piston machine is preferred in which the material of the pot-shaped part of the guide sleeve is hardened, while the material of the bearing sleeves is not hardened. Here the advantage is derived that the tolerances of the bearing sleeves to be positioned with axial precision are not affected by thermal deformation.
A reciprocating piston machine is also preferred in which the pot-shaped part of the guide sleeve and the bearing sleeve are joined together by connection means, in particular by soldering. This advantageously makes it possible for a hardened and an unhardened component part to be united in a simple and reliable manner to form one assembly.
The reciprocating piston machine according to the present invention that the pot-shaped part of the guide sleeve may have bushings made of friction-bearing material in the guidance portion on the drive shaft. This advantageously minimizes wear to the shaft, since the hardened guide sleeve no longer executes axial movements on the shaft surface. It is thus possible to reduce wear in the guidance portion of the guide sleeve and the drive shaft.
A reciprocating piston machine is also preferred in which a bushing, in particular the bushing on the side where a return spring is located between the guide sleeve and the shaft, is designed as a collared bushing. Here the advantage is derived that this bushing is able to function simultaneously as a limit stop for the return spring, and, consequently, that the return spring, as well, is able to move against an antifriction bearing material while being subject to relatively little wear.
In addition, a reciprocating piston machine is preferred in which the bushings are pressed in place into the pot-shaped part of the guide sleeve. Here the benefit is derived of a simple fastening method that does not require any additional connection means.
A reciprocating piston machine according to the present invention may have the feature that the contact surfaces between the pivot ring and the bearing sleeves of the guide sleeve are constituted of plane surfaces. In this case, one obtains the advantages of reduced wear and simpler parts manufacturing since the contact surface area is larger than that of bearing sleeve surfaces having a spherical segment shape within an annular inner circumferential wall of the pivot ring. The planar contacting instead of the linear contacting also leads to a more efficient damping of the vibrational response between the pivot ring and the bearing sleeves.
A reciprocating piston machine is preferred in which the pivot ring has two flattened wall regions on the annular inner peripheral wall, so that the inner peripheral wall of the pivot ring has the shape of an oval. Thus, the plane contact surface is formed on the pivot ring side.
A reciprocating piston machine is also preferred in which, in the unmachined state, the pivot ring is formed as a forged part. The advantage of such a fabrication process is that it economizes on material and does not require a substantial outlay for machining.
In addition, a reciprocating piston machine is preferred in which the bearing sleeves each have a plane axial (contact) surface.
Another reciprocating piston machine according to the present invention may have the feature that the pins are press-fitted into the bores of the pivot ring and are rotatably supported in the bearing sleeves of the guide sleeve. In this case, the play between the cylinder-pin location hole in the pivot ring and the pins themselves is advantageously avoided, so that the amount of noise and vibration generated may be reduced.
Also preferred is a reciprocating piston machine in which the pins are supported by a convex end portion in the bearing sleeves of the guide sleeve. The narrow tolerances necessitated by the coaxiality of the cylinder-pin location holes may advantageously be avoided, since contacting now takes place at the surface area of the convex end portions, making it possible to compensate for angular errors in the axial direction.
A reciprocating piston machine is also preferred in which the pins, on the longitudinal sides thereof, have two flattened surfaces which are configured in the pivot ring in such a way that the interference fit between the pins and the pivot ring bores does not deform the sliding-shoe bearing surfaces of the pivot ring. A machine is preferred in which the flattened surfaces of the pins are positioned in parallel to the sliding-shoe bearing surfaces of the pivot ring. This makes it possible to advantageously prevent any warping of the sliding-shoe bearing surfaces when the pins are pressed in place.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is described in the following with reference to the figures, which show:
FIG. 1 a pivot ring assembly including the drive shaft and the guide sleeve in accordance with the related art;
FIGS. 2 a and 2 b the contact surface between the bearing sleeves and the pivot ring in accordance with the related art;
FIGS. 3 a and 3 b the contact surfaces between the bearing sleeves and the pivot ring in accordance with the present invention;
FIGS. 4 a and 4 b a guide sleeve according to the present invention;
FIG. 5 a pin according to the present invention for press-fitting into the pivot ring;
FIG. 6 the interference fit between the pivot ring and a pin according to the present invention.
DETAILED DESCRIPTION
FIG. 1 illustrates the assembly of a pivot ring machine according to the related art including drive shaft 5 , guide sleeve 9 and pivot ring 1 . In response to rotation of drive shaft 5 , pivot ring 1 is set into rotation by a driving pin 3 which is fixed to drive shaft 5 . In addition, pivot ring 1 has two bores 7 for receiving pins about which the pivot ring is able to execute a rotary motion. Also accommodated on shaft 5 is guide sleeve 9 which has two radially projecting bearing sleeves 11 for receiving the pins. Guide sleeve 9 is slidable on shaft 5 . For this purpose, guide sleeve 9 has a recess 13 , which allows guide sleeve 9 to be supported axially movably on shaft 5 relative to driving pin 3 . Driving pin 3 engages by its upper end in a bore 15 of the pivot ring and allows the pivot ring to execute a pivoting movement to pivot about this upper end of driving pin 3 . Piston shoes for the pistons of the reciprocating piston machine which slide on surfaces 17 and 19 of the pivot ring. In this context, the pins supported inside of pivot ring bores 7 and bearing sleeves 11 form a swivel axis for pivot ring 1 that is displaceable in the axial direction of machine shaft 5 . The function of such a pivot ring drive for reciprocating piston machines is generally known and described in the related art, so that there is no need for further clarification here.
In a plan view, FIG. 2 shows the contact surfaces between pivot ring 1 and bearing sleeves 11 in accordance with the related art. The same components are denoted here by the same reference numerals as in FIG. 1 . In FIG. 2 b , guide sleeve 9 and pivot ring 1 are shown in a plan and part-sectional view. It is discernible, in particular in enlarged representations Z of FIG. 2 a and X of FIG. 2 b , that contact surfaces 21 of bearing sleeves 11 contacting pivot ring 1 must have an approximately spherical segment shape, in order not to hinder pivot ring 1 , whose inner circumferential surface is circular, in its rotational and slewing motion and to sufficiently support the same. As may be inferred from enlarged representations Z and X, the contact made between the inner circumference of pivot ring 1 and bearing sleeves 11 is a linear contacting represented by line 20 passing orthogonally through point 22 . It is also expensive and complicated to manufacture the spherical segment-shaped end faces of bearing sleeves 11 . Therefore, FIG. 3 shows the inventive modification to the contact surfaces between improved pivot ring 23 and improved bearing sleeves 25 . Bearing sleeves 25 now have a plane surface section 27 , while pivot ring 23 likewise has a plane inner peripheral surface at contact surface 27 thereof, inner periphery 29 of improved pivot ring 23 consequently having the shape of an oval. Thus, between pivot ring 23 and bearing sleeves 25 , a planar contacting is provided which, due to the larger area of contact, produces less wear than the linear contacting known from the related art ( FIG. 2 ) and renders possible an improved damping in response to vibrations of the pivot mechanism. Moreover, the contact surfaces of bearing sleeves 25 are simpler and less expensive to manufacture. Thus, the contact surfaces between pivot ring 23 and bearing sleeves 25 are planar in both dimensions, as illustrated by enlarged representations Z and X in FIGS. 3 a and 3 b.
Two embodiments of the guide sleeve according to the present invention are shown in FIG. 4 . The guide sleeve has a pot-shaped part 31 , which assumes the function of part 9 of FIG. 1 , but in this inventive case, is made of deep-drawn sheet metal, for example, and is thus able to be mass-produced at a lower cost. Guide sleeve part 31 is bearing-supported in bores 33 and 35 on shaft 5 of FIG. 1 and, via these bearings, is slidable on the shaft. A lateral bore 37 in the circumferential wall of guide sleeve part 31 corresponds to bore 13 of guide sleeve 9 of FIG. 1 and thus creates the clearance space required for driving pin 3 of FIG. 1 that extends from shaft 5 into bore 15 of pivot ring 1 and is configured not to hinder the axial mobility of guide sleeve 31 . Accommodated in two radial bores 39 of guide sleeve part 31 are two bearing sleeves 41 , which provide guidance for the pins that form a swivel axis for pivot ring 1 . While guide sleeve part 31 may be made of hardened, deep-drawn sheet steel in order to increase strength and reduce wear, bearing sleeves 41 may remain in the unhardened state and are, therefore, not subject to the inherent deformation risks of a thermal treatment process. Bearing sleeves 41 may be fastened in guide sleeve part 31 using connection means, such as soldering.
Also introduced into guide sleeve part 31 in FIG. 4 b are two bushings made of a friction-bearing material. Thus, for example, bore 33 has a collared bushing 43 inserted therein, which, on the one hand, acts as a friction bearing against shaft 5 and, on the other hand, together with collar 47 , forms a limit stop for a return spring, which, when the compressor is at a standstill, presses the pivot ring into a starting position. Inserted into bore 35 is a second friction-bearing bushing 45 . Wear to the shaft, as encountered in related art methods, is avoided through the use of friction-bearing bushings 43 and 45 . Also discernible in FIGS. 4 a and 4 b is plane contact surface 49 according to the present invention, as already depicted in FIG. 3 as contact surface 27 . Friction-bearing bushings 43 and 45 may be fastened using joining techniques, such as press-fitting of the same in guide sleeve part 31 .
In a perspective view, FIG. 5 shows one of the two pins 51 , which, together with guide sleeve 9 , form the swivel axis of pivot ring 1 in the pivot ring mechanism. In this context, pins 51 are press-fitted in the pivot ring, into bores 7 of FIG. 3 , and supported by their spherical segment-shaped end portions 53 in bearing sleeves 25 in FIG. 3 , respectively 41 in FIG. 4 . Cylindrical section 55 of pins 51 that is press-fittable in pivot ring 23 into bores 7 thereof has two flat portions 57 , which, in FIG. 6 , are positioned in pivot ring 23 to extend in parallel to sliding surfaces 59 of pivot ring 23 . Sliding shoes, which are suitably supported in the axially reciprocating pistons of the reciprocating piston machine, glide on sliding surfaces 59 of the pivot ring. In FIG. 6 , it is discernible that the interference fit between pins 51 and cylindrical end section 55 thereof and pivot ring 23 is only effected at lateral surfaces 61 and, thus, that that area of bore 7 in pivot ring 23 which faces sliding surfaces 59 is not deformed by the pressing in place of pins 51 . Thus, in comparison to the related art, pins 51 , as shown in FIGS. 5 and 6 , are designed in such a way that the interference fit is shifted from guide sleeve 9 into pivot ring 23 , and a convex contact region is formed between bearing sleeves 25 of guide sleeves 9 and cylindrical pins 51 . Noted advantages are a broadening of tolerances with respect to the pin guidance in bearing sleeves 25 and, at the same time, a reduced play in the entire assembly between guide sleeve 9 , cylindrical pins 51 and pivot ring 23 . These measures result in reduced costs, a simplified assembly and, at the same time, in an improved noise and vibrational response of the pivot ring drive. Cylindrical pins 51 may also be optionally produced using deep-drawn blanks. To facilitate insertion of cylinder pin 51 during the press-fit operation, also discernible in FIG. 5 in end region 63 is a grooved end section having a slot 65 for positioning pin 51 during assembly to the desired position, as shown in FIG. 6 . A constricted region 67 between part 53 and cylindrical part 55 provides ease of mobility in the transitional region between bearing sleeves 25 and, respectively 41 , and pivot ring 23 in FIG. 3 .
LIST OF REFERENCE NUMERALS
1 pivot ring
3 driving pin
5 drive shaft
7 bore in the pivot ring
9 guide sleeve
11 bearing sleeve
13 recess for driving pin
15 bore of the pivot ring for driving pin
17 sliding shoe surface of the pivot ring
19 sliding shoe surface of the pivot ring
20 line of contact between the contact surfaces of the pivot ring and bearing sleeve
21 spherical-segment shaped contact surface between the bearing sleeve and the pivot ring
22 pass-through point of the linear contacting
23 improved pivot ring
25 improved bearing sleeve
27 plane surface section of the bearing sleeve/contact surface to the pivot ring
29 inner periphery of the improved pivot ring
31 pot-shaped part of the guide sleeve
33 bearing bore for the shaft
35 bearing bore for the shaft
37 bore for the driving pin
39 radial bore for the bearing sleeves
41 improved bearing sleeves
43 collared-bushing friction bearing
45 friction-bearing bushing
47 collar of the collared bushing
49 plane contact surface of the bearing sleeve
51 cylindrical pins
53 spherical segment-shaped end part of the cylindrical pins
55 cylindrical section of the cylindrical pins
57 flat portions of the cylindrical pins
59 sliding surfaces of the pivot ring for piston shoes
61 lateral surface of pivot ring bore 7
63 end region of cylindrical pins 51
65 positioning slot of the cylindrical pins
67 constricted region of the cylindrical pins | A reciprocating piston machine, such as an air-conditioning compressor for motor vehicles, including a pivot ring and a guide sleeve that is provided axially slidably on a drive shaft and is provided with radially projecting bearing sleeves. The pivot ring and the guide sleeve are interconnected by pins so as to be rotatable relative to each other while being axially joined in a fixed manner, the pins being mounted in bores of the pivot ring and in bores of the bearing sleeves of the guide sleeve. | 5 |
This application is a continuation-in-part of U.S. Ser. No. 412,930 filed Nov. 5, 1973, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to negative electron beam resists for photomask fabrication and for semiconductor device fabrication.
2. Description of the Prior Art
A resist is an adhering layer of a material with patterned openings on a support which is used as a mask for etching, either partially or completely through, the support exposed by the openings in the resist. The use of light as the irradiator or energy source for fabricating photoresists in the semiconductor art has been common for many years. The photoresist method of semiconductor manufacture was adequate until the advent of small geometry high frequency devices and integrated circuits requiring the formation of patterns with line widths in the neighborhood of 1 micron. Although 1 micron line openings, or resolution, can be obtained from photoresists in the laboratory, such line widths are not reproducible due to diffraction problems, with the practical limit of production produced openings being in the neighborhood of 5 to 6 microns in width.
The step from the use of light to electrons to form resists was a logical one. Theoretically, since the size of an electron is only 1/1000th the size of a quantum of light, an electron beam should produce openings with line widths 1/1000th the size of openings obtained with photoresists. However, due to electron bounce-back or back scatter from the surface supporting the resist, such small width openings are not obtainable, only 1000 A being the practical lower limit in size. Election beam microdefinition technology differs quite drastically from photoresist technology in that in photoresist technology, designers make large patterns out of a sheet of red plastic with the definition of the different elements of the pattern resulting from the cutting out of certain areas. The large plastic sheet is then photographed and reduced a number of times to bring the pattern down to the correct size so that the pattern can be transferred by light to the photoresist. In production, this procedure usually takes from one to two weeks from the design stage to the patterned resist.
In the case of electron beam technology, an electron beam is scanned across the resist itself to form the desired pattern. The electron beam is controlled by a computer which has been fed the coordinates of the pattern as previously determined by a designer. Thus, the use of the electron beam has eliminated all the time lost in preparing the reduction photography required to from a patterned photoresist. However, due to the pattern in the electron beam resist resulting from the scan of a very narrow electron beam, the reaction time of the resist to the electron beam is the time drawback to the production use of electron beam resists.
Obviously, then, in addition to the characteristics required of a good photoresist, such as: good adhesion to many materials, good etch resistance to conventional etches, solubility in desired solvents, and thermostability, an electron resist must react to the electron beam irradiation fast enough to allow a reasonable scan time of the electron beam. In order to bring electron beam technology into production status, resists composed of thin polymer films that are capable of retaining an image of one micron or less at very high scanning speeds of the electron beam are required.
A number of approaches have been taken in the past to develop practical electron beam resists. The first approach and one that proved to be the least successful was the use of convention photoresists, which are also polymers. Although capable of being exposed at relative high scan rates, such exhibit line widths, i.e., resolutions, greater than one micron in width.
The most widely used electron beam resist today is polymethyl methacrylate (PMMA), a positive resist. PMMA is characterized by excellent resolution and line width characteristics and by good processability. However, PMMA requires a relatively slow exposure rate, of approximately 5 × 10 -5 coulombs/cm 2 , and has the inability to withstand strong oxidizing acids and base etches. A good electron beam resist must react at least ten times faster than PMMA and must withstand strong oxidizing acids and base etches.
A random copolymer of styrene-butadiene has also been proposed. See U.S. Pat. No. 3,794,510.
Therefore, an object of this invention is to provide a method of forming a negative electron beam resist which can be scanned by a beam of electrons at a rate greater than 5 × 10 -5 coulombs/cm 2 .
Another object of this invention is to provide a method of forming a negative electron beam resist that can withstand strong oxidizing acids and base etches.
Another object of this invention is to provide a method of forming a negative electron beam resist having good adhesion to many support materials.
Another object of this invention is to provide a method of forming an improved styrene-diene negative electron beam resist.
Another object of this invention is to provide a method of forming a negative electron beam resist that is thermostable.
A further object of this invention is to provide a negative electron beam resist that can withstand strong oxidizing acids and base etches; has good adhesion to many support materials; and is soluble in many common solvents.
SUMMARY OF THE INVENTION
Briefly, the invention involves the use of a styrenediene block copolymer as a negative electron beam resist material (a negative resist being defined as one that cross links upon being irradiated thus becoming insoluble in many solvents while a positive resist is defined as one that is insoluble until irradiated when it degrades and becomes soluble). The copolymer is applied as a liquid to a support and allowed to dry to a thin film. An electron beam is caused to sweep or scan across the surface of the copolymer in the desired pattern to form a negative resist by imparting sufficient energy to break the double bonds of the diene groups. Cross linkage occurs in the diene groups and the styrene groups, thereby making the irradiated portion insoluble in certain solvents. After the electron beam scanning is completed, the resist is subjected to a solvent of the ketone class and the non-irradiated portion of the resist is removed, thereby leaving openings in the resist that correspond to the desired pattern.
Block copolymers are copolymers composed of two or more monomers that are not arranged randomly in the polymer. Block copolymers are like several minipolymers tied together. Styrene-butadiene block copolymers are blocks of styrene polymer tied to blocks of butadiene polymers. This arrangement allows this rubber to behave as a thermoplastic resin. For purposes of the present disclosure a block copolymer is defined as having at least three monomer units in each homopolymer block. The unique properties obtained by block copolymerization versus random copolymerization offer, as it turns out, several distinct advantages for the copolymer when used as an electron-beam resist.
The novel features believed characteristic of this invention are set forth in the appended claims. The invention itself, however, as well as other objects and advantages thereof, may best be understood by reference to the following detailed description.
DETAILED DESCRIPTION OF THE INVENTION
Dienes are double olefin groups and furnish the double bond reaction sites necessary for the cross linkage that results upon the copolymer being irradiated with an electron beam. The diene can be a butadiene ##STR1## the specific example described herein, or can be any diene, such as styrene diene, where some or all of the hydrogen atoms of the butadiene are replaced by other atoms. Any diene with the number of carbon atoms between olefin groups between 0 and 3 forms an effective negative electron beam resist with styrene. The diene homopolymer could be used as the electron beam resist material itself since the requirement of the double bond reaction sites would be met. However, the dienes by themselves are very rubbery and are too flexible to be used for a resist because the material will not retain its shape through the required processing steps.
However, this inventor has discovered that by block copolymerizing diene and styrene ##STR2## an electron beam active monomer, an ideal electron beam resist material is obtained. Styrene by itself has a reaction time to electron beam irradiation which is 100 times slower than the styrene-butadiene block copolymer. Upon irradiation, added energy is introduced and the styrene is in an excited state. However, the benzene ring is extremely stable and will react only with difficulty.
In the pure styrene polymer, a styrene chain finds only other styrene chains to cross link with. However, when the copolymer of diene and styrene is irradiated with an electron beam the excited styrene molecules (the electron beam activated species) cross link with the diene molecules quite readily. Styrene diene block copolymers can be scanned with an electron beam at speeds much faster than PMMA. After cross linkage occurs, the styrene diene copolymer is insoluble in certain solvents, resulting in an excellent electron beam resist. A representative block copolymer covered by this invention is styrene-butadiene block copolymer.
A styrene-butadiene block copolymer can be purchased from Phillips 66 under the tradename Solprene with an average molecular weight ranging from 100,000 to 200,000. The reaction rate of the styrene diene copolymer is directly proportional to the molecular weight. A copolymer with a molecular weight of 120,000 has a reaction time one-half that of a copolymer having a molecular weight of 60,000. However, as the molecular weight of a copolymer is increased by increasing the chain linkage, the solubility of the copolymer decreases. The practical average molecular weight of styrene-dienes range from 10,000 to 500,000 with the reaction rate changing by a factor of 50 through that range.
Suitable block copolymers for use in the invention contain 15-85% by weight styrene, and preferably 25-40% by weight styrene.
The Solprene is purchased from Phillips 66 as a solid and is mixed with an aromatic solvent, such as xylene or toluene to form a 2% to 5% solution by weight, for example. The solution percentage is determined by the requirement of having as thin a film as possible to decrease the difficulties caused by the bounce-back of the electrons. The solid Solprene goes into solution very easily at room temperature with a minimum amount of stirring. However, as a precaution to remove any impurities, such as dust from the solution, the solution is filtered prior to being placed on the support.
While a method of forming a patterned electron beam resist will be described in order to form a mask on a chromium plate or support for subsequent use as a photoetch mask to etch semiconductor wafers, the method of this invention is also used for direct application of the resist to the semiconductor wafer with the chrome etch being replaced by a semiconductor etch.
The block copolymer solution is applied to the support and the chrome support with the covering copolymer is spun at a speed of approximately 3000 rpm, for example, in order to form a uniform layer of copolymer. The chrome support with the covering layer of copolymer is then baked in a nitrogen atmosphere at any temperature from room temperature to 75° C, with an optimum temperature of 45° C, for approximately 15 minutes to remove all of the solvent, leaving a dried thin film of from 1000 A to 6000 A in thickness.
The chrome substrate with the baked on copolymer is then placed in an electron irradiator and the electron beam allowed to scan the surface of the copolymer in a predetermined pattern as controlled by a computer. The styrene-butadiene, being a negative resist, will cross link in the portion of the copolymer subjected to the electron beam, which portion will become insoluble and will not be affected by the subsequent development with a solvent such as cyclohexanone. The copolymer is developed by spraying or dipping the copolymer covered chrome support in a cyclohexanone solution for approximately 30 seconds which will be a sufficient length of time to dissolve and remove the unirradiated portion of the copolymer leaving the desired pattern of openings in the resist. The cyclohexanone is removed by a rinse in isopropyl alcohol for 15 seconds, for example. To harden the cross linked copolymer pattern remaining on the chrome support, the copolymer covered support is baked at 120° C in air for 30 minutes which completes the copolymer resist, the final bake promoting further cross linkage.
Although not a part of this invention, the copolymer coated chrome support, with its completed resist, is finally subjected to a conventional chrome etch for a period of time sufficient to remove the chrome exposed by the openings in the patterned electron beam resist. Finally, the resist is removed by dipping the copolymer coated chrome support in diethylphthalate at 170° C for 60 minutes. The patterned chrome support is now ready to be used to form an image on a photoresist placed on a semiconductor wafer. The specific temperature and times previously furnished are not critical to the invention. Any pattern defining system can replace the use of a computer.
Although in the example given, the electron beam resist was used only to form a metal mask to be used for subsequent photoengraving, the same process steps are used when the electron beam resist is applied to a semiconductor wafer.
As a further example, two commercial styrene-butadiene copolymers were compared. They were both from the same manufacturer. The random copolymer (Solprene 1204) had a molecular weight of 359 × 10 3 and a styrene content of 26.6 percent. The block copolymer (Solprene 406) has a molecular weight of 83 × 10 3 and a styrene content of 25.6 percent. The random copolymer was twice as sensitive as the block copolymer, but based on the molecular weight differences (linear increase of sensitivity with molecular weight) the random copolymer should have been three times as fast. A block copolymer with half the molecular weight of the random copolymer gave the same speed. Thus showing the block polymers are basically more sensitive. In addition, the block-copolymer can retain 0.7 μ line and space separation over a 50% broader dose range than the random copolymer. This demonstrates a higher contrast for the block copolymer and manifests itself as better edges and less stringent process conditions. All tests were run under the same coating, exposure, and development conditions.
Because of the fast scanning rates that can be used due to the reaction rate of the styrene-butadiene block copolymer being forty times faster than PMMA, styrene-butadiene block copolymer electron beam resists compete quite favorably in cost with conventional photoresists. Obviously, since the chrome mask will subsequently be used for photoengraving of the semiconductor wafer the electron beam technology is not used to form very narrow width lines in the resist, although line widths of from 0.3 to 0.5 microns have been obtained with styrene-butadiene block copolymer resists.
The styrene-butadiene block copolymer resist has excellent adhesion to chrome, gold, silicon and silicon dioxide; excellent resistance to chrome, gold, silicon and silicon dioxide etches; is very soluble in the solvents given and has excellent thermostability. Any high energy irradiation, such as x-rays and alpha particles can be used to furnish the necessary energy to cause the cross linkage required.
Although, a specific embodiment of the invention has been described in detail, it is to be understood that various changes, substitutions and alterations can be made therein without departing from the spirit and the scope of the invention as defined by the appended claims. | Disclosed is a method of forming patterned electron beam resists from styrene-diene block copolymers and the resists formed thereby. A thin film of a styrene-diene block copolymer is applied to a support and is subjected to an electron beam scan. An electron beam irradiates a portion of the copolymer film according to a programmed pattern; the copolymer cross links where irradiated, thus causing the irradiated portion of the copolymer to become insoluble in a solvent. The balance of the copolymer remains soluble in the solvent, dissolves and is removed, resulting in the desired pattern of openings. | 6 |
BACKGROUND
[0001] 1. Technical Field
[0002] The present disclosure relates to improving the launch performance of a vehicle.
[0003] 2. Background Art
[0004] It is known that a vehicle with a smaller displacement engine exhibits greater fuel efficiency than the same vehicle with a larger displacement engine. However, the ability of the vehicle to accelerate is impaired by the smaller displacement inducting less air into the engine to thereby produce power. It is also known that by pressure charging the engine, performance of the smaller displacement engine, at many operating conditions, can be similar to that of the larger displacement engine. More commonly, pressure charging is provided by a turbocharger in which exhaust enthalpy, which would otherwise be exhausted, is recovered as work in an exhaust turbine. The exhaust turbine has a common shaft with a compressor in the intake. The work extracted in the exhaust turbine is used to compress the intake gases to improve power density of the engine. Turbo lag is a known disadvantage of a turbocharged engine. That is, at low engine speed, such as at vehicle launch, little mass is flowing through the engine so that the exhaust turbine spins at a low speed. The engine/turbo system spins up when demanded by the vehicle operator by depressing the accelerator pedal, however with an undesirable delay. If turbo lag could be addressed, fuel efficiency of vehicles could be significantly improved by downsizing and turbocharging without the performance disadvantage at certain low-speed operating conditions. Any improvement in launch performance may also be applied to naturally-aspirated engines.
SUMMARY
[0005] To address launch performance, a vehicle is disclosed which has a brake system, including: brakes coupled to vehicle wheels, hydraulic lines coupled to the brakes, an actuation force on the brakes is related to pressure in the hydraulic lines, and a pressure sensor coupled to the hydraulic lines. The vehicle also includes an internal combustion engine, a turbocharger coupled to the engine, a throttle valve disposed in an intake of the engine, a vehicle speed sensor, and an electronic control unit (ECU) electronically coupled to the engine, the throttle valve, the vehicle speed sensor, and the pressure sensor. An incipient launch of the vehicle is determined when a vehicle speed sensor indicates that the vehicle is stopped and a signature from the signal from the pressure sensor indicates that brake pedal release is imminent. In response, the ECU commands the throttle valve toward a more open position. In one embodiment, brake pedal release is indicated when the pressure sensor indicates that pressure in the hydraulic lines decreases below a threshold pressure. Alternatively, brake pedal release is indicated based on rate of decay of pressure in the hydraulic lines.
[0006] The vehicle may include a bypass duct coupled upstream and downstream of an exhaust turbine of the turbocharger and a wastegate valve disposed in the bypass duct. Upon determination of incipient launch of the vehicle, the ECU further commands the wastegate to a substantially completely closed position.
[0007] In gasoline engine applications, spark plugs are disposed in engine cylinders and electronically coupled to the ECU. The ECU further commands a retarded spark timing to the spark plugs based upon determination of incipient launch of the vehicle.
[0008] In some alternatives, the ECU discontinues the commanding the throttle valve to the more open position upon elapse of a predetermined interval. That is, the launch anticipation is aborted when, for example, the operator of the vehicle fails to command a launch within a certain period of time, e.g., when the operator is slowing moving in a parking lot or other slow-speed maneuver.
[0009] In some embodiments, the ECU further commands hydraulic pressure to be applied to at least one brake coupled to a vehicle wheel upon determination of incipient launch of the vehicle to avoid an unintended launch feel.
[0010] Also disclosed is a method to control a vehicle in which an incipient launch is detected, the incipient launch being when both the vehicle is stopped and an indication that a brake pedal coupled to the vehicle is being released is detected. In response, an increase in engine torque in commanded.
[0011] The indication that the brake pedal is being release is based on a signal from a sensor with the sensor being one of: a brake on-off switch coupled to the brake pedal, a brake pedal position sensor coupled to the brake pedal, and a pressure sensor coupled to hydraulic lines of the brake system of the vehicle.
[0012] In one embodiment, spark timing is retarded substantially simultaneously with the throttle valve command to the more open position.
[0013] A method is disclosed in which an incipient launch is determined based on the vehicle being stopped and an indication that release of a brake pedal coupled to the vehicle is imminent. In response, an increase in exhaust enthalpy provided to an exhaust turbine of the turbocharger is commanded. The increase in enthalpy may be provided by: opening a throttle valve coupled to an intake of the engine, retarding spark timing commanded to spark plugs coupled to cylinders of the engine, adjusting timing of a variable camshaft timing (VCT) system coupled to the engine and closing completely a wastegate valve provided in a bypass duct coupled to the exhaust turbine.
[0014] In some embodiments, brakes coupled to wheels of the vehicle are actuated substantially simultaneously with the commanding an increase in exhaust enthalpy. The brakes may be actuated to cause the vehicle to remain stopped. Or, the brakes are actuated so as to allow the vehicle to creep. If the brake pedal is reapplied, actions to increase exhaust enthalpy are discontinued. If the accelerator pedal is depressed, then the normal engine operating strategy is employed.
[0015] In one embodiment, the actions are applied for forward launches only. The engine is coupled to a transmission having a plurality of forward gears and a reverse gear wherein the commanding an increase in exhaust enthalpy is further based on the transmission being in a forward gear.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 is a schematic of a vehicle;
[0017] FIG. 2 is a flowchart of an algorithm for launching vehicles according to embodiments of the disclosure;
[0018] FIG. 3 is a graph of pressure in the hydraulic lines as a function of time during a brake release;
[0019] FIG. 4 is a graph of brake pedal position as a function of time during a brake release;
[0020] FIG. 5 is an adaptive routine according to an embodiment of the disclosure; and
[0021] FIGS. 6 and 7 are plots of example applications of anticipating vehicle launch according to multiple embodiments of the disclosure.
DETAILED DESCRIPTION
[0022] As those of ordinary skill in the art will understand, various features of the embodiments illustrated and described with reference to any one of the Figures may be combined with features illustrated in one or more other Figures to produce alternative embodiments that are not explicitly illustrated or described. The combinations of features illustrated provide representative embodiments for typical applications. However, various combinations and modifications of the features consistent with the teachings of the present disclosure may be desired for particular applications or implementations. Those of ordinary skill in the art may recognize similar applications or implementations consistent with the present disclosure, e.g., ones in which components are arranged in a slightly different order than shown in the embodiments in the Figures. Those of ordinary skill in the art will recognize that the teachings of the present disclosure may be applied to other applications or implementations.
[0023] In FIG. 1 , a vehicle 10 is illustrated that is used to describe several types of vehicle configurations. Not all components shown in FIG. 1 are included in each variation. For example, as described below, the transmission may be an automatic transmission or a conventional manual transmission, the former of which normally includes no clutch pedal, the latter of which does include a clutch pedal. In even other configurations, the transmission is a manual transmission with automatic shifting capability.
[0024] Vehicle 10 includes an internal combustion engine 12 with a turbocharger 14 . Turbocharger 14 has an exhaust turbine 20 disposed in an exhaust duct 22 of engine 10 ; a compressor 16 disposed in an intake duct 18 of engine 10 ; and a shaft 24 coupling turbine 20 and compressor 16 . In intake duct 18 is a throttle valve 24 that is actuated under command of an electronic control unit (ECU) 30 to control flow of air into engine 10 . A bypass duct 26 to turbine 20 has a valve 28 disposed therein that is actuated under control of ECU 30 . Bypass duct 26 and valve 28 are commonly called a wastegate.
[0025] In the present disclosure, a single ECU 30 is shown in FIG. 1 . However, this configuration is shown for convenience. It is understood that the functions described in reference to ECU 30 may be performed across multiple ECUs.
[0026] Vehicle 10 includes operator controls, such as an accelerator pedal 32 and a brake pedal 34 , which the operator of the vehicle uses to indicate a desire for forward acceleration. Accelerator pedal 32 is coupled to a sensor 36 that communicates accelerator pedal 32 position to ECU 30 . In conventional braking systems, brake pedal 34 is coupled to a brake booster 35 that connects to hydraulic lines and actuates calipers to clamp down on discs at the wheels 38 . The operator actuates brake pedal 34 and such actuation is assisted by brake booster 35 to thereby actuate brakes 40 coupled to wheels 38 are actuated. In conventional braking systems, brakes 40 may be actuated independently of operator activity such as for roll stability control or electronic stability control. ECU 30 may command actuation of one or more brakes 40 to improve vehicle stability in response to destabilizing maneuvers or to prevent roll over of the vehicle. The ECU 30 can command a brake to act upon one of the vehicle wheels independent of the operator depressing a brake pedal. Some vehicles are equipped with electric brakes in which brake pedal 34 has a brake sensor 46 to detect operator input to brake pedal 34 . The output of brake sensor 46 is provided to ECU 30 ; and ECU 30 commands a pressure to apply to calipers of brakes 40 based on a signal from sensor 46 . A pressure sensor 48 in brake booster 35 indicates the pressure acting upon brakes 40 . Pressure sensor 48 is coupled to ECU 30 . In such a brake-by-wire configuration, ECU 30 can also command the brakes to be applied to one or more wheels independent of an operator commanding braking by depressing the brake pedal.
[0027] Engine 10 is coupled to a transmission 52 . In one embodiment, transmission 52 is an automatic transmission with a torque converter. The torque converter causes the vehicle to creep when transmission 52 is in gear and neither accelerator pedal 32 or brake pedal are depressed. In another embodiment, transmission 52 is a conventional manual transmission with a clutch (not individually shown in FIG. 1 ) coupled between engine 12 and transmission 52 . The clutch is controlled by the operator of vehicle 10 by clutch pedal 54 . In some embodiments, a clutch pedal sensor 56 may be coupled to clutch pedal 54 . A signal from clutch pedal sensor 56 is coupled to ECU 30 . In another alternative, transmission 52 is a dual clutch transmission (DCT) that is essentially two manual transmissions in one unit. Odd gears are coupled to one clutch and even gears are coupled to a second clutch. The transmission can be fully automatic with ECU 30 or gear selection is controlled by the vehicle operator. The clutches remain under control of ECU 30 . In yet another alternative, transmission 52 is an automatic shifting manual (ASM) that is very much like a conventional manual transmission except that the clutch is under robotic control. The gears may be controlled by ECU 30 or by the vehicle operator. Transmission 52 is coupled to wheels 38 via a drive train including a shaft 53 coupled to vehicle wheels 38 . The embodiment in FIG. 1 shows a two-wheel drive configuration. However, the present embodiment applies to any suitable configuration, such as, but not limited to, four-wheel drive vehicles.
[0028] Engine 10 has fuel injectors 60 which are coupled to engine cylinders, such as is the case with direct-injection gasoline or diesel engines. In port-injected, gasoline engine, fuel injectors are located in intake manifold 18 . Pulse width and timing of the fuel injection is controlled via ECU 30 . Fuel injectors 60 are supplied pressurized fuel from a fuel tank via at least one pump, the fuel system not shown in FIG. 1 . In a gasoline engine, engine cylinders are also provided with spark plugs 62 , the timing of which is controlled by ECU 30 . Engine 12 is provided with a variable cam timing (VCT) device 64 to adjust the timing of the intake valves with respect to the piston position. Cam timing is controlled via ECU 30 . In other embodiments, an exhaust VCT is provided, also.
[0029] A flowchart illustrating an embodiment of the disclosure is shown in FIG. 2 . The algorithm begins in 70 with entry conditions that vehicle speed is zero, i.e., the vehicle is stopped, that the vehicle operator is depressing brake pedal 34 , and transmission 52 is not in a reverse gear. That is, launch performance enhancement is not used for backing up the vehicle. Control passes to decision block 72 in which it is determined whether brake pedal release is imminent. Such determination will be discussed in more detail below. If brake pedal release is not imminent, control remains in decision block 72 until the brake pedal is released or release is imminent, in which case control passes to 74 in which a counter, i, (or alternatively a timer) is reset. Control now passes to block 76 in which actions are taken to cause a greater exhaust enthalpy to be delivered to cause the exhaust turbine to spin up. Such actions may include one or more of: opening throttle valve 24 , retarding spark timing, completely closing the wastegate valve 28 in the event that it is not already closed, adjusting the variable cam timing (VCT) system coupled to the engine. When the spark timing is retarded, the amount of torque produced by the engine decreases and the exhaust temperature rises. To counteract the drop in engine rpm that would accompany the torque drop, throttle valve 24 is opened further. In one embodiment, engine rpm is maintained at normal idle rpm. In one alternative, engine rpm is allowed to increase slightly, although not so much to alert an operator of the vehicle. In the embodiment, in which engine rpm is allowed to increase, a vehicle with an automatic transmission would creep forward at a greater rate than would otherwise be the case. To avoid an unexpected forward movement, a brake is applied in block 74 under control of ECU 30 . In one embodiment, a brake is applied to at least one wheel to cause the vehicle speed to remain stationary. In another embodiment, the brake is applied to cause the vehicle to creep per a conventional strategy as with a vehicle with a torque converter. In embodiments with ASM or DCT transmissions, when the operator releases the brake pedal, a brake is applied under control of ECU 30 at least in situations where vehicle 10 is on an incline to thereby prevent roll back or roll forward. Typically, in embodiments with a conventional manual transmission, the vehicle operator controls the brakes by actuating the brake pedal. In some situations with a conventional manual transmission, the brake is not applied by ECU 30 . In block 78 , i is incremented. Control passes to decision block 80 , in which it is determined whether the operator has depressed the brake pedal, the accelerator pedal, or neither. If the operator has depressed the accelerator pedal, the brake is released and normal operation ensues in block 82 . If the operator has depressed the brake pedal, control passes to block 84 in which brake application by ECU 30 is released and is replaced by brake application due to brake pedal depression by the vehicle operator. Furthermore, actions in block 74 are aborted and normal strategy takes over. If neither are depressed, control passes to block 86 in which counter, i, is compared to a threshold. The actions taken in block 76 are intended to be temporary, e.g., for the 0.5 to 1 sec between the operator removing their foot from the brake pedal to the accelerator pedal to launch the vehicle, i.e., to anticipate the operator's intent to launch. However, for variety of reasons, the operator may not choose to launch, e.g., a car stalls or stumbles in front of them at a traffic light or in parking lot maneuvers. Thus, a counter, or alternatively a timer, is used to limit the predetermined time that the actions in 76 are allowed to run. The predetermined time may be in the range of 0.25 to 3 seconds, although such example is non-limiting. Thus, in decision block 86 if it is found that the counter has exceeded the threshold, control is passed to block 88 in which the normal idle strategy is employed is commanded, i.e., a strategy outside the scope of the present disclosure. If in decision block 86 it is found that the counter has not exceeded the threshold; actions in block 76 are allowed to continue.
[0030] In decision block 72 , a determination is made as to whether the brake pedal is being released. In one embodiment, the brake pedal is coupled to an on-off switch and coupled to brake lights on the exterior of the vehicle. When the brakes are determined to be off, the measure(s) to spin up the turbocharger are invoked. In vehicle embodiments that include a pressure sensor in the brake hydraulic lines, the actual release of the brakes may be anticipated by evaluating the signature of the pressure curve when the operator releases the brakes. An example of such a pressure curve as a function of time is shown as curve 100 in FIG. 3 . In one embodiment, imminent release of the brake is based on the pressure dropping below a threshold pressure, in which case 102 indicates the time at which imminent brake release is determined and the measure(s) to spin up the turbocharger are invoked. In another embodiment, the measure(s) are based on the rate of decay, dP/dt, being below a threshold dP/dt. (Recall that dP/dt threshold in FIG. 2 is a negative number. Thus, the decay rate is exceeded when the decay rate is below, or more negative, than the threshold rate.) Imminent brake release is 104 for the example rate of decay determination in FIG. 2 . To obtain a sufficiently robust derivative of pressure, suitable averaging, filtering, or other techniques may be employed to avoid false detection of imminent brake release.
[0031] In yet another embodiment, a brake pedal position sensor is provided on the brake pedal. An example curve 110 is shown in FIG. 4 in which the brake is depressed at the left hand side of the graph. At some time later, the operator lifts their foot from the brake pedal and the signal from the position sensor indicates that the pedal rises. At a threshold position, imminent brake release is detected, and shown as occurring at time 112 in FIG. 4 .
[0032] According to some embodiments of the disclosure, one or more measures are undertaken to spin up the turbocharger that are employed in the time between the operator providing an indication that they are releasing the brake and the time that their foot is on the accelerator pedal. Such interval of time is highly dependent on the driving style of the operator of the vehicle. Some drivers are very casual, releasing the brake and slowly moving their foot over to the accelerator pedal to begin acceleration. Other drivers are aggressive and perform the movement rapidly. The aggressiveness with which the measures to overcome turbocharger lag are employed may be based on the operator's driving style. For example, if the driver is aggressive, the time for spinning up the turbocharger is more limited than for a casual driver. In one embodiment, the measures taken to spin up the turbocharger are applied more aggressively. In some embodiments, the time for applying the measures, i.e., before aborting the measures is based on the expected time until the driver calls for a launch by depressing the accelerator pedal. For example, if the driver takes two seconds between providing an indication of releasing the brake pedal and actually depressing the accelerator pedal, it may be possible to merely open the throttle slightly, possibly with spark retard, to obtain the desired turbocharger speed increase. Also, the time threshold during which the measures are allowed to proceed without aborting the measures to spin up the turbocharger may be increased. That is, for a slower acting operator, the actions to bring the turbocharger to a higher speed may be applied longer in waiting for the operator to depress the accelerator pedal. Consequently, in one embodiment, the driving style of the driver, in regards to time to move from the brake pedal to the accelerator pedal, is determined and the thresholds and the measures associated with spinning up the turbocharger are altered accordingly.
[0033] In vehicles without a turbocharger, it is also helpful to prepare for a launch. For example, one of the delays in a naturally-aspirated, spark-ignition engine in providing a fast launch is manifold filling. That is, at idle, the pressure in the manifold may be in the range of negative one-third atmosphere. Bringing the pressure nearer atmospheric to obtain torque quickly at the wheels can take about 0.25 seconds. Launch response can be improved by at least that much by anticipating the operator's intention for a launch. That is, if the throttle valve in the intake is opened slightly prior to the operator depressing the accelerator pedal, the vehicle launch is faster. Retarding spark is not so important in a naturally aspirated engine to improve launch performance. However, it can be employed to bring exhaust aftertreatment devices, such as a three-way catalyst, to temperature in anticipation of an increased NOx engine out emission upon launch. Of course, upon the actual launch when the operator depresses the accelerator pedal, spark timing is advanced to provide the desired torque.
[0034] In the example adaptive routine shown in FIG. 5 , many of the blocks are similar to those in FIG. 2 . The identifying numerals of FIG. 2 are employed here for efficiency's sake. In block 80 , in which actuation of brake pedal, accelerator pedal, or neither is queried. If the brake pedal is actuated, the routine of FIG. 5 is aborted in block 120 . If the accelerator pedal is depressed, control passes to block 122 in which the value of the counter is stored. The value of the counter indicates the time that it takes for this vehicle operator to move their foot from the brake to the accelerator pedal. If neither pedal is depressed, control passes to block 86 in which it is determined whether the counter has exceeded the threshold. If not, the actions in 78 continue. If the threshold is exceeded by the counter in decision block 86 , control passes to block 124 to store the value of the counter. If block 124 is accessed, the vehicle operator has not depressed a pedal in the time allotted for preparation for a launch. This could be due to the operator being a more casual driver and taking more time to call for a launch. Control passes from 124 to block 128 in which the value of the threshold may be adapted (increased) and the aggressiveness of the actions taken in block 76 reduced. From block 122 , control passes to block 126 in which the value of the threshold may be adapted (decreased) and the aggressiveness of the actions taken in block 76 increased.
[0035] In FIG. 5 , the algorithm shows a dashed link between blocks 122 and 126 and between blocks 124 and 128 . According to one embodiment, the adaptations in blocks 126 and 128 are not performed for each time that a counter value is stored. Instead, multiple values of the counter are determined before adapting the routine. For example, a more aggressive driver may be in a parking lot and does not perform a launch. Thus, the counter exceeding the threshold does not indicate a change in the driver's general style, but a different driving scenario. Thus, adaptations in block 126 and 128 are performed after collecting data from multiple launches. Furthermore, the adaptation may be slowly invoked. E.g., if the last 10 launches have occurred with counter, i, well below the threshold, the threshold may be reduced in block 122 . However, rather the reduction would be limited and only after several adaptations would the value of the threshold approach the value appropriate for the current driver. Of course, vehicle may have multiple drivers with varying driving styles. In such a case, the adaptations would adjust slowly for the current driver. Or, if the driver changes rapidly, little or no adaptation takes place as the values of the counter vary so widely so that no new direction is clearly indicated.
[0036] Different operators of the vehicle are likely to have varying driving styles. The launch interval, i.e., time from brake pedal release until accelerator pedal depression, may vary greatly from driver to driver. Thus, in some embodiments, a launch interval is determined for each operator, i.e., a launch interval is associated with each operator. The operator may be detected by the key fob 150 (as shown in FIG. 2 ) that is used. In one embodiment, adjustment of the driver's seat 152 as determined by a sensor 154 is used to distinguish among operators of the vehicle. Or, in another embodiment, sensor 154 is a weight sensor that can be used to distinguish among operators of the vehicle. Alternatively, position sensor 158 is coupled to a mirror 156 is used to detect a particular operator. In yet another embodiment, driving style, such as rate of depressing the accelerator pedal, aggressiveness of braking maneuvers, etc. are used to detect the driver of the vehicle.
[0037] If the launch interval is relatively short, the action or actions taken to prepare for the launch are undertaken more aggressively. In one embodiment, engine speed is increased during the launch interval. One action to increase engine speed is to open the throttle valve to a greater angle when the launch interval is shorter. In an alternative embodiment, the rate at opening the throttle valve can be greater when the launch interval is shorter.
[0038] In embodiments with a turbocharger coupled to the engine, it may be useful to retard the spark timing or injection timing to increase exhaust enthalpy to the turbocharger. The rate at which these actions are taken or the magnitude of the action are increased when the launch interval is decreased.
[0039] The term timer counter is used in reference to FIG. 2 . In one embodiment, the algorithm is performed on a clocked basis, e.g., every 100 msec. In such a case, the counter is proportional to time and can be used directly. Alternatively, the counter should be related to real time so that the algorithm is not skewed by the time it takes to perform portions of the algorithm. In another alternative, a timer based on a clock is used in place of the counter.
[0040] Referring to Figures and 7 , two example launch intervals are shown, fast and slow, respectively. Before incipient launch, the throttle angle is at a first throttle angle, i.e., for normal engine idle. When incipient launch is detected, in one embodiment, the throttle valve is commanded more open to a second throttle angle, as shown by a dotted line. The second throttle angle is maintained until the end of the launch interval or until the operator of the vehicle intervenes by depressing on the accelerator pedal. Alternatively, the throttle valve is opened progressively over a period of time, shown as dθ/dt, fast and dθ/dt, slow in FIGS. 6 and 7 , respectively. When it is known that the operator has a more rapid driving style, the throttle is opened more rapidly to sufficiently prepare for the launch, per FIG. 6 . Conversely, the throttle is opened more slowly in FIG. 7 . In some applications, it may be desirable to open the throttle more slowly to be less distracting to the operator of the vehicle. In other applications, it may be desirable to open the throttle directly to the desired position to ensure an aggressive launch feel. Or, in other applications, a combination may be employed.
[0041] While the best mode has been described in detail, those familiar with the art will recognize various alternative designs and embodiments within the scope of the following claims. Where one or more embodiments have been described as providing advantages or being preferred over other embodiments and/or over prior art in regard to one or more desired characteristics, one of ordinary skill in the art will recognize that compromises may be made among various features to achieve desired system attributes, which may depend on the specific application or implementation. These attributes include, but are not limited to: cost, strength, durability, life cycle cost, marketability, appearance, packaging, size, serviceability, weight, manufacturability, ease of assembly, etc. The embodiments described as being less desirable relative to other embodiments with respect to one or more characteristics are not outside the scope of the disclosure as claimed. | Turbo lag is a known impediment of a turbocharged, small displacement engine providing the feel of a large displacement engine. A method of spinning up the exhaust turbine during an interval between the time that the operator moves his/her foot from the brake pedal to the accelerator pedal to initiate a launch. A non-exhaustive list of actions that can be taken to increase exhaust enthalpy provided to the turbine include: opening the throttle, retarding the spark, and closing the wastegate. Additionally, a brake can be applied at one of the vehicle wheels to keep the engine from launching forward during this interval. | 8 |
CROSS-REFERENCE TO OTHER APPLICATIONS
[0001] This application claims the benefit of U.S. provisional patent application No. 62/322,363, filed 14 Apr. 2016 and entitled Wire Cover and Mounting Bracket, the disclosure of which is incorporated by reference.
REFERENCE TO APPENDIX
[0002] Attached as part of this application is an Appendix to the Specification, which includes digital images/photograph/line drawings, identified as sheets A through T, of the technology disclosed herein. Upon allowance of this application and payment of the Issue Fee, this Appendix may be deleted.
BACKGROUND OF THE INVENTION
[0003] Solar photovoltaic (PV) panels are typically provided of rigid planar form with each panel having a similar size, typically rectangular and approximately two to three feet in a shorter dimension and four to six feet in a longer dimension. Solar cells are provided upon a front surface of the solar panel. These individual cells are electrically connected together. A junction box is provided on a rear surface of each panel which gathers up the electric power generated by the cells on the panel and passes this electric power onto wires. These wires from the junction box can facilitate wiring together of multiple panels of an array to produce the overall power generated by the array of panels.
[0004] Solar panels are required to be deployed in an outside environment exposed to solar radiation, where the panels are also exposed to extremes of temperature and moisture. Furthermore, birds and other animals typically have access to the panels and the wiring connecting the panels together. One of the significant benefits of solar power systems of the PV panel variety is that they have no moving parts which must require maintenance or periodic inspection/replacement, as is the case with other distributed power assets such as wind turbines. However, the outside exposure experienced by the panel and its associated wires can result in damage occurring to the panels even without the panels experiencing any motion. Some solar panel arrays are mounted in a movable fashion to “track” the sun. Such tracking systems can be kept quite simple and easy to maintain, so that the panels do not require significant maintenance or inspection for reliable operation.
[0005] Perhaps the greatest source of PV panel array failure is presented in association with the wires that connect the individual panels together. The wires have connectors where they are joined to other segments of wire or to the junction boxes of various panels. If the wires become damaged, the system of PV panels can fail. The wires also benefit from minimizing expense through only providing an amount of exterior insulation necessary and to otherwise structure the wire with a relatively light and low cost configuration, including diameter, conductive material, insulating material, insulating material thickness, etc. Furthermore, the wires themselves can be extensive in length and represent a significant value for the overall panel system. It is known in certain instances for thieves to steal wire, such as the wire joining PV panels together, to recycle the wire for its inherent value in the conductive metals contained therein, or to repurpose the wire in other ways.
SUMMARY
[0006] A simplified summary is provided herein to help enable a basic or general understanding of various aspects of exemplary, non-limiting implementations that follow in the more detailed description and the accompanying drawings. This summary is not intended, however, as an extensive or exhaustive overview. Instead, the sole purpose of this summary is to present some concepts related to some exemplary non-limiting implementations in a simplified form as a prelude to the more detailed description of the various implementations that follow.
[0007] A photovoltaic panel wire cover assembly is used with a PV panel having a perimeter trim piece, the perimeter trim piece having a thickness. The assembly includes a plurality of clips, an elongate wire cover and fastener structure. Each clip includes a proximal end, a long leg and a short leg, the long leg parallel with and joined to the short leg at the proximal end of the clip, the long leg having a distal end. There is a gap between the long leg and the short leg of the clip sized for receipt of the perimeter trim piece of the PV panel. The elongate wire cover includes a wire-covering housing, the wire-covering housing having first and second opposite sides and a first flange extending away from the first opposite side. The wire-covering housing defines a housing interior. The first flange is positioned against the long leg of the clip. The fastener structure engages the short leg of the clip and the first flange to bias the first flange and the long leg of the clip therewith towards the short leg of the clip. The wire cover can be fastened to the perimeter trim piece of the PV panel through the clips without penetrating the PV panel.
[0008] Examples of the photovoltaic panel wire cover assembly can include one or more the following. The short leg can have holes adjacent to the proximal end aligned with each other and passing through the short leg and the long leg; the first flange can include a plurality of slotted holes therein; and the fastener structure can include a fastener passing through the slotted holes in the wire covers and into the holes in the clip. The clip can include a trim engagement element, such as a curved distal end, at the distal end of the long leg. The hole in the long leg can be a through hole through which a fastener can freely pass and the hole in the short leg can be configured, such as with threads, to engage the fastener. The wire cover can have a second flange extending away from the second opposite side, the second flange including a plurality of second slotted holes and positioned against the long leg of a second clip, the second clip engaging a second perimeter trim piece. Further fastener structure can engage the short leg of the second clip and the second flange to bias the second flange and the long leg of the second clip therewith towards the short leg of the second flange. In this way the wire cover can be fastened to the second perimeter trim piece of the PV panel through clips without penetrating the PV panel. The elongate wire cover can have an open end, and the assembly can include a closed end cap mountable to the open end of the elongate wire cover to prevent access to the housing interior. The assembly can also include an open end cap, having a wire passage opening, mountable to an open end of the elongate wire cover, and a jumper tube extending from the open end cap to provide a wire passageway from the wire passage opening through the jumper tube, whereby the open end cap and jumper tube extending therefrom prevents access to the housing interior other than through the wire passageway.
[0009] Other features, aspects and advantages of technology disclosed can be seen on review the drawings, the detailed description, and the claims, which follow.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The included drawings are for illustrative purposes and serve only to provide examples of possible structures and process operations for one or more implementations of this disclosure. These drawings in no way limit any changes in form and detail that may be made by one skilled in the art without departing from the spirit and scope of this disclosure. A more complete understanding of the subject matter may be derived by referring to the detailed description and claims when considered in conjunction with the following figures, wherein like reference numbers refer to similar elements throughout the figures.
[0011] FIG. 1 is a rear perspective view of a conventional array of PV panels mounted to a common tracking bar.
[0012] FIG. 2 is a rear perspective view of an array of PV panel wire cover assembly used with an array of PV panels mount to a common tracking bar.
[0013] FIG. 3 is a view similar to that of FIG. 2 during the installation of wire covers to the array of PV panels, showing wires covered by a wire cover and wires to be covered by a subsequently installed wire cover.
[0014] FIG. 4 is an enlarged view of a portion of the structure of FIG. 3 showing clips engaging trim pieces at opposed edges of adjacent PV panels.
[0015] FIG. 5 is an enlarged perspective view a portion of the structure of FIG. 2 showing an end of one wire cover overlapping the end of an adjacent wire cover.
[0016] FIG. 6 shows an end cap covering the outermost end of the wire cover at the end of the array of photovoltaic panels.
[0017] FIG. 7 shows a jumper tube extending between open end caps to protect wires passing between space-apart PV panels.
[0018] FIG. 8 is a top, front, right side isometric view of a wire cover.
[0019] FIG. 9 is a top plan view of the wire cover of FIG. 8 .
[0020] FIG. 10 is an end view of the wire cover of FIG. 8 .
[0021] FIG. 11 is a left side view of the wire cover of FIG. 8 .
[0022] FIG. 12 is a top, front, right side view of a clip partially shown in FIG. 4 together with a fastener.
[0023] FIG. 13 is a bottom, front, right side view of the clip of FIG. 12 .
[0024] FIG. 14 is a front, top, right side view of the closed end cap shown in FIG. 6 .
[0025] FIG. 15 is a top plan view of the end cap of FIG. 14 .
[0026] FIG. 16 is a rear elevation view of the end cap of FIG. 14 .
[0027] FIG. 17 is a front, top, right side view of the open end cap shown in FIG. 7 .
[0028] FIG. 18 is a top plan view of the end cap of FIG. 17 .
[0029] FIG. 19 is a rear elevation view of the end cap of FIG. 17 .
[0030] FIG. 20 is a simplified edge view showing a clip mounted to a trim piece of the solar panel with a flange of the wire cover about to be secured to the clip by a fastener.
DESCRIPTION OF THE INVENTION
[0031] To protect the wires and to hide them from view, it is desirable to provide a cover for the runs of wire which join PV panels together. Such covers would both protect the wires and make the wires less enticing to thieves, and present some degree of impediment to thieves interested in stealing the wires. While a basic cover could be provided over runs of wire joining panels together including a cover element and with a flange having a hole therein which can receive a fastener, a significant problem is encountered in that the flange of such a basic cover requires a hole in the panel through which a fastener can pass for connecting the cover to a panel. PV panels are typically substantially free of fastener holes thereon, other than fastener holes which are already dedicated to other purposes, including panel mounting purposes. Without a hole available for securing such a cover to the panel, one is left with the undesirable prospect of perhaps drilling an additional hole in the panel (which may void its warranty), which not only has significant propensity to damage the panel, it involves significant additional work. Accordingly, a need exists for a system for a wire-covering system for an array of photovoltaic panel which does not require drilling of holes into the panels, but can still allow for a wire cover to be mounted to the panels in a simple manner.
[0032] FIG. 1 is a rear perspective view of a conventional array 22 of PV panels 14 mounted to a common tracking bar 24 . A junction box 26 is seen mounted along an edge of each PV panel 14 with exposed wires 12 extending from the junction boxes.
[0033] With this technology, a PV panel wire cover assembly 8 , see FIG. 2 , includes a wire cover 10 , also referred to as cover 10 , for covering wires 12 which join photovoltaic (PV) panels 14 together so that they cannot be seen and to help protect the wires from the weather, vandalism, theft and animals. PV panels 14 are also referred to as panels 14 or solar panels 14 . Assembly 8 also includes a clip 16 which can be easily attached to a panel 14 without requiring drilling of holes thereinto, and which clip 16 presents a hole 18 to which a fastener 20 , such as a screw or bolt, can join after having interfaced with a wire cover 10 , so that between the wire cover 10 and a series of such clips 16 , the wire cover 10 can be coupled to the panels in a manner overlying the wires thereof
[0034] FIG. 3 shows a wire cover 10 during installation with wires 12 extending from the open end of a wire cover 10 prior to installation of the next wire cover 10 . FIGS. 8-11 illustrate how the wire cover 10 has a pair of flanges 28 , 30 and a wire-covering housing 32 defining a housing interior 34 between the flanges. Wire-covering housing 32 is sized, in particular to have sufficient depth 36 , to accommodate the wires 12 bundled therein. The flanges 28 , 30 include slots. These slots are preferably of a variety which is elongate in form with rounded ends and with a length thereof parallel with a length of the wire-covering housing 32 of the wire cover 10 . Such slots are provided on each flange 28 , 30 directly adjacent to this wire-covering housing 32 . Because the panel-to-panel spacing 46 between solar panels 14 in array 22 can vary slightly, slots 38 , 40 are provided rather than a single hole, to accommodate some variation in panel-to-panel spacing. Longer flange 28 includes a notch 42 at each end. Notch 42 is useful in placing cover 10 under the edge of the PV panel frame thus reducing the need for clips and speeding up installation. However, for some types of equipment notch 42 can be omitted to create a notch less wire cover 10 indicated by the dashed lines 44 in FIG. 8 .
[0035] Details of the clips 16 are shown in FIGS. 12 and 13 , as well as FIG. 4 Each clip 16 can be a bent piece of spring steel (or optionally other material) which fits over a piece of trim 48 along the lateral sides 50 of the PV panels 14 ; see FIGS. 2-5 . Trim 48 extends generally perpendicular to the side-to-side orientation of wires 12 and wire covers 10 . Trim 48 is offset a distance slightly from a rear surface 54 of the panel with a width a distance sufficient to allow a short leg 58 of the clip 16 to reside therein. The clip 16 has a long leg 60 opposite the short leg 58 with the two legs substantially parallel to each other and joined together at a proximal end 62 of the clip. The long leg 60 ends at a trim engagement element 64 , also called a tooth 64 , at a distal end 66 thereof which can wrap around and grip somewhat an outer edge 68 of the trim 48 . The proximal ends of each leg of the clip 16 are joined together so that the clip 16 is, in this example, a continuous piece of metal. A spacing or gap 69 between the legs 58 , 60 of the clip 16 is preferably similar to a thickness of the trim 48 on the panel 14 , so that somewhat of a friction fit is provided when the clip 16 is slid over the trim 48 with the trim 48 between the legs 58 , 60 .
[0036] FIG. 20 is a simplified edge view showing a clip 16 mounted to a trim piece 48 of the solar panel 14 with a flange 28 , 30 of the wire cover 10 about to be secured to the clip by a fastener 20 . An overall width of the clip 16 between the distal tooth 64 at the tip of the long leg 60 and a curve at the proximal end 62 where the long leg 60 and short leg 58 are joined together, see dimension 70 in FIG. 13 , is greater than the width 56 of the trim 48 by an amount sufficient so that hole 18 , which in this example includes a top through-hole 72 and a bottom threaded hole 74 , passing through the clip 16 can be positioned off of the trim 48 . See FIGS. 13 and 20 . These holes 72 , 74 pass through both the long leg 60 and the short leg 58 of the clip 16 with the holes adjacent to the curving proximal end 62 of the clip 16 which joins the long leg 60 and the short leg 58 together. The holes preferably are similar in size and aligned together, but, in this example, with the hole 74 in the short leg 58 being threaded and the hole 72 in the long leg 60 being a through hole and not threaded. It is also conceivable that both of the holes could be threaded or neither of the holes could be threaded and still function according to this technology if, for example, using non-threaded fasteners or if a threaded fastener pair such as a bolt and nut are used together. Most preferably, however, the short leg 58 has its hole 74 threaded and the long leg 60 does not have its hole 72 threaded.
[0037] In one embodiment, if the trim 48 has a one inch width 56 , the long leg 60 could have a two inch length and the short leg 58 could have a one and a half inch length. In such a configuration a quarter inch hole could be provided which is spaced approximately a quarter inch to a half inch away from the curving proximal end 62 of the clip 16 where the long leg 60 and short leg 58 come together. The clip 16 could have various different widths 76 ; clip 16 is shown with approximately a three-quarter inch width in the embodiment depicted.
[0038] If the clip 16 is formed of materials other than spring steel (e.g., aluminum or plastic) it still preferably functions to clamp and hold to the trim 48 . The clip 16 will then have a tendency to stay where initially placed. Furthermore, once a fastener 20 passes through the non-threaded hole 72 in the long leg 60 and then threads into the threads in the threaded hole 74 in the short leg 58 , the long leg 60 and short leg 58 are drawn together and further pinch the clip 16 tightly against the trim 48 . The clip 16 thus conveniently tends to stay where positioned before use, but can be repositioned fairly easily before it has been used, such as by sliding along the trim 48 with the tooth 64 at the distal end 66 of the long leg 60 keeping the clip 16 aligned where it is desired to be.
[0039] Once the clips 16 are positioned where desired, a wire cover 10 would be placed over wires 12 joining panels 14 together and with the elongate hole or slots 38 , 40 in one of the flanges 28 , 30 overlying the clip 16 and aligned with the holes in the clip 16 . A fastener 20 , such as a bolt, would then be passed through the elongate hole 38 , 40 in the flange 28 , 30 and then passed through the non-threaded hole 72 in the outer, long leg 60 of the clip 16 , and then threaded into the threaded hole 74 in the short leg 58 of the clip 16 . See FIG. 20 . Once the fastener 20 has been tightened, not only has the clip 16 been secured in position against the trim 48 of the panel, but also the wire cover 10 has been secured to the panel as well. This process is repeated with additional clips 16 at corresponding locations on other portions of the wire covers 10 to securely cause the wire covers 10 to be mounted to overlie wires 12 joining the panels 14 together.
[0040] FIG. 6 shows a closed end cap 82 covering the outermost end of the wire cover 10 at the end of the array 22 of photovoltaic panels 14 . Details of end cap 82 are shown in FIGS. 14-16 . FIGS. 7 and 17-19 illustrate an open end cap 84 secured to the outermost end of a wire cover 10 . Open end caps 84 are used when there is a gap between PV panels 14 , such as when there is a motor or other obstruction in the way on tracked arrays of PV panels. Open end cap 84 defines a wire passage opening 90 and has a curved extension 86 over which a jumper tube 88 , see FIG. 7 , is mounted. Wires 12 pass between the spaced-apart PV panels 14 along a wire passageway through wire passage opening 90 , through curved extension 86 and through jumper tube 88 . Use of closed end caps 82 and open end caps 84 , together with jumper tube 88 , helped to protect wires 12 from the elements, degradation or destruction by animals, and also helps to keep animals from entering housing interior 34 . Jumper tube 88 can be made with somewhat flexible material, such as PVC or ABS, with a slit along its length to permit it to be placed over curved extensions 86 and the wires 12 extending between space-apart open end caps 84 as shown in FIG. 7 . The length of jumper tube 88 is made to be slightly shorter than the distance between open end caps 84 so that it maintains contact with the curved extensions 86 of the open end caps.
[0041] If desired for further theft prevention, fasteners 20 having unique torque receiving surfaces can be used so that it is less likely that a thief has access to a proper tool for removal of such fasteners. The fasteners could be provided of a type which can allow for ready installation but does not allow for ready disassembly. For instance, rivets could be used instead of threaded fasteners or threaded fasteners with heads which allow for torque to be applied for fastening but not to be applied for removal. As a still further option, the fasteners could have heads which snap off after the fastener has been used, so that the torque applying head is removed and unavailable for theft access after installation.
[0042] Typically, wire covers 10 are provided which are of standard lengths which allow for convenient handling thereof, such as six foot lengths or ten foot lengths. The wire covers 10 can overlap each other somewhat at ends thereof to allow for continuous covering of the wires 12 . Each wire cover 10 would typically have a length which spans two or more panels 14 . The positions of the slotted holes 38 , 40 are preferably selected to generally match widths 78 of the panels 14 but with the slotted holes sufficiently long to accommodate variations in panel size as well as spacing 46 between adjacent panels 14 .
[0043] Covers 10 can be made of bent metal, such as galvanized sheet steel or of sheet aluminum. Covers 10 can also be made of polymer materials, such as PVC, typically through extrusion or molding techniques. While clips 16 are preferably made of materials such as spring steel to aid proper positioning; in some examples clips 16 may be made materials, such as layered materials, which may or may not exhibit the degree of resilience provided by spring steel. The covers 10 and clips 16 could alternatively be made of non-metal materials or metals of other varieties to optimize desired performance characteristics or to minimize expense or otherwise provide for benefits associated with particular materials selected.
[0044] This disclosure is provided to reveal a preferred embodiment of the technology and a best mode for practicing the technology. Having thus described the technology in this way, it should be apparent that various different modifications can be made to the preferred embodiment without departing from the scope and spirit of this disclosure. When structures are identified as a means to perform a function, the identification is intended to include all structures which can perform the function specified. One or more elements of one or more claims can be combined with elements of other claims. Any and all patents, patent applications and printed publications referred to above are incorporated by reference. | A photovoltaic panel wire cover assembly, used with a PV panel having a perimeter trim piece, includes clips, an elongate wire cover and fastener structure. Each clip includes a proximal end and long and short legs, the long leg parallel with and joined to the short leg at the clip proximal end. A gap between the long and short legs is sized for receipt of the trim piece. The wire cover includes a wire-covering housing defining a housing interior and having first and second opposite sides and a first flange extending from the first opposite side and positioned against the long leg. The fastener structure engages the short leg and the first flange to bias the first flange and the long leg therewith towards the short leg. The wire cover can be fastened to the trim piece through the clips without penetrating the PV panel. | 7 |
BACKGROUND AND SUMMARY OF THE INVENTION
The present invention relates to three-axis positioning jacks, capable of supporting objects whose weights can be as high as several hundred metric tons whilst allowing their positioning with an accuracy of the order of one micrometer.
At present, when a structure has to be positioned or shaped with respect to a foundation, jacks are used which are disposed between that foundation and the structure. These jacks are adjusted manually or electrically by agents who will carry out iterative adjustment operations until the desired position is reached. It is however extremely difficult in practice, if not impossible, to obtain high accuracy in such a context.
For the positioning of these structures, the actuators normally used are jacks, the two best known types of which are:
mechanical jacks,
hydraulic jacks.
The mechanical solution, which is the most conventional one, uses a micrometric ball screw driven by a stepper motor. A compensation system often relieves the screw for heavy load applications. The principle of the hydraulic jack is itself so well known and its use is so widespread that a description of this type of jack would be superfluous if our new jack did not exhibit similarities with this technology.
In a hydraulic jack, a piston, provided with a fluid-tight seal, is free to move in the base of the jack, whose chamber is filled completely with a liquid which is only very slightly compressible. The piston moves, either because the volume of liquid in the chamber is modified by the injection or evacuation of the liquid via a pipe, a pump, a stop valve and a reservoir, or because an actuating piston, which is also provided with a fluid-tight seal, driven for example by a screw/nut assembly, modifies the shape of the chamber. As the liquid is virtually incompressible, the piston moves such that the volume of the chamber remains practically constant.
However, this type of jack which makes it possible to apply very high forces has three disadvantages:
the equipment is often dirty, the fluid-tightness of the hydraulic chambers becoming relative because of the wear and ageing of the seals;
micrometric positioning is impossible, the slight leakages and the high coefficient of expansion of the liquids used give rise to this positioning inability;
the manufacturing cost is generally high, the friction surfaces necessitating precise and high-quality practices.
From the French patent FR 2179572 there is known a force multiplier device comprising a first hydraulic jack, whose piston rod is mounted slidingly in an enclosure integral with the base of that jack and constituting the chamber of a second jack also equipped with a sliding piston subjected to the action of an elastomer confined in that chamber and transmitting pressures in a hydrostatic manner.
There is also known, from the German patent DE 3916539, a transmission and/or pressure device comprising a principal piston driven by a rod subjected to a pressure. This piston acts on an elastomer mass confined in a chamber and which provides transmission of pressure to two actuating pistons. These actuating pistons are controlled in displacement by piezoelectric actuators.
These force multiplier devices use an elastomer mass as a working fluid. They cannot however provide the function of a positioning jack offering the accuracy required here. In fact, in the device described in the document FR 2179572, the first jack or actuating jack is a hydraulic jack, which makes it difficult to attempt to achieve high accuracy. Furthermore, the transmission device divulged in the document DE 3916539 is not a force multiplier and cannot be used as a positioning jack since its principal piston has a cross-section less than that of the actuating pistons controlled by the piezoelectric actuators and small travels are therefore obtained at the level of the actuating pistons and a large travel of the principal piston is obtained, which would not make it possible to obtain the required level of accuracy.
The purpose of the present invention is to overcome these disadvantages by proposing a three-axis positioning jack which procures a high positioning accuracy whilst being of less expensive and more reliable construction than those of jacks of the prior art.
This purpose is reached with a three-axis positioning jack with at least one motorised axis, comprising:
a base comprising movable supporting means and means for vertically displaying said movable supporting means, and
a rod providing a link between the movable head of said jack and said base.
According to the invention, the linking rod is designed to form a double connection of the ball joint type providing with a lateral displacement of the head with respect to the base, and the movable supporting means comprise an elastomer mass on which the lower end of the linking rod is supported.
Such a jack allows, by means of the double link of the ball joint type, a more accurate tridimensional positioning than what can be expected from present jack techniques. Implementing a piece made with an elastomer material procures effort transmission and damping functions that are particularly appreciated in position controls for heavy structures.
Moreover, in a first embodiment of jacks according to the invention, the piece made from an elastomer material can be advantageously used as a working fluid.
Thus, there is proposed a three-axis positioning jack having at least one motorised axis, comprising:
a base comprising a bore containing a chamber in which there is confined a working fluid and a rod providing a link between the head of the jack and the base,
and means for modifying the shape of the confinement chamber for the purpose of obtaining a vertical displacement of the head, these means comprising at least one motorised actuating piston, characterized in that the working fluid is constituted by the elastomer mass.
In this first embodiment, the solid elastomer mass, which behaves like a quasi-fluid when under load, is deformed by an actuating piston which is motorised. This deformation has the effect of displacing the working piston in order that the volume of the chamber remains constant. The servo-control of a one-axis motorised jack according to the invention with respect to an absolute reference allows easy use of the latter in installations requiring an alignment of deformable structures. Furthermore, one-axis jacks according to the invention can be designed such that they are extra-flat.
The condition for correct operation of this new type of jack is that the pressure generated by the load applied to the piston which compresses the elastomer must be sufficient for the latter to behave like a quasi-fluid without, however, its viscosity lowering to such an extent that the polymer can be extruded through the construction clearance between the piston and the bore made in the base of the jack. This jack has minimum and maximum loads proportional to the cross-section of the bore-piston pair and to the Shore hardness of the elastomer used.
In a second embodiment of the present invention, there is proposed a three-axis positioning jack, characterised in that the movable supporting means comprise a movable piece for receiving the elastomer piece acting as a ball joint, said movable piece being slidingly mounted with respect to the base and being actuated by micrometric ball screw means.
This jack further comprises preferably a second elastomer piece acting as a ball joint between the higher end of the connecting rod and the movable head.
A bone-shaped connecting rod with complex-shaped ends can be provided, with said elastomer pieces preferably having housings or hollows fitted for receiving the respective ends of the connecting rod. Cylinder-shaped elastomer pellets can also be used with plane supporting faces against which plane or substantially plane ends of a connecting rod are supported.
Jacks according to the invention are compact and of small size. Furthermore, they are easy to produce and are therefore economical. Their functioning is reliable since there is no longer any risk of a sealing breakdown. Furthermore, coupled with servo-control means, jacks according to the invention allow very accurate positioning because of a high positioning resolution.
In this way there are available, with three-axis positioning jacks according to the invention, particularly effective actuators for carrying out positioning of a heavy structure with respect to an absolute reference or of several structures with respect to each other, with a high level of accuracy, since by combining several three-axis jacks according to the invention (for example three three-axis jacks of which two axes are motorised), it is possible to control the six degrees of freedom of an object.
Within the framework of the present invention, it is possible to provide:
a three-axis positioning jack, two of the axes being motorised, one of them being vertical and the other planimetric, the remaining axis being free or guided;
a three-axis positioning jack having a vertical motorised axis, the other two planimetric axes being free or guided.
A three-axis positioning jack of which two axes are motorised can furthermore comprise a motorised stop to procure a lateral displacement of the head of the jack along a first horizontal axis. This motorised stop comprises for example an actuating screw driven by a motor reduction gear.
Furthermore, in order to achieve manual guidance or displacement of the head of the jack along the non-motorised horizontal axis, it is possible to provide a screw and its thrust ring for this purpose.
Three-axis positioning jacks according to the invention can advantageously be servo-controlled in position with respect to an absolute reference, along at least one of the said motorised axes.
According to particular embodiments of one or three-axis jacks according to the invention,
additional actuating pistons can be distributed over the periphery of the chamber in order to increase or pre-adjust the travel of the jack; these actuating pistons are then driven by a screw-nut system which can be motorised or hand-driven;
a mechanical system for pre-loading (by springs) the elastomer can be provided for use under very light loads;
a displacement sensor can be associated with the jack for the servo-controlled versions.
Displacement sensors can be associated with all of these embodiments, allowing a relative servo-control of these jacks.
According to yet another aspect of the invention, there is proposed a method for the servo-control of the position of a structure supported by positioning jacks according to the invention, comprising measurements of the position of this structure and with each jack being servo-controlled on the basis of these measurements and of position commands.
Advantageously, it is possible to use a set of N jacks with one servo-controlled axis, to act on a deformable solid and to define its geometry, for example for the servo-levelling or servo-alignment of large machines or of long tubes, or for correcting the shape of a deformable solid of large size, or for achieving the flatness of a frame of a large machine tool or the straightness of the movement of translation of a large mass.
Servo-controls of N jacks according to the invention using the appropriate number of sensors measuring with respect to one or more absolute references are also included within the scope of the present invention.
Other features and advantages of the invention will furthermore appear in the following description. In the accompanying drawings given by way of non-limitative examples:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a cross-section of an embodiment of a three axis jack, according to the invention, of which two axes are motorised;
FIG. 2 is a cross-sectional plan view of the jack shown is FIG. 1;
FIG. 3 is a cross-sectional view of an embodiment of a three-axis jack, according to the invention, of which one axis is motorised;
FIG. 4 is a cross-sectional plan view of the top part of the jack shown in FIG. 3;
FIG. 5 is a cross-sectional view of a first example of another embodiment of a three-axis jack according to the invention;
FIG. 6 is a cross-sectional view of a second example of said other embodiment of a three-axis jack according to the invention;
FIG. 7 shows an example of the use of three jacks according to the invention in order to control the six degrees of freedom of a structure;
FIG. 8 shows a first combination of sensors used for providing a spatial position with respect to absolute references of a non-deformable structure;
FIG. 9 shows a second combination of sensors used for providing a spatial position of a structure in the servo-control method;
FIG. 10 shows a third combination of sensors used for providing a spatial position of a structure in the servo-control method according to the invention; and
FIG. 11 shows an example of the use of a set of one-axis jacks according to the invention for the alignment of long tubes.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Several embodiments of jacks according to the invention, with three axes of displacement, with one or two motorised axes, will now be described with reference to FIGS. 1 to 6 .
These jacks are particularly appropriate when an object has to be positioned and servo-controlled in space. In fact, in order to position and maintain an object in space, it is necessary to manage its six axes of freedom. These axes are generally controlled by three actuators which manage the different axes and support the weight of the object to be positioned. The solution traditionally employed uses three jacks oriented along the vertical axis Z which manage and control that vertical axis by simultaneous movements, and the rotations in the horizontal plane Ox, Oy by differential movement. A cross-movements table placed under one of the jacks manages the horizontal displacements of the X and Y axes. A third means of simple translation is disposed under one of the other two jacks and oriented along the Y axis is also necessary in order to manage the last axis Oz.
The use of three three-axis jacks therefore has the advantage of combining the two movements, vertical and planimetric respectively, whilst taking up very little volume. The six degrees of freedom of an object can be controlled by supporting it with three three-axis jacks. The positional servo-control of the object to be supported is then controlled by sensors which measure the displacements of the structure directly. The measurements are made either with respect to the ground (relative servo-control), or with respect to absolute references such as a taut line, a light beam, a liquid surface or any other equivalent means. This therefore makes it possible to position two or more blocks with respect to each other.
According to particular variant embodiments of the invention, it is possible to devise:
a jack 40 allowing motorised displacements along two axes, the vertical axis Z and the lateral axis X (FIGS. 1 and 2 );
a jack 60 allowing motorised displacement along the vertical axis and displacements by manually adjustable stops along its horizontal axes X and Y (FIGS. 3 and 4 ).
With reference to FIG. 1, the base 41 of the jack 40 according to the invention comprises a bore 410 which receives a first elastomer pellet 2 and a bone-shaped piston 43 of the double ball joint type whose lower end bears against the pellet 2 . The jack furthermore comprises a movable head 45 comprising a bore 456 containing a second elastomer pellet 455 against which the upper end of the piston 43 bears, and a peripheral cylindrical section 450 .
The vertical movement Z is obtained by the action of actuating pistons 44 , 4 on the elastomer 2 , manually adjustable actuating pistons 44 providing the initial adjustment of the positioning, and at least one actuating piston 4 being motorised for the positional servo-control. Besides the vertical movement, the geometry of the piston allows the rotations about the X and Y axes which then generate movements of translation along the X axis and the Y axis respectively of the head of the jack 40 . The elastomer pellet 455 is confined in the second chamber whose shape is modified by the displacement of two actuating pistons 451 , 452 controlled manually by adjusting screws 453 , 454 .
This makes it possible to increase the vertical travel and to tolerate non-parallelism of the base of the jack with respect to its head.
The motorisation on the horizontal axis X is achieved by means of a motorised stop bearing against the external periphery 42 of the base 41 and driven by a motor reduction unit 48 for the driving along the axis in question and comprising:
a thrust ring 461 which provides the guidance on the axis in question X and adjustment of the operational play, and
a drive screw 46 .
The motor reduction unit 48 is attached to the head 45 of the jack 40 by attachment means 49 . The drive screw 46 is displaced in translation by a motorised yoke 47 driven by the shaft of the motor reduction unit 48 . The second horizontal axis Y is simply blocked by the intermediary of unlockable stop screws 50 , 51 , as shown in FIG. 2 .
In a variant of this embodiment, shown in FIGS. 3 and 6 wherein identical references have been used for identical elements already shown in FIGS. 1 and 2, the two horizontal axes X, Y are acted upon by non-motorised manual stops 610 , 620 ; 660 , 670 which can be adjusted by screws 61 , 62 ; 66 , 67 traversing the top part 65 of the jack 60 . This jack 60 comprises a bore 410 receiving an elastomer pellet 2 and a piston 63 whose ball-joint shaped base rests on the elastomer pellet 2 and whose upper end comprises a housing 433 designed for receiving a ball 431 providing the second ball joint function, the top part 65 also comprising an appropriate housing 432 for receiving this ball.
In another embodiment of a three-axis according to the invention, the ball joints are made in elastomer material and the following displacement of the connecting rod is achieved by a micrometric ball-screw device, with reference to the examples of embodiment illustrated by FIGS. 5 and 6 wherein common elements feature common references.
Thus, the jack 50 comprises a base 51 provided with a higher cylindrical part 52 comprising a bore 521 wherein a movable piece 550 slides whose positioning is controlled by a micrometric screw-ball device 510 . The movable piece 550 is designed for receiving a first piece 554 made in elastomer material wherein a lower end 532 of a bone-shaped piston 53 of the double ball-joint type. The higher end 531 of the piston 53 is housed in a second piece 555 in elastomer material fitted into a bore 556 of a movable head 55 of the jack 50 .
The vertical movement along Z of the movable head 55 is obtained by acting on the micrometric ball-screw device 510 which can be actuated by a stepper motor. The two elastomer pieces 554 , 555 achieve both a function of ball-joint link and a function of damping.
In addition to the vertical movement, the geometry of the piston 53 allows rotations around the axes X and Y which therefore generate translations respectively on the axis X and the axis Y of the head of the jack 50 . Motorisation on the horizontal is achieved by means of a motorised stop supported on the external periphery of the higher part 52 of the base 51 and actuated by a motoreductor 58 for control on the considered axis, and comprising:
a thrust stop 561 which ensures guiding on the considered axis X and adjusting of the working looseness; and
an action screw 56 .
The motoreductor 58 is mounted on the peripheric cylindrical part 551 of the head 55 of the jack 50 by mounting means 59 . The action screw 56 is displaced in translation by means of a motorised nut 57 driven by the shaft of the motoreductor 58 . The second horizontal axis Y is merely blocked by means of stop screws.
In a second example of this embodiment with a micrometric ball-screw illustrated by FIG. 5, the piston 33 of the jack 30 comprises respectively lower and higher substantially plane ends 332 , 331 which bear against respectively a first and a second pieces 354 , 355 in elastomer material. Said first and second pieces 354 , 355 , which for example are shaped as cylindrical pellets, are respectively housed inside the sliding movable piece 550 and into the bore 556 provided inside the movable head 55 .
There will now be described an example of the use of the positioning servo-control method using jacks according to the invention and combinations of sensors used for measuring the position of a structure, with reference to FIGS. 7 to 11 .
The servo-control method according to the invention can for example be used for maintaining the geometry of a deformable structure. The use of N jacks with one motorized axis servo-controlled with respect to external absolute references therefore makes it possible to compensate for ground movements, mechanical stresses, etc., for example for the alignment of a long tube or the levelling of a machine tool.
In a first configuration shown in FIG. 11 which represents a system for the alignment of a long tube, the absolute reference is defined by a taut wire F. A long tube 111 rests on a first set of one-axis jacks V 1 -V 6 according to the invention disposed in the axis Z to be corrected, whilst a second set of one-axis jacks V′ 1 -V′ 6 according to the invention is disposed along the tube 111 and in the horizontal axis X. A set of biaxial deviation measuring devices E 1 -E 6 makes it possible to take biaxial deviation measurements with respect to this line in order to correct the alignment of the tube 111 .
In a second configuration, the reference can be defined by a stretch of water defining horizontality.
In a third configuration, the reference can be defined by one-axis or two-axis inclinometers.
Three-axis jacks according to the invention can for example be used for the spatial position servo-control of two or of N non-deformable structures 80 . There is carried out, using the servo-control method according to the invention, a control of the six degrees of freedom of non-deformable structures 80 each supported by three three-axis positioning jacks 81 , 82 , 83 according to the invention disposed on the ground 84 , each of these positioning jacks 81 , 82 , 83 being allocated to one vertical displacement axis A 1 , A 2 , A 3 and one lateral displacement axis A 5 , A 4 , A 6 . Each positioning jack 81 , 82 , 83 according to the invention is provided with a first motor reduction unit 812 , 822 , 832 for driving an actuating piston controlling the vertical displacement Z and the tilts Θx, Θy of the structure. Two positioning jacks 81 , 82 are furthermore provided with a second motor reduction unit 818 , 828 for driving a motorized stop controlling the displacement Y and Θz of the structure. The third positioning jack 83 is provided with a manually adjustable stop controlling the displacement along the horizontal axis X.
This servo-control method comprises a detection of the spatial position of each structure 80 with respect to an absolute reference R, and a closed loop servo-control of three positioning jacks 81 , 82 , 83 with respect to this reference.
In a first configuration, shown in FIG. 8, the absolute reference is defined by two taut wires and the position measurements comprise:
a uniaxial measurement of deviation ECZ from a wire made at a first point in the structure 80 along a vertical axis Z, with respect to a first taut wire F 1 along a first horizontal axis X, and
two bi-axial measurements of deviation ECD 1 , ECD 2 each made along the vertical axis Z and along the second horizontal axis Y at two other different points, with respect to a second taut line F 2 along a second horizontal axis X.
In a second configuration, shown in FIG. 9, the absolute reference is defined by two taut wires and the position measurements comprise:
a uniaxial measurement of deviation ECZ along a vertical axis Z, with respect to a first taut wire F 1 along a first horizontal axis X,
two uniaxial measurements of deviation ECY 1 , ECY 2 made at two different points along a second horizontal axis Y related to a second taut wire F 2 along a second horizontal axis, and
two clinometric measurements IN to provide two measurements Dx, Dy of the inclination of the structure 80 with respect to the vertical axis Z, about the first horizontal axis X and about the second horizontal axis Y respectively.
In a third configuration shown in FIG. 10, the position measurements comprise:
an altitude measurement AL made at a first point in the structure 80 along a vertical axis Z,
two uniaxial measurements of deviation ECY 1 , ECY 2 made at two different points along a second horizontal axis Y, with respect to a taut wire F 2 along a first horizontal axis X, and
two biaxial clinometric measurements IN to provide two measurements Dx, Dy of the inclination of the structure 80 with respect to the vertical axis Z about the first horizontal axis X and about the second horizontal axis Y respectively.
The position measurements are for example made at the locations of the jacks, but can very well be made at other points in the structure. With each positioning jack 81 , 82 , 83 there is associated a measurement along the vertical axis Z, and with two of the said positioning jacks 81 , 82 there are associated the two measurements along the second horizontal axis Y.
The invention is not of course limited to the examples which have just been described and many developments can be applied to these examples without departing from the scope of the invention. It is possible, for example, to design other embodiments of the positioning jacks. Other combinations of position sensors can also be envisaged. It is possible to use polyurethane or natural rubber for producing the elastomer mass. This mass can consist of a multitude of elastomer balls. | A positioning actuator with three axes includes a base having a movable supporting member and a device for moving the member up and down, and a shaft connecting the movable head of the actuator to the base. The connecting shaft forms a swivel-type double linkage enabling sideways movement of the head relative to the base, and the lower end of the connecting shaft engages a part made of elastomeric material and is provided within the movable supporting member. | 5 |
FIELD OF THE INVENTION
[0001] The present invention relates to an apparatus for installing a workpiece below a surface, e.g., in an underground location. More particularly, the present invention relates to an apparatus and method for installing an inground anchor, particularly a plate or wing-type anchor.
BACKGROUND OF THE INVENTION
[0002] There are occasions when it is necessary to install a workpiece in a substrate below a surface over the substrate; e.g., below the surface of a underground location. The two “substrate” as used herein is intended to mean any solid medium having a surface albeit that the materials forming the surface and the substrate may be different. The workpiece can take the form of an anchor which is used in a variety of uses in the utility, civil engineering and construction fields. For example such anchors can be used for guying utility poles, retaining walls, sheet piles, and seawalls; for buoyancy control of pipelines, for erosion control systems; and in underwater applications for anchoring moorings, docks and the like.
[0003] Types of anchor commonly used for the above described application are disclosed in U.S. Pat. Nos. 3,969,854, 4,044,513, 4,096,673, 4,802,317 and 5,031,370 and are generally referred to as plate or wing-type anchors.
SUMMARY OF THE INVENTION
[0004] In a preferred embodiment of the invention, there is provided an apparatus for installing a workpiece at a location below a surface. The apparatus includes an elongate track member having a first end positionable proximate, the surface, and a second end positionable distal the surface. A carriage is slidably mounted on the track member. A hammer assembly is mounted on the carriage, the hammer assembly having a hammer head which is reciprocally movable relative to the carriage in a direction toward and away from the first end of said track member. An operator effects reciprocation of the hammer head. There is also an actuator to compressively urge the carriage toward the first end of the track member.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] [0005]FIG. 1 is a side, elevational view showing the apparatus of the present invention installing an anchor in an underground location.
[0006] [0006]FIG. 2 is a side, elevational view of the apparatus of the present invention showing the apparatus being used to set the anchor which has been placed in an underground location.
[0007] [0007]FIG. 3 is a view taken along the lines 3 - 3 of FIG. 1.
[0008] [0008]FIG. 4 is a view taken along the lines 4 - 4 of FIG. 1.
[0009] [0009]FIG. 5 is a cross-sectional view taken along the lines 5 - 5 of FIG. 3.
[0010] [0010]FIG. 6 is a cross-sectional view taken along the lines 6 - 6 of FIG. 3.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0011] Turning first to FIG. 1, the apparatus of the present invention shown generally as 10 is seen as being positioned on the surface S of the ground G at a desired location. Apparatus 10 comprises an elongate track member shown generally as 12 , a carriage, shown generally as 14 , slidably mounted on track member 12 , and a hammer assembly, shown generally as 16 , mounted on carriage 14 . In the embodiment shown in FIG. 1, track member 12 is attached by means of a bracket 18 to a support assembly shown in phantom generally as 20 and comprised of a movable boom 22 and a piston/cylinder assembly 24 . Boom 22 and piston/cylinder assembly 24 are both pivotally attached to bracket 18 and accordingly can be used to move track member 12 and hence apparatus 10 to various desired attitudes or altitudes relative to the surface S of ground G. It will be understood that boom 22 and piston/cylinder assembly 24 can form part of a backhoe or other similar apparatus, commonly used in the construction field.
[0012] A hydraulic cylinder/piston assembly, shown generally as 26 , is comprised of a cylinder 28 in which is disposed a piston (not shown) and a piston rod 30 and is operatively interconnected between track member 12 and carriage 14 . As is well known to those skilled in the art, connected to cylinder 28 are hydraulic hoses attached to a suitable hydraulic power source, none of which are shown. As will be seen hereafter, two such cylinder/piston assemblies 26 can be used. One end 32 of cylinder 28 is attached to a lower or first end 34 of track member 12 via a clevis arrangement 35 while the end 36 of piston rod 30 which extends from cylinder 28 is attached to carriage 14 via another clevis arrangement 15 . Pivotally attached to the lower end 34 of track member 12 is a footer 38 which rests on the surface S of the ground G. It will thus be seen that if the piston rod 30 is moved in the direction of arrow A, carriage 14 will move in the direction of arrow B, i.e., toward end 34 of track member 12 .
[0013] Hammer assembly 16 is provided with a hammer head 40 which engages the outermost end of a driving rod 42 of an anchor assembly, shown generally as 44 . Anchor assembly 44 , commonly referred to as a “plate” or “wing type” anchor, is described in one or more of U.S. Pat. Nos. 3,969,854, 4,044,513, 4,096,673, 4,802,317, and 5,031,370 (hereinafter Anchor Patents) incorporated hereinafter by reference for all purposes, and comprises an all-thread pull or setting rod 46 attached to the anchor 45 . It will be understood that while the apparatus 10 of the present invention is being described with reference to a particular anchor assembly, i.e., anchor assembly 44 as described in various of the Anchor Patents, the invention is not so limited and can be used to position a number of different types of workpieces, anchors or the like at a desired underground location. Thus, the term “workpiece” as used herein is intended to include any member or assemblage of members which has at least one end which can be forced, e.g., hammered, into a position in a substrate below a surface which overlies the substrate, and at least a second end which can be engaged by the hammer head 40 of the apparatus of the present invention. It is also to be understood that the term “surface” as used herein is intended to include the surface of materials such as asphalt, concrete and the like as will as referring to seabeds, lakebeds, riverbeds and the like. Further, the term “surface” or “ground surface” is not limited to generally horizontal surfaces but is intended to include any surface at any angle whether it be horizontal or at some angle to the horizontal.
[0014] Hammer assembly 16 is conveniently of the hydraulic or air hammer type which effects percussive movement of hammer head 40 as indicated by multiple arrows C. As is well known, percussion, jack or air hammers are generally of a type which are activated by compressive engagement with the tool or surface to be struck. Accordingly, as hammer head 40 engages the end of drive rod 42 it acts to percussively drive rod 42 and hence anchor assembly 44 into the ground G. As hammer head 40 percussively drives drive rod 42 of anchor assembly 44 into the ground G, the compressive force exerted on carriage 14 by piston/cylinder assemblies 26 ensures that hammer head 40 stays in percussive driving engagement with drive rod 42 .
[0015] As shown in FIG. 1, anchor assembly 44 has been driven to the desired depth into the ground G. At the commencement of installing the anchor assembly 44 into the ground G, the cruciform end portion 48 of the anchor 45 of anchor assembly 44 could be driven, manually if necessary, a short distance below the surface S for purposes of positioning it at the desired location and attitude relative to surface S. At this point, apparatus 10 could be positioned such that hammer head 40 was generally concentrically aligned with drive rod 42 . Piston/cylinder assembly 26 could then be actuated to compressively urge carriage 14 toward drive rod 42 , i.e., towards the end 34 of track member 12 , until hammer head 40 compressively engaged drive rod 42 whereupon hammer head 40 would begin its percussive striking of drive rod 42 . As disclosed in the Anchor Patents, successive sections of drive rod 42 can be secured together by couplings such that anchor assembly 44 can be driven to virtually any desired depth. As taught in at least some of the Anchor Patents, the drive rod 42 is removably attached to anchor assembly 44 . Accordingly, when the depth desired of anchor assembly 44 is reached, the drive rod(s) 42 can be removed.
[0016] Turning now to FIG. 2, there is shown the apparatus 10 of the present invention used to set the anchor assembly 44 . As noted above, anchor assembly 44 includes an all thread setting rod 46 which, as shown in FIG. 2 can be extended to virtually any length by a series of threaded couplings 50 which can be used to secure excessive lengths of setting rod 46 together. In any event, the end of setting rod section 46 distal anchor 45 below ground is attached to a threaded eye 52 . A yoke or harness assembly 54 is attached to eye 52 and to carriage 14 . In effect, harness 54 is comprised of a section of cable 55 welded or otherwise secured on each end to an eye 56 which can be secured to carriage 14 by means of a nut/bolt combination 58 which extends through carriage 14 .
[0017] As described in U.S. Pat. No. 4,802,317, to set the anchor 45 of anchor assembly 44 , the pull or setting rod 46 is pulled by a suitable pulling tool in a direction generally along the axis of the pull rod 46 . This results in the cruciform end 48 of anchor assembly 44 being pulled to the position shown in FIG. 2, i.e., with the anchor 45 basically pulled to a traverse or flat position in the ground. The apparatus of the present invention serves not only to position the anchor assembly 44 at a desired location below the surface S, but performs the function of a pulling or setting tool. Thus, if piston rod 30 is extended to the position shown in FIG. 2, i.e., in the direction of arrow D, carriage 14 will move in the direction of arrow D and exert an upward force on pull or setting rod 46 , the upward force being transmitted through the harness assembly 54 and the eye 52 to pull setting rod 46 up and move anchor 45 to the set position shown in FIG. 2.
[0018] Reference is now made to FIGS. 3 - 6 for a detailed description of the construction of the apparatus 10 of the present invention. With reference first to FIGS. 3 - 6 , it can be seen that track member 12 is comprised of an elongate box beam 60 having welded or otherwise secured thereto on opposite sides angle irons 62 and 64 . As can be seen, angle irons 62 , 64 form flanges 66 and 68 , respectively, which extend laterally outwardly from opposite sides of box beam 60 .
[0019] Carriage 14 as best seen in FIGS. 3, 5 and 6 comprises a pair of spaced side plates 70 and 72 which are held together by a series of nut and bolt assemblies 74 as described more fully hereafter. Welded or otherwise secured to the inside surface of side plate 70 are first and second spaced ribs 76 and 78 , ribs 76 and 78 projecting laterally inwardly from side plate 70 toward side plate 72 . As best seen in FIG. 3, a key plate 78 extends generally parallel to side plate 70 and is welded or otherwise secured to ribs 76 and 78 . Key plate 78 is provided with a dog 80 which projects laterally inwardly from key plate 78 , i.e., towards side plate 72 . In like fashion, side plate 72 is attached to spaced ribs 82 and 84 which project laterally from the inside surface of side plate 72 and are connected to a longitudinally extending second key plate 86 , key plate 86 carrying a dog 88 which projects laterally from key plate 86 toward side wall 70 . The purpose of dogs 80 and 86 will be described hereafter.
[0020] Carriage 14 is provided with a first set of upper roller assemblies and a second set of lower roller assemblies, described hereafter. The upper set of roller assemblies, best seen with reference to FIGS. 5 and 6, are comprised of a shaft 90 on which is rotatably mounted a sleeve 92 , sleeve 92 being attached at opposite ends to wheels 94 and 96 . Although not shown, there are bushings between side plates 70 and wheel 94 and side plate 72 and wheel 96 to maintain the roller assemblies in a predetermined position between the side plates 70 , 72 . Shaft 90 is threaded at its opposite ends and extends through suitable holes in plates 70 and 72 , the threaded ends of shaft 90 being secured to the carriage 14 by means of nuts 98 . There are a series of three such upper roller assemblies spaced along the length of carriage 14 as best seen with reference to FIGS. 3 and 6. It will be appreciated that the upper roller assemblies described above also serve the purpose of urging side plates 70 and 72 together.
[0021] In addition to the upper set of roller assemblies discussed above, there are a lower set of roller assemblies, which number 3 , and are also attached to carriage 14 and spaced along the length thereof. Two of the lower roller assemblies are as described above with respect to the upper roller assemblies. The third lower roller assembly differs in that they are not comprised of a shaft which extends through both the side plates 70 and 72 . Rather, as seen in FIGS. 5 and 6, the third lower roller assembly comprises a mount 100 secured to leg 63 of angle iron 62 . Fixedly received in mount 100 is one end of a shaft 101 , shaft 101 extending through side plate 70 and being secured thereto by nut 106 . Rotatably mounted on shaft 101 is a sleeve 108 , sleeve 108 carrying a wheel 102 and being rotatable around shaft 101 . In a similar fashion, and as seen in FIGS. 5 and 6, a second such lower roller assembly is disposed between side plate 72 and one leg 65 of angle iron 64 .
[0022] As can be seen, the upper and lower roller assemblies are positioned on carriage 14 such that the flanges 66 and 68 are sandwiched between the wheels, flanges 66 and 68 effectively forming a rail or track for the wheels of the roller assemblies. Thus, carriage 14 via the roller assemblies and flanges 66 and 68 , can move reciprocally along the length of track member 12 . While carriage 14 has been described in connection with the use of roller assemblies to enable carriage 14 to move along track member 12 , it is to be understood that the use of rollers is not necessary and that provision could be made to slidably mount carriage 14 on track member 12 , i.e., the use of rollers could be dispensed with. To this end, carriage 14 could be provided with pads made of a low friction material which would slide on a suitable surface(s) forming part of track member 12 . It will be apparent that other assemblies can be used to permit the reciprocal movement of carriage 14 along track member 12 .
[0023] Turning now to FIGS. 3 and 6, the hammer assembly 16 is shown in greater detail. Hammer assembly 16 includes a housing 110 which, as seen in FIG. 3, has a pair of slots or keyways 112 and 114 on opposite sides of housing 110 , keyway 112 opening in a direction toward side plate 70 , keyway 114 opening in a direction toward side plate 72 . Received in keyway 112 is dog 80 which acts as a key. As well, dog 88 acts as a key and is received in keyway 114 . It can be seen that this keyed relationship between carriage 14 and hammer assembly 16 prevents any relative longitudinal movement between carriage 14 and housing 110 . However, it can also be seen than when mounting hammer assembly 16 in carriage 14 , and prior to nut and bolt assemblies 74 being engaged, hammer assembly 16 can be effectively inserted into carriage 14 in a direction transverse to the longitudinal axis of carriage 14 so that the keys 80 , 88 engage the keyways 112 , 114 , respectively. Although not shown, it will be apparent to those skilled in the art that when hammer assembly 16 is of the percussion type, e.g., a hydraulic or air hammer it would be supplied with suitable compressed fluid or air via a suitable source and hoses (not shown) to power hammer head 40 in its percussive movement. Preferably, hammer assembly 16 is of the hydraulic powered type which obviates the necessity for having a compressed air source for a pneumatic hammer and a hydraulic fluid source for the piston/cylinder assemblies 26 , i.e., both the hammer assembly 16 and the piston/cylinder assemblies 26 can utilize the same power source.
[0024] As described above, apparatus 10 is provided with support assembly 20 which acts to hold the apparatus 10 in a predetermined position. As was also noted above, the support assembly 20 can be part of a backhoe or other motorized piece of construction equipment commonly used to hold and, if necessary or desired, to vary the position or angle of the member being held. However, it will be recognized that such a support assembly is not necessary. For example, apparatus 10 could be provided with a plurality of footers such that the apparatus could be moved to the desired location and placed there. Once the job of installing the workpiece was completed, the apparatus could then be picked up and moved to another location. However, it is more convenient, particularly when multiple workpieces, e.g., anchors, are being installed to have apparatus 10 mounted on a backhoe or the like to facilitate positioning it in a predetermined location and changing its attitude with respect to the surface into which the workpiece is being driven. A support such as support assembly 20 can be employed to maintain or exert a downward force on the apparatus 10 such that footer 38 is held firmly against the surface S. However, the apparatus could simply be made heavy enough such that, once placed in a desired location, the weight would be sufficient to withstand the reactive forces generated by compressively urging the carriage 14 in a generally downward direction coupled with the reactive forces generated by hammer assembly 16 . In this regard it is to be noted that while the actuator to compressively urge the carriage 14 and hence the hammer head 40 against the drive rod 42 is shown as a conventional hydraulic piston/cylinder arrangement, it is to be understood that the piston/cylinder assemblies could be dispensed with in favor of other mechanisms. For example, carriage 14 could be mounted on a rack and pinion mechanism, the pinion being rotatably attached to the carriage 14 and being driven in a suitable fashion. Additionally, a powered jack screw could be employed to compressively urge the carriage 14 against the workpiece. It is also to be understood that while far less desirable, a weight suspended from the boom of a crane or like could be positioned on and lifted off of carriage 14 , the weight serving as the actuator to compressively urge carriage 14 towards the first or lower end 34 of the track member number 12 .
[0025] While preferred embodiments of the present invention have been illustrated in detail, it is apparent that modifications and adaptations of the preferred embodiments will occur to those skilled in the art. However, it is to be expressly understood that such modifications and adaptations are within the spirit and scope of the present invention as set forth in the following claims. | An apparatus for installing a workpiece such as an anchor at a location underneath a surface such as the surface of the earth comprising an elongate track member having a first end positionable proximate as on the surface and a second end positionable distal the surface, a carriage slidably mounted on the track member for reciprocal movement therealong, a hammer assembly mounted on the carriage and having a hammer head reciprocally movable relative to the carriage in a direction toward and away from the first end of the track member, an operator to effect reciprocation of the hammer head and an actuator to compressively urge the carriage toward the first end of the track member. | 4 |
BACKGROUND OF THE INVENTION
[0001] The present invention generally relates to the treatment of equine hernias and more particularly pertains to a device and method that provides for the continuous and automatic manipulation of a hernia to promote healing.
[0002] Equines are fairly susceptible to hernias. Many such hernias are ‘umbilical hernias’ that are caused at birth such as when the mare rises too soon and thereby subjects the umbilical cord that is still attached to the foal to an excessive amount of tension. Such tension may cause a tear in the abdominal wall leaving only the skin covering the abdominal area to provide support. Hernias may additionally be caused by rearing, kicking, jumping or straining and are common to post-operative abdominal surgery. Ventral rupture may arise from an external injury. A hernia appears as a bulge in the animal's abdominal region which at the very least is considered unsightly and at worst may lead to complete failure of the abdominal wall and loss of all support for the intestines. The hernia may become strangulated which is a serious condition causing swelling, pain, hemorrhage, exudation, peritonitis and if not relieved, necrosis which can be fatal. Hernias are especially problematic in four-legged animals as the orientation of their abdominal region causes the entire weight of the intestines to be borne by the abdominal wall. This is further aggravated in horses in view of the immense size and weight of their intestines.
[0003] Surgery is common practice for the repair of equine hernias. In addition to the substantial cost involved, surgery always poses some degree of risk, including adverse reaction to anesthesia, infection as well as other potential complications along with an extended period of convalescence. Many heretofore employed methods for treating hernias in actuality merely amount to an effort to stabilize the herniation pending surgery by trussing or bandaging the region. While this typically prevents the hernia from increasing in size and may ease some of the discomfort that may be associated with the condition, it rarely if ever causes the hernia to heal or even shrink in size. The standard accepted method for the treatment of umbilical hernias in equine foals if the hernia is relatively small has been to wait until they are at least six months old to determine whether the hernia will heal on its own while optionally manipulating the hernia a few times a day during this period of time. Such manipulation includes applying pressure to the distended intestine so as to urge it back into the abdominal cavity while massaging the hernial ring in an effort to stimulate it to close. Some success can be realized with the massaging of the hernia. It has been theorized that such manipulation of the hernial ring actually induces the formation of new cell growth or scar tissue and the gradual tightening and closing of the ring. Additionally, the distended materials are forced back through the hernial ring and into the abdominal cavity to relieve some of the tension that the hernial ring is subjected to. The disadvantage associated with such approach is that the massaging sessions are time consuming and must be performed repeatedly. If by the sixth month the hernia has not healed, a clamp is attached to the skin where the hernia is located and tightened on a daily basis until the veterinarian determines the hernia to be ready for surgical repair. The clamp is painful to the foal and the entire approach is rather labor intensive insofar as daily attention is required.
[0004] An approach is needed for treating equine hernias that effectively promotes the healing rather than the mere stabilization of the hernia and that requires a minimal amount of expertise and effort to practice.
SUMMARY OF THE INVENTION
[0005] The present invention overcomes the shortcomings of the previously employed approaches for treating hernias in horses as well as other large four-legged animals. A non-invasive device and method are provided by which the hernia is automatically and continually manipulated to promote and expedite the healing process.
[0006] The method of the present invention provides for the continual and automatic manipulation of the hernia for an extended period of time. Pressure is focused on the herniated area while the precise positioning of the pressure within such area is subject to constant variation. In a preferred embodiment, the horse's own movements, especially the movements associated with walking, are relied upon to induce the slight shifting of the focus of pressure.
[0007] The device of the present invention consists of a relatively compliant support element that is adjustably fitted about the animal's abdomen wherein such element includes means for positioning a relatively rigid manipulator element directly over the hernia. The support element consists of a section of fabric configured to wrap around the animal's abdominal area and includes a series of straps to hold the fabric in place. The length of each of the straps is adjustable to allow the fabric to be tensioned to varying degrees and thereby tailored to a particular horse's needs. The manipulator element consists of a relatively stiff and hard mass of material which is positioned over the herniated region by the support element. The hard mass serves to focus pressure on the herniated intestines which not only serves to urge the herniated section of intestine back into the abdominal cavity, but tends to shift slightly whenever the animal moves and with each step as the animal walks. This constant shifting in effect causes the hernial ring to be continually manipulated which will eventually cause the hernial ring to close.
[0008] In a preferred embodiment, the manipulator element is held in a pocket formed in the support element. The size of the manipulator element and its shape may be tailored to suit the requirements of a particular patient. Various mechanisms may be employed to further stabilize the support element so as to keep it from shifting fore or aft along the horse's abdominal area. Hook and loop fasteners may be employed to seal the pocket and to facilitate adjustment of the support straps.
[0009] These and other features and advantages of the present invention will become apparent from the following detailed description of a preferred embodiment which, taken in conjunction with the accompanying drawings, illustrates by way of example the principles of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] [0010]FIG. 1 is a perspective view of the device of the present invention fitted about a horse;
[0011] [0011]FIG. 2 is a enlarged plan view of the device of the present invention laid out on a flat surface;
[0012] [0012]FIG. 3 is a further enlarged cross-sectional view taken along lines 3 - 3 of FIG. 2; and
[0013] [0013]FIG. 4 is a perspective view of an embodiment of the manipulator element.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0014] The Figures generally show the device of the present invention. The device is fitted about a horse or other four legged animal suffering from a hernia and provides for the automatic and continual manipulation of the hernia. Walking or any other significant movement made by the animal will cause pressure focused by the device on the hernia to continually shift slightly thereby inducing a massaging action that has been found to be effective in expediting the healing process.
[0015] [0015]FIG. 1 shows the device 12 of the present invention fitted about a horse. The device generally consists of a generally rectangular support element 14 that includes a plurality of adjusting straps 16 . The support element is dimensioned to fit about horse's entire torso and abdomen while the adjustment straps are of sufficient length to engage rectangular slides and allow for a range of adjustment. Any of a variety of securing mechanisms may alternatively be employed including for example a belt and buckle combination. A rectangular slide in combination with a hook and loop fastener is preferred due to its infinite adjustability and due to the fact that it can be quickly and easily fitted and adjusted. Additional straps may optionally be fitted to positively maintain the device in position, including for example a crupper 15 and/or various breast straps 17 , 19 , 21 .
[0016] The support element 14 includes a pocket 20 formed therein configured for receiving a manipulator element therein. The pocket is oriented on the support element so as to allow a manipulator element contained therein to be positioned directly over the hernia. The pocket further provides for the manipulator element to be securely sealed therein yet allows for quick and easy access thereto.
[0017] [0017]FIG. 2 is an enlarged view of the device 12 of the present invention spread out on a flat surface. The support element 14 has a generally rectangular shape. A slightly trapezoidal shape may be desirable for some applications. The support element may be made of a fabric and has a leading edge 22 , a trailing edge 24 and two lateral edges 26 , 28 . Extending from one lateral edge 26 is a series of straps 16 . The straps may be attached to the entire width of the support element in order to enhance the support provided by the support element. Alternatively, a shorter section of strap may be attached to the support element. A section of hooks 32 and a section of loops 30 of a hook and loop fastener combination may be attached to the surface of the strap. In the preferred embodiment shown, the loop surface 32 is present near the distal end of each of the straps while a section of the complementing hook surface 30 is attached to each of the straps proximally thereto. A series of rectangular slides 18 , configured to receive the straps 16 , are attached to the support element adjacent the opposite lateral edge 28 . The length of the distal ends of the straps is selected to extend from lateral edge 26 , through the respective rectangular slide on the opposite lateral edge 28 and back so as to allow the loop surface 32 to engage the hook surface 30 . Pocket 20 is positioned adjacent the trailing edge 24 of the support element. It is preferable that the pocket is offset with respect to the centerline of the device in order to ensure that the rectangular slides do not press on the horse's backbone when fitted. The pocket may be configured to open along the trailing edge where a hook and loop fastener 33 is fitted so as to allow a manipulator element to be accessibly retained within the pocket. The bulge 31 shown in the center of the pocket is formed by the manipulator element 32 contained therein in combination with a dense foam material 35 that surrounds the manipulator element to prevent damage to the skin caused by a concentration of pressure.
[0018] [0018]FIG. 3 is a cross-sectional view of the support element 14 showing the manipulator element 32 wrapped in a dense foam-like material 31 in place within pocket 20 . The pocket is dimensioned to maintain the manipulator element therein in position. The manipulator element and foam-like material is easily removable through the opening formed along trailing edge 24 . The opening is preferably sealed using a strip of hook and loop fastener 33 .
[0019] [0019]FIG. 4 is an enlarged view of the manipulator element 32 . The element is formed of a relatively rigid material such as a plastic and has a generally rectangular shape with rounded corners. The element includes a convex surface or dome 34 , that may preferably be defined by a compound curve, to further serve to focus pressure applied therewith to the hernia. The manipulator element may optionally a cut-out section 36 for use on a male horse to avoid interference with the genitalia. While the dimensions of the manipulator element will be dictated by the size of the horse and hernia, a 4″×6″ size would be required for a new born foal while a 6″×8″ size may be required for a yearling. A dense foam-like material may additionally be disposed about the manipulator element to prevent damage to the surrounding skin.
[0020] The shape of the support element 14 and manipulator element 32 may have a slightly cut out configuration to accommodate the male equine genitalia. Additionally, because the various breeds differ slightly in shape and confirmation, attachments may be used to prevent the support element from shifting. A type of breast collar may be used to keep the device from moving aft on the male and a crupper strap may be used to keep the trailing edge from rolling over or twisting.
[0021] In use, a manipulator element 32 of the appropriate size is first selected to treat the particular herniation of a particular horse. The manipulator element is inserted into the pocket 20 of the support element 14 and the opening is sealed by aligning the hook and loop strips 30 fitted along the trailing edge of the pocket. The support element is then attached to the patient by maintaining the manipulator element directly over the hernia while tightening the adjustment straps. The tension in the straps must be adjusted to maintain the support element and manipulator element in position and such that the manipulator element focuses a sufficient amount of pressure on the hernia without causing undue discomfort to the horse. The device may be left in place around the clock but should be checked periodically to ensure the device is properly positioned and that no sores are being formed. Additionally, the condition of the hernia should be monitored periodically. It has been found that use of the device and method of the present invention can cause the hernia to heal within a matter of a few weeks.
[0022] While a particular form of the invention has been illustrated and described, it will also be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention. For example, the device can be adapted for use with any of a large number of similarly shaped animals that may suffer from hernias. The support element may also be used without the manipulator element as a post-surgical pressure bandage. Various adjustment mechanisms may be used to maintain the support element and manipulator element in place. Additionally, any of various materials may be used to form both the support element as well as the manipulator element. Finally, it is additionally contemplated that an active massaging device, such as a battery operated massager may be positioned within the pocket formed on the support element to further augment the massaging action generated by the animal's own movements. Accordingly, it is not intended that the invention be limited except by the appended claims. | A device and method for treating equine hernia wherein a manipulator element is held in place to exert pressure on the affected abdomen to thereby push the bowel into the abdominal cavity. Any movements made by the horse, especially as by the act of walking or exercising, cause the manipulator element to shift slightly and thereby automatically manipulate the hernial ring. Such manipulation serves to expedite the healing process often obviating the need for surgical intervention. | 8 |
SUMMARY DESCRIPTION OF THE DEVICE PRODUCED BY THIS INVENTION
The ceramic device of this invention has a plurality of parallel walls connected to each other by spacers and arranged in a regular pattern which may be in the form of a spiral or be in the form of flat sheets stacked upon each other as shown in FIGS. 1-2 respectively. The arrangement of the walls forms a multiplicity of channels running through the device which are interrupted only by the spacers joining adjacent walls, and are open at both ends. Spacers connect adjacent walls at regular intervals through the structure to give the device integrity and strength. The spacers may have any cross section but circular or rectangular cross sections are preferred. They may be arranged regularly (e.g., in parallel rows) or irregularly. The composition of the walls and spacers may be of any desired ceramics: examples include petalite, cordierite, alumina silicates, alumina-silica-magnesia, zircon, mullite or alpha alumina. If desired the walls may have one or more layers of differing ceramic materials.
In the preferred embodiment of the invention the walls range between 0.005 inch to 0.012 inch in thickness and the distance separating walls is in the range 0.005 inch to 0.030 inch. The width of the spacers is in the range 0.010 inch to 0.300 inch: they may be of any desired length. This distance between spacers is in the range 0.010 inch to 0.300 inch. This invention is not however limited to producing a device with the dimensions here indicated.
The object of the invention is to provide a method of constructing a ceramic device which may serve as a catalyst support, whereby the device is formed in a substantially continuous process on conventional machinery with or without minor modifications obvious to those skilled in the art. It should be further understood that this ceramic catalyst support, on coating with an appropriate catalyst, for instance a metal or metals from Group IIA, IB, VB, VIB, VIIB, and VIII, could be suitable for use as a catalytic converter for the conversion of harmful automobile pollutants into innocuous materials.
Several patents describe methods of constructing a ceramic device having thin microporous walls and channels open at both ends. U.S. Pat. Nos. 3,824,196 and 3,983,283 describe the extrusion of structures containing many channels from a plastic composition of the desired ceramic. Other patents describe methods of producing sheets of ceramic. These sheets are then stacked together in a manner that provides for channels between adjacent sheets. In most cases the sheets must be wavy or corrugated.
U.S. Pat. No. 3,926,702 describes the preparation of sheets by preparing a fluid suspension of ceramic powder in a phenolic resin that has been dissolved in alchohol and flowing this into a wavy mold that is subsequently heated to drive off the alchohol, then further heated to fire the ceramic. The single sheet produced from the mold is combined with sheets produced similarly to produce the device.
U.S. Pat. No. 3,982,981 describes a method whereby sheets of ceramic are prepared in a continuous process on a fourdrinier paper machine from a suspension of ceramic powder and natural or synthetic fibers. After sheets so produced have been corrugated they are assembled with each other into a device.
U.S. Pat. No. 3,948,810 describes a device whereby sheets of ceramic (formed in a process not described in the patent) are assembled in layers alternating with layers of ceramic balls or sheres that have been formed in a separate process not specified in the patent.
U.S. Pat. No. 3,963,504 describes a process by which a thermoplastic composition of ceramic powder, high molecular weight polyolefin, and plasticizer are formed into a sheet by pressing between two platens in an hydraulic press. After the sheets are assembled together the plasticizer is removed by solvent causing the sheets to become inflexible.
The instant invention described herein differs from those mentioned in that it describes formation of a ceramic sheet by coating onto a substrate sheet. None of the patents cited make use of a coating process. Further the substrate sheets performs several unique functions:
1. It supports the ceramic film
2. In the second embodiment of the invention, it serves to define the form of the ceramic sheet (the production of extensions in in the film that become spacers).
3. When the sheets are assembled into a device, it serves to space the sheets of ceramic equidistant and prevent their premature collapse by physically occupying the space that will remain open in the finished device.
4. In the first embodiment, it physically occupies the space that later will become open; thus allowing spacers to be produced by the technique to subsequently be described herein.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a view of a ceramic device made by rolling a bicomponent sheet upon itself.
FIG. 2 is a view of a ceramic device made by stacking bicomponent sheets one upon the other.
DESCRIPTION
The essence of the present invention lies in the construction of a unique bicomponent film. The film is formed by coating a suspension of ceramic powder in an organic binder over a film composed of wax, plastic, or paper. In the simplest embodiment of this invention, a fluid mixture of solvent, organic binder, and ceramic powder is coated onto a flexible sheet by any of the many methods common to the art. This flexible sheet may be self-supporting or be supported by a paper web. The flexible sheet may also be formed by coating the film-forming material directly onto a properly prepared paper web.
The solvent is evaporated off to provide a bicomponent film composed of a continuous layer of ceramic in binder and a continuous layer of the flexible sheet. The organic binder may be any one of a number of substances capable of being cured to a rigid insoluable form. Preferred are thermosetting resins such as phenolics, urea-formaldehyde, melamine-formaldehyde, and epoxy resins. The flexible sheet is composed of any one of many materials that either form films or are available commercially as films and can be removed by heat, solvents or chemical attack. Suitable materials include waxes and modified celluloses. The bicomponent film so produced may be rolled up into a spiral cylinder or cut into sheets and the sheets stacked together.
If a paper web has been used for support, this is separated and discarded. Paper coated with release agent is preferable since it facilitates this separation and may be re-used. Gaps are formed perpendicular to the plane of the sheets by drilling, punching, or sawing. These gaps are filled with a suspension of ceramic in binder preferably but not necessarily similar to that used in the coating process.
The ceramic in the gaps ultimately forms the supporting spacers. When these operations have been completed, the organic binder is cured to a rigid insoluable form. Following this, the removable layer is extracted typically, though not necessarily, by dissolution in a suitable solvent, or by melting. The structure so formed is heated to carbonize the binder and then heated further to fire the ceramic. Similar carbonization and firing sequences are described in U.S. Pat. No. 3,926,702 and other patents.
In a second embodiment of this invention, a unique bicomponent film is prepared having spacers as an integral part of the film rather than requiring their formation at a later stage, as described in the first embodiment of the invention. This film is produced by the following steps:
1. A sheet of suitable material is perforated. The composition of this sheet would correspond to that of the removable layer previously described. The perforations, whose shape determines the cross section of the spacers, may be of any design, but may conveniently be made circular or rectangular.
2. The sheet so prepared is laminated to a support sheet (for instance a paper web) in such a way that the two sheets may be separated by peeling them apart. This second sheet will be-called the release sheet.
3. A coating material is prepared from a suitable binder and selected ceramic powder and may include a solvent for the binder. This suspension is coated by conventional methods well known in the art on to the composite sheet prepared according to step two. The coating must remain fluid long enough for it to fill the perforations. The solvent is then removed by evaporation.
4. Prior to assembling the film into the structure of the support, the release sheet is removed as indicated in the description of the first embodiment.
5. The finished support is heated to carbonize the binder and then heated further to fire the ceramic. During the firing process the carbon burns off.
Bicomponent films of this type differ from these discussed in the first embodiment of the invention in having a multiplicity of ridges or pillars that penetrate the second layer and are flush with the surface of this layer. When this bicomponent film is rolled up or assembled into a stack of sheets these pillars or ridges make contact with the adjacent ceramic layer. During the curing process these points of contact band together, thus forming the spacer supports. In either embodiment, application of the ceramic binder layer is not limited to one coating pass. In some cases it may be desirable to have two ceramics in the finished support or may be desirable to use two different binders to facilitate the shaping of the support. Both of these objectives can be accomplished by applying a second coating over the first after the first layer is hardened. In another variation of this invention, wax is coated directly onto release paper. This wax may be coated using a special roll that leaves portions of the release sheet without a coating of may be coated solid and later perforated without perforating the release sheet.
EXPERIMENTAL
100 Parts of wt. of resin PMH707 were added to 45 parts of wt. of PMH707 hardener (Palmer Products, Inc.) and the resulting mixture dissolved in tolulene. To one part of the resin and hardener 4 parts by wt. of #613 calcined alumina A-10 (Whittaker, Clark, and Daniels, Inc.) were added. The alumina, resin and solvent were thoroughly mixed to produce a coating slurry. An 0.018 inch thick beeswax sheet from A.I. Root Co. was perforated with holes about 0.035 inch in diameter and spaced about 0.250 inch apart in a staggered pattern using a hollow punch.
Layers of tape were placed 0.500 inch apart on the punched out section of the beeswax sheet and the sheet was placed on release paper. The coating was spread between the pieces of tape by use of a stiff blade. The coating was about 0.009 inch thick. After the solvent was evaporated, the coated area was cut from the beeswax sheet and wrapped around a 0.500 inch spindle. The sample had seven layers. The epoxy was allowed to harden at room temperature for 10 days. The sample was put in an oven at 200° F. and the wax melted out. Subsequently the binder was carbonized at 500° F.
The resulting sample was circular and measured 13/16 inch in diameter, had a 1/2 inch open area in the center, and was 3/8 inch high. The sample had six channels which were open along their entire length except for their spacers. | A method of producing a ceramic device having thin walls of microporous ceramic material, channels open at both ends, and a large exposed internal surface area. The method comprises preparation of a unique bilayer film and assembly of this film into a ceramic device by rolling it upon itself into a spiral cylinder or by arranging it in stacks of sheets. One layer of the film is composed of ceramic powder in an organic binder; the other of a material which may be removed by physical or chemical means. | 8 |
BACKGROUND
[0001] This section provides background information to facilitate a better understanding of the various aspects of the disclosure. It should be understood that the statements in this section of this document are to be read in this light, and not as admissions of prior art.
[0002] The present disclosure relates generally to wellbore operations and equipment and more specifically to actuation devices for downhole tools (e.g., subsurface tools, wellbore tools) and methods of operation.
[0003] Hydrocarbon fluids such as oil and natural gas are produced from subterranean geologic formations, referred to as reservoirs, by drilling wells that penetrate the hydrocarbon-bearing formations. Once a wellbore is drilled, various forms of well completion components may be installed in order to control and enhance the efficiency of producing fluids from the reservoir and/or injecting fluid into the reservoir and/or other geological formations penetrated by the wellbore. In some wells, for example, valves are actuated between open and closed states to compensate or balance fluid flow across multiple zones in the wellbore. In other wells, an isolation valve may be actuated to a closed position to shut in or suspend a well for a period of time and then opened when desired. Often a well will include a subsurface valve to prevent or limit the flow of fluids in an undesired direction.
SUMMARY
[0004] A downhole tool in accordance to aspects of the disclosure includes a housing forming a bore to convey a wellbore fluid, an actuating piston moveably disposed in a cylinder located in the housing adjacent to the bore and a barrier fluid isolating the actuating piston from the bore. The downhole tool may include a compensator piston in communication with the barrier fluid and the bore that is moveable to balance the pressure between the barrier fluid and the bore. The downhole tool may include a check valve device, for example disposed with the compensator piston, which is adapted to selectively allow fluid to flow across the compensator piston between the bore and the barrier fluid.
[0005] A method according to one or more aspects of the disclosure includes utilizing a downhole tool in a wellbore, the downhole tool including a housing forming a bore to convey a wellbore fluid, an actuating piston moveably disposed in a cylinder that is located in the housing, a barrier fluid isolating the piston seal from the bore; and balancing pressure between the barrier fluid and the bore in response to moving a compensator piston in communication between the barrier fluid and the bore.
[0006] A well system includes a downhole tool connected in a tubular string and disposed in a wellbore, the downhole tool including a housing forming a bore to convey a wellbore fluid, an actuating piston moveably disposed in a cylinder located in the housing adjacent to the bore, a barrier fluid isolating the actuating piston from the bore, and a compensator piston in communication with the barrier fluid and the bore that is moveable to balance the pressure between the barrier fluid and the bore.
[0007] This summary is provided to introduce a selection of concepts that are further described below in the detailed description. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of claimed subject matter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] The disclosure is best understood from the following detailed description when read with the accompanying figures. It is emphasized that, in accordance with standard practice in the industry, various features are not drawn to scale. In fact, the dimensions of various features may be arbitrarily increased or reduced for clarity of discussion.
[0009] FIG. 1 a schematic of a well system incorporating an embodiment of a downhole tool incorporating an isolated tool actuator according to one or more aspects of the disclosure.
[0010] FIG. 2 is a schematic illustration of a wellbore tool utilizing an isolated tool actuator according to one or more aspects of the disclosure.
[0011] FIGS. 3 and 4 are schematic views of a compensator piston of an isolated tool actuator located at travel limits according to one or more aspects of the disclosure.
[0012] FIG. 5 is a schematic illustration of a prior art subsurface valve with a balanced piston actuator.
DETAILED DESCRIPTION
[0013] It is to be understood that the following disclosure provides many different embodiments, or examples, for implementing different features of various embodiments. Specific examples of components and arrangements are described below to simplify the disclosure. These are, of course, merely examples and are not intended to be limiting. In addition, the disclosure may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed.
[0014] As used herein, the terms connect, connection, connected, in connection with, and connecting may be used to mean in direct connection with or in connection with via one or more elements. Similarly, the terms couple, coupling, coupled, coupled together, and coupled with may be used to mean directly coupled together or coupled together via one or more elements. Terms such as up, down, top and bottom and other like terms indicating relative positions to a given point or element may be utilized to more clearly describe some elements. Commonly, these terms relate to a reference point such as the surface from which drilling operations are initiated.
[0015] In a non-limiting embodiment the downhole tool is a subsurface flow control device or valve in which the tool actuator engages and opens a valve closure member (e.g., flapper, ball, sleeve, etc.). In another embodiment, the tool actuator can progressively operate a variable choke member. The tool actuator includes without limitation devices which are known in the art and commonly referred to as flow tubes and sleeves. The closure member may include various devices such as and without limitation to flappers, ball valves and sleeves. The term piston is utilized in the disclosure to refer to a device that is moved in response to a control signal to actuate a downhole tool. The signal may be, for example, an electric, mechanical, and/or fluidic signal urging the piston to move at least in a first direction. The piston and the control signal (e.g., driving force) may include without limitation a fluidic piston, an electric solenoid, a gear device, and combinations thereof.
[0016] Subsurface valves are commonly actuated to a first position (e.g., open) by the application of hydraulic pressure, for example from the surface, and biased to the second position (e.g., closed) by a biasing mechanism (stored energy assembly), such as an enclosed pressurized fluid chamber or a mechanical spring. The fluidic pressure may be applied to a piston and cylinder assembly, for example, that acts against the biasing force of the biasing mechanism to open and hold the valve opened. The biasing force acts on the piston to move it to a position allowing the closure member to move to the closed position when the actuating fluid pressure is reduced below a certain value. Examples of some subsurface valves are disclosed in U.S. Pat. Nos. 4,161,219 and 4,660,646 and U.S. Patent Application Publications 2009/0266555, 2010/0006295 and 2010/0139923, which are all incorporated herein by reference.
[0017] FIG. 1 is a schematic of a well system 10 incorporating an embodiment of a downhole tool 12 comprising an actuator assembly 14 according to one or more aspects of the present disclosure. Depicted well system 10 includes a wellbore 16 extending from a surface 18 and lined with casing 20 . A tubular string 22 is disposed in wellbore 16 . Downhole tool 12 is depicted in FIG. 1 as non-limiting embodiment of a subsurface valve or flow control device, e.g., a subsurface valve. Valve 12 is connected within tubular string 22 for selectively controlling fluid flow through tubular valve 12 and tubular string 22 . For example, subsurface valve 12 may be used to block the flow of reservoir fluid 2 through tubular string 22 to the surface when fluid 2 flows from formation 4 through tunnels 6 and into wellbore 16 and tubular string 22 under a greater pressure than desired.
[0018] Depicted valve 12 is operated in this example to an open position in response to a signal (e.g., electric signal, fluidic signal, electro-fluidic signal, mechanical signal) provided via control system 24 . Depicted control system 24 includes a power source 26 operationally connected to actuator apparatus 14 to operate a tool member 30 (e.g., valve member) from the one position to another position. In FIG. 1 , the valve member is in a closed position blocking fluid flow through the bore of the tubular string 22 . In the non-limiting embodiment depicted in FIG. 1 , control system 24 is a fluidic (e.g., hydraulic) system in which fluidic pressure 26 is provided through control line 28 to actuator apparatus 14 which applies an operational force that moves the actuator apparatus in a first direction engaging and actuating tool member 30 to an open position allowing the reservoir fluid in tubular string 22 to flow across tool member 30 . Hydraulic pressure is maintained above a certain level to hold the tool member 30 in the open position. To actuate subsurface valve 12 to the closed position, as shown in FIG. 1 , the hydraulic pressure via control line 28 is reduced below a certain level. As is known in the art, the hydraulic pressure is reduced below the level of the force that biases the valve member 30 to the closed position.
[0019] FIG. 2 illustrates an embodiment of a downhole tool 12 in the form of a subsurface valve and isolated actuation assembly 14 according to one or more aspects of the disclosure. Valve 12 includes a housing 32 having a longitudinal bore 34 . Valve member 30 is a flapper in this embodiment. An engaging member 36 (e.g., flow tube, sleeve, tubular member) having a central longitudinal bore co-axially aligned with bore 34 of housing 32 is movably disposed within housing 32 . Engaging member 36 is referred to herein as a flow tube. In this embodiment, the valve actuation assembly or apparatus 14 comprises an actuation piston 38 operational disposed with the flow tube 36 . Piston 38 is moveably positioned within a cylinder 40 . In this example, piston 38 is a balanced piston and a biasing energy source 42 biases piston 38 toward the closed position (upward in the illustrated embodiment). In the depicted embodiments piston 38 is not fixedly, or permanently, connected to the flow tube 36 and a second biasing mechanism 44 biases flow tube 36 toward the closed position. In some embodiments the piston 38 and flow tube may be interconnected to move together in both the first and second directions. Biasing energy source 42 is illustrated as a pressurized fluid and second biasing mechanism 44 is illustrated as a spring.
[0020] Actuating piston 38 includes piston seals 46 sealing the piston in the cylinder 40 . In a traditional balanced piston valve design, as illustrated for example in FIG. 5 , the piston seals 46 are exposed to the wellbore fluid 2 . The isolated actuating assembly or apparatus 14 as depicted for example in FIGS. 2-4 isolates the piston seals 46 from the wellbore fluid.
[0021] The isolated from wellbore fluid actuator assembly 14 includes a barrier fluid 48 that is contained with seals 50 on the flow tube 36 and an additional piston 52 disposed in a second cylinder 54 to balance the pressure of the barrier fluid 48 to the wellbore fluid 2 , thus reducing the minimum pressure across the flow tube. This additional piston 52 , referred to as a compensator piston, is designed so that if it reaches a maximum or minimum position (so that it can no longer balance pressure) it activates a flow control device, e.g., check valves or other process, to allow for fluid (barrier or wellbore) to bypass the compensator piston.
[0022] The barrier fluid 48 may be a fluid that is clean relative to the wellbore fluid and may be a selective to be less corrosive than the wellbore fluid. The barrier fluid 48 may provide protection to the piston 38 and/or piston seals 46 from wellbore pressure, chemical properties, state (fluid/gas) and debris in the wellbore fluid. The free floating compensator piston 52 balances, or substantially balances, the pressure across the flow tube 36 . The thickness of the flow tube 36 may be minimized as it will not have to withstand high pressure differentials.
[0023] As there may be minimal fluid losses (or gains) in the barrier fluid 48 volume, due for example to leakage across the seals 50 , the compensator piston 52 must allow fluid bypass if it is no longer able to equalize the pressure. As such, once the compensator piston reaches its maximum operational travel limit positions (uphole or downhole), it will active a check system 58 to allow fluid bypass from the wellbore fluid to the barrier fluid zones.
[0024] FIG. 3 illustrates downhole tool 12 with the compensator piston 52 located at a first travel limit 56 , for example a maximum travel limit in response to wellbore fluid pressure. This limit may be reached for example in response to the loss of barrier fluid 48 across seals 50 . At this first travel limit the wellbore fluid 2 may flow through a check valve system 58 of the compensator piston 52 as illustrated by the arrows and thereby equalize the pressure across the flow tube 36 (between the barrier fluid and the wellbore fluid).
[0025] FIG. 4 illustrates downhole tool 12 with the compensator piston 52 located at a second travel limit 60 , for example maximum travel limit in response to barrier fluid pressure. At this second travel limit 60 the barrier fluid 48 may flow through the check valve system 58 of the compensator piston 52 as illustrated by the arrows and thereby equalize the pressure across the flow tube.
[0026] To open subsurface valve 12 , fluid pressure 26 is applied through control line 28 to piston 38 positioned in the cylinder 40 providing a downward force on flow tube 36 . The terminal end of the flow tube 36 physically contacts member 30 (valve member), or a lever or other closure member device, moving tool member 30 about a pivot connection to an open position permitting fluid flow through bore 34 opened through valve 12 and flow tube 36 toward the surface. Subsurface valve 12 is maintained in the open position by the maintenance of hydraulic pressure against piston 38 .
[0027] To close subsurface valve 12 , for example due to a pressure kick in the well, the hydraulic pressure can be relieved from control line 28 to a level such that biasing mechanisms 42 moves piston 38 upward and biasing mechanism 44 moves flow tube 36 upward permitting valve member 30 to close. As noted above, the piston and flow tube may be connected in a manner to move in unison in the upward and in the downward directions.
[0028] The foregoing outlines features of several embodiments so that those skilled in the art may better understand the aspects of the disclosure. Those skilled in the art should appreciate that they may readily use the disclosure as a basis for designing or modifying other processes and structures for carrying out the same purposes and/or achieving the same advantages of the embodiments introduced herein. Those skilled in the art should also realize that such equivalent constructions do not depart from the spirit and scope of the disclosure, and that they may make various changes, substitutions and alterations herein without departing from the spirit and scope of the disclosure. The scope of the invention should be determined only by the language of the claims that follow. The term “comprising” within the claims is intended to mean “including at least” such that the recited listing of elements in a claim are an open group. The terms “a,” “an” and other singular terms are intended to include the plural forms thereof unless specifically excluded. | A downhole tool in accordance to aspects of the disclosure includes a housing forming a bore to convey a wellbore fluid, an actuating piston moveably disposed in a cylinder located in the housing adjacent to the bore and a barrier fluid isolating the actuating piston from the bore. The downhole tool may include a compensator piston in communication with the barrier fluid and the bore that is moveable to balance the pressure between the barrier fluid and the bore. | 4 |
BACKGROUND
[0001] The subject matter of the present invention is a device and a method for acquiring and processing measurement quantities in a sewing machine.
[0002] It is known that in sewing machines a camera can be provided that monitors the article being sewn during the sewing process. In this way, differences in quality that may be caused by different transport characteristics of different types of sewn articles can be acquired.
[0003] As is disclosed for example in DE 19850742, the camera can be used to determine the position of two adjacent stitch points of the sewing needle on the article being sewn. A comparator device determines deviations of the actual values from stored target values for the position of these stitch points, and influences the advance of the material in such a way that subsequent stitch points deviate as little as possible from the desired target positions.
[0004] Although the characteristics of the article being sewn, which can vary greatly, in interaction with the device for transporting the article being sewn are not the only factors responsible for the problem-free functioning of a sewing machine, up until now a camera has been used only to monitor the article being sewn.
SUMMARY
[0005] Therefore, the object of the present invention is to create a device and a method for using a camera to acquire and process measurement quantities in a sewing machine that ensure problem-free operation of the sewing machine.
[0006] This objective is achieved by a device and a method for acquiring and processing measurement quantities in a sewing machine. With the method according to the present invention and the device according to the present invention, sewing machine elements and their disposition on the sewing machine can be monitored. Thus, for example, items of information concerning the type of particular sewing machine elements and their correct disposition on the sewing machine can be acquired. The acquisition and evaluation take place using one or more cameras connected to an image processing unit. According to the position of the camera, or of an imaging optical system allocated to the camera, imaging information on sewing machine elements can be acquired from the inside of the lower arm (e.g., spool, spool capsule, or throat plate) or from above the throat plate (e.g., sewing needle, sewing foot, throat plate, hoop). The cameras and/or the imaging optical systems, or parts thereof, can be situated so as to be capable of movement. They can for example be mounted so as to be capable of pivoting about one or more pivot axes, and/or so as to be capable of movement along an axis of translation. Changes of position can be brought about for example using step motors or other drive means that can be controlled by the sewing machine control unit. The image information is evaluated by an image processing unit. The image processing unit can use features, or comparison or target quantities, that are stored in a target quantity memory. In a preferred construction of the present invention, the image processing unit can in addition also store information or target quantities in the target quantity memory. Such target quantities can for example include color or character codes, or information concerning shape, contour, structure, or position of a sewing machine element.
[0007] The image processing unit can be functionally connected with the sewing machine control unit or can be a component thereof. The image processing unit can check for the presence and/or the correct mounting of one or more sewing machine elements and/or their spatial position on the sewing machine. Various functions of the sewing machine control unit that use the information from the image processing unit can contribute to the automation, simplification, or improvement of operating, monitoring, and control tasks, the issuance of warnings when errors occur or the execution of certain subsequent operations, the prevention of accidents, or the ensuring or improvement of the quality of the sewing process.
[0008] In addition to the acquisition and evaluation of information concerning sewing machine elements that are components or accessories of the sewing machine, the image processing unit can also be fashioned for the acquisition and evaluation of information concerning sewing elements. The category of sewing elements includes the article being sewn and the threads used for the processing of the article being sewn before and after the processing. The information concerning sewing elements can also be used by the sewing machine control unit in particular for the controlling or regulation of sewing processes, for example for influencing the longitudinal and/or transverse movement of a material transport device.
[0009] The camera can also be used to determine criteria of comparison for the target quantity memory. Alternatively, or in addition, such features or target quantities can also be read into the target quantity memory via an interface.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The present invention is explained in more detail in the following with reference to the drawing Figures.
[0011] FIG. 1 shows a sewing machine in a side view;
[0012] FIG. 1A is a detail view taken from FIG. 1 in the indicated area A in the area of the shuttle in an enlarged, partially exploded view;
[0013] FIG. 2 shows a schematic diagram of a part of a sewing machine having an acquisition device;
[0014] FIG. 3 a is a view of a first throat plate;
[0015] FIG. 3 b is a view of a second throat plate;
[0016] FIGS. 4 a - 4 d are views of four different types of sewing feet;
[0017] FIG. 5 a shows a side view of a sewing machine with a correctly fastened sewing foot;
[0018] FIG. 5 b shows a side view of a sewing machine with an incompletely fastened sewing foot;
[0019] FIG. 5 c shows a side view of a sewing machine in which the sewing foot lies flat;
[0020] FIG. 5 d shows a side view of a sewing machine in which the sewing foot lies obliquely;
[0021] FIGS. 6 a - 6 i are views of nine different sewing needle types.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0022] FIGS. 1 and 1 A schematically show a sewing machine 1 having a base 3 , a pedestal 5 that is fastened to and supported on base 3 , and a free or lower arm 7 fastened thereto, as well as upper arm 9 . A display unit 10 , or a display screen and operating elements 12 , are situated laterally on the upper arm 9 . The front end of upper arm 9 is formed as a sewing machine head 11 . On the lower side of sewing machine head 11 , extends a needle bar 13 having a needle holder 15 , a sewing needle or needle 17 placed in needle holder 15 , a sewing foot holder 19 having a sewing foot 21 placed therein, and a threading device 23 . Two cameras 25 , represented by broken lines, are integrated into the sewing machine head 11 , or in an additional module 27 that is fastened laterally thereon and that can be removed, in such a way that they can acquire one or more of the sewing machine elements or parts thereof that are visible between the sewing machine head 11 and the lower arm 7 . An additional camera 25 , likewise represented by broken lines, is situated in the front area of the lower arm 7 in such a way that it can acquire sewing machine elements or parts thereof that are visible there. Alternatively, cameras 25 can also be situated in other areas of the sewing machine 1 , for example in the area of the pedestal 5 or of the upper arm 9 . In addition, optical elements, such as for example light waveguides 29 , lenses 31 , or mirrors for the formation of an acquisition area, can be placed on the camera 25 . In this way, even unfavorably situated areas of acquisition can be imaged using a camera 25 . Cameras 25 can thus be situated on the sewing machine 1 where there is available space for them, largely independent of their areas of acquisition. In this way, even sewing machine elements that are difficult to access can be acquired. In the simplest embodiment of the present invention, one camera 25 is sufficient. A plurality of cameras 25 can however also work together in such a way that objects such as sewing machine elements or sewing elements can be acquired from a variety of directions.
[0023] The designation “sewing machine elements” includes components and accessory parts that are situated fixedly on the sewing machine 1 as well as parts and accessories that can be detached from the sewing machine; for example, the needle bar 13 , the needle holder 15 , the needle 17 , the sewing foot holder 19 , the sewing foot 21 , the threading device 23 , a throat plate 33 , a hook 35 , a bobbin case 37 placed in the hook 35 , or a bobbin 39 placed in the bobbin case 37 that is empty or is partially or completely equipped with thread. For better visibility of the sewing machine elements, in FIG. 1 a cover 41 , situated on the front side of the lower arm 7 , is opened. Additional possible sewing machine elements include detachable work supports, straightedges, additional apparatuses, or hoops (not shown).
[0024] FIG. 2 shows a schematic diagram of the design of the device for acquiring measurement quantities. The cameras 25 can for example comprise black-and-white or color CCD or CMOS image sensors having a one-or two-dimensional array of light-sensitive pixels. They are connected to an image processing unit 43 that processes the image information acquired by the cameras 25 . Alternatively, a separate image processing unit 43 can be allocated to each of the cameras 25 . This image processing unit can for example be completely or partially integrated on the same chip as the camera 25 .
[0025] The image processing unit 43 is functionally connected to a target quantity memory 45 , for example in a non-volatile flash memory. In addition, there is a functional connection between the image processing unit 43 and the sewing machine control unit (called machine control unit 47 for short). Of course, the image processing unit 43 can also be integrated completely or partially into the machine control unit 47 . The machine control unit 47 comprises a plurality of interfaces, for example to operating elements 12 , to the display unit 10 , to an acoustic signal transducer 49 , and to main drive 51 , which, depending on the design of the sewing machine 1 , is used for example to drive the needle bar 13 and the hook 35 .
[0026] In FIGS. 3 a and 3 b, two different throat plates 33 are shown having stamped-in length scales and pass-through slots 53 for a clutch feed 34 ( FIG. 5 c and 5 d ). The two throat plates 33 differ in the size or length of a needle pass-through opening 55 and/or of a code 57 that is printed or stamped on the upper side and/or the underside of the throat plate 33 . The code 57 can for example be fashioned as a bar code, as a number, or as a color code, and is uniquely assigned to a particular type of throat plate.
[0027] In FIGS. 4 a - 4 d, four different types of sewing feet are shown. They differ not only in their shape or design, but also by a visibly printed or stamped code 57 in the form of a number. The code “ 1 ” characterizes a back-transport foot for useful and decorative stitching, code “ 2 ” designates an overlock foot, code “ 9 ” designates a darning foot, and code “ 37 ” designates a patchwork foot.
[0028] Sewing machine elements need not necessarily be characterized with a code, if a unique identification is also possible on the basis of other features.
[0029] In FIGS. 5 a and 5 b, the fastening of a sewing foot 21 to the sewing foot holder 19 is shown schematically. Here, a cup-type recess 59 on the upper side of the sewing foot 21 is pushed from below over a peg 61 that protrudes downward on the sewing foot holder 19 . Subsequently, the sewing foot 21 is clamped fast on the sewing foot holder 19 using a knee lever 63 . If the sewing foot 21 is not seated properly on the sewing foot holder 19 , this can be recognized for example by a lowered and/or oblique position of the sewing foot 21 , or by a changed pivot position of the knee lever 63 in comparison with a position it should have when the sewing foot 21 is correctly fastened.
[0030] FIGS. 5 c and 5 d show the different positions of the sewing foot 21 , or of a sewing foot sole 22 coupled to the sewing foot 21 at the bottom, for the case of a flat seating on clutch feed 34 ( FIG. 5 c ) and during the crossing of a seam 65 of an article 67 that is being sewn.
[0031] FIGS. 6 a - 6 i show a plurality of different types of sewing needles. They comprise differing features, such as for example needle diameter d, type of point (cutting point, rounding diameter of a ball point), number of needles 17 in the case of multiple needles, distances s between individual needles 17 of such a group, shape of the needles (e.g., round needles, sword-shaped needles). Needles 17 shown in FIG. 6 a - 6 i are, respectively: a sword-shaped needle 17 a, a drilling needle 17 b, a double needle 17 c, a needle 17 d having a cutting point, a needle 17 e having a fine point, two needles 17 f and 17 g having medium ball points, a needle 17 h having a fine ball point, and a universal needle 17 i having a slightly rounded point.
[0032] In the target quantity memory 45 there may be stored, in suitable form, target quantities and/or comparative values and/or criteria for comparing measurement quantities that are acquired by the cameras 25 and prepared by the image processing unit 43 .
[0033] One or more of the cameras 25 can be situated such that, in addition to at least one sewing machine element, they can also acquire sewing elements or parts thereof before, during, or after the processing by the sewing machine 1 . The term “sewing elements” includes for example the article being sewn 67 , threads such as the upper thread and the bobbin thread, a hem, seam, or stitching pattern on the article being sewn 67 , a pattern for a hem or a stitching pattern, or the like. Partial areas of such sewing elements are also designated as sewing elements. Sewing elements can thus be brought into the stitch formation area between the lower arm 7 and the upper arm 9 during sewing and/or embroidering and/or quilting or similar processes, and can be processed or acquired there.
[0034] In the target quantity memory 45 , as target quantities or comparison quantities there can be stored information concerning sewing machine elements, or individual features of such sewing machine elements, such as their situation, size, color, shape, and position, e.g. in relation to the sewing machine 1 or in relation to other sewing machine elements. Thus, for example concerning the sewing feet 21 an item of visual information can be stored concerning how they can be recorded by one of the cameras 25 when the sewing foot 21 is correctly fastened to the sewing foot holder 19 . Alternatively, or in addition, an image of the contours or edges of a sewing foot 21 fastened in this way to the sewing foot holder 19 , or of a code 57 situated on the sewing foot 21 , can also be stored. Instead of, or in addition to, the items of visual information concerning correctly mounted sewing machine elements, typical images of incorrectly mounted sewing machine elements can also be stored in the target quantity memory 45 . The image processing unit 43 can process the items of image information recorded by the camera or cameras 25 in accordance with the rules given in a program memory (not shown) as to whether and, if so, which, of the features stored in the target quantity memory 45 agree sufficiently with the features acquired by the camera or cameras 25 , or deviate from these features. If an agreement of features can be determined, the image processing unit 43 can also check the position and orientation thereof. If the image processing unit 43 determines for example that a sewing foot 21 has the number three as code 57 , but that this number three is not situated in the expected orientation and/or at the expected location in the image segment recorded by the associated camera 25 , this is an indication that the sewing foot 21 is not correctly fastened to the sewing foot holder 19 . An additional indication of an incorrectly mounted sewing foot 21 can be the determination that the knee lever 63 on the sewing foot holder 19 is in an open position ( FIG. 5 b ). The image processing unit 43 can cause the machine control unit 47 to warn the user, by means of a warning tone or a warning message spoken by a synthesized voice, of the problem of an incorrectly mounted sewing foot 21 . Alternatively, or in addition, a warning message can also be outputted on the display device 10 , indicating the determined problem. Analogous to the determination as to whether and which sewing foot 21 is fastened to the sewing foot holder 19 , and whether the fastening is free of problems, the present and correct fastening of other sewing machine elements can also be checked. In addition to, or instead of, warning messages, the machine control unit 47 can also initiate other measures. Such processes may include those described non-definitively below:
[0035] Through comparison of the camera image with image information stored in the target quantity memory 45 , the image processing unit 43 recognizes that a particular type of sewing foot is correctly placed in the sewing foot holder. This information is relayed to the machine control unit 47 . Subsequently, the machine control unit 47 displays for selection on the display 10 , which is fashioned as a touch screen, only sewing stitches or stitch types that are compatible with this sewing foot type.
[0036] On the basis of data requested by the image processing unit 43 , the machine control unit 47 recognizes that a double needle 17 c has been placed in the needle holder 15 , and that a throat plate 33 that is not compatible with this needle type is fastened to the lower arm 7 , for example by a snap connection, screw connection, or magnetic connection. As a first measure, the machine control unit 47 prevents the main drive 51 from being able to be activated, or decouples the needle bar 13 from the main drive 51 . As a further measure, a warning is outputted on the display 10 and/or the acoustic signal generator 49 , as described above.
[0037] The machine control unit 47 receives from image processing unit 43 a communication that a foreign object, such as for example a pin, a scissors, or the finger of a person, is situated in the stitch formation area under the needle 17 . As described, the machine control unit 47 prevents the sewing process from starting. Of course, safety-relevant quantities can also be acquired in redundant or parallel fashion by additional acquisition means.
[0038] The machine control unit 47 initiates the storing of data currently acquired by the image processing unit 43 in a temporary working memory (not shown) and continuously updates these data. The sequence and frequency of these updatings and/or of the acquisition of individual sewing machine elements by the image processing unit 43 can depend for example on actions of the operator such as the operation of the foot switch for starting the sewing process, on a possible risk of injury, and on the risk of damage to the sewing machine 1 .
[0039] The machine control unit 47 signals the image processing unit 43 to acquire items of information such as for example the presence, the correct mounting, or the type of various sewing machine elements.
[0040] Analogous to items of information concerning the sewing machine elements, the image processing unit 43 can also acquire, process, and store in the target quantity memory 45 items of information concerning sewing elements, their structural features, and their situation and orientation, for example in relation to the sewing machine 1 or in relation to sewing machine elements. Thus, for example, for one or more different types of material or fabric, and for particular orientations of the material given a flat seating on the lower arm 7 in the area of the throat plate 33 , the typical directions of the thread orientations, the thread thickness, and/or the distance between adjacent threads and/or the number of threads per length unit in one or more directions or dimensions, and/or the color, can be stored. In addition, in the target quantity memory 45 images can be stored of the upper thread threaded in the needle 17 , or of the course of the upper thread in the area of the needle 17 or in the area between the sewing machine head 11 and the throat plate 33 , as well as images of the bobbin thread in the area of the hook 35 .
[0041] In the following, additional sewing elements or features of such sewing elements are stated in a non-conclusive list:
[0042] Color of threads or of seams,
[0043] Thickness of threads or of seams,
[0044] Thread orientation without and with broken thread,
[0045] Brightness, color, shape, design, contour, structure, size, position, or orientation of a sewing element or of a part thereof,
[0046] Seam appearance (in particular, the design of a seam, the thread entry and/or knotting),
[0047] Various types of material, seated flatly,
[0048] Embroidery pattern or images, or applications,
[0049] Shapes or contours of the article being sewn, with correct and/or incorrect (e.g. bunched or twisted) seating.
[0050] The storing of features or target quantities of the sewing machine elements and the sewing elements can for example take place from an external data carrier via a communication interface of the sewing machine 1 , the data carrier being able to be connected to the sewing machine 1 directly or via a communication network and/or via the Internet (not shown).
[0051] Alternatively, or in addition, the image processing unit 43 can be designed to acquire images of sewing elements and of sewing machine elements that are positioned correctly on the sewing machine 1 , and to store them in the target quantity memory 45 . For this purpose, the user activates a learning mode at one of the operating elements 12 . Subsequently, the cameras 25 acquire, in immediate succession, an image of the correctly positioned sewing machine element or sewing element and an image without this element. From these images, the image processing unit determines an image of the element itself as a difference between the images. This image of the element can be stored in the target quantity memory 45 directly or after a subsequent further processing by the image processing unit 43 using known image processing methods, such as edge extraction or Fourier transformation. Information concerning the sewing machine elements that have been detached from the sewing machine 1 or are fastened correctly or incorrectly on the sewing machine 1 or on the mounting devices thereof can for example be stored in the target quantity memory 45 . The target value memory 45 can also include information concerning a plurality of possible dispositions, operating positions, or orientations of sewing machine elements on the sewing machine 1 .
[0052] In addition to the target quantity memory 45 , the sewing machine 1 can comprise a data memory unit (not shown). This can be physically identical with the target quantity memory 45 , or can alternatively be fashioned as an additional storage medium. In the data memory, images recorded by the camera or cameras 25 can be stored as needed. In this way, for example current sewing operations can be documented, or patterns can be stored. In addition, the sewing machine 1 can comprise a modem, or in general a communication interface, for the creation of communication connections via a network and/or the Internet. Images recorded by the cameras 25 of a problem situation can thus easily be communicated to a help desk, for example. In the reverse direction, images, or any information, can be loaded into the data memory via the Internet. In order to support or facilitate operational steps, such as for example the threading of a thread into the eye of the needle 17 , or the precise positioning of the article being sewn 67 under the needle 17 , images acquired by the camera or cameras 25 can also be displayed on an LCD and/or on the display unit 10 .
[0053] The cameras 25 can be fashioned such that both the acquisition of individual images and also of rapid image sequences are possible. The image processing unit 43 can be fashioned such that, in particular, the following monitoring, auxiliary, storage, measurement, control, or regulatory functions are possible in connection with the machine control unit 47 :
[0054] monitoring of the upper thread and/or of the bobbinthread for thread breakage,
[0055] monitoring of the advance of the material,
[0056] recognition of stretching and/or twisting or bunching, i.e., the drawing together of the material,
[0057] monitoring of the thread entry and/or of the knotting of the bobbin thread and upper thread,
[0058] recognition of shifting of the position of the material during the processing of a stack having a plurality of layers of material,
[0059] monitoring of the seam quality,
[0060] recognition of different types of material,
[0061] recognition of the movement of the material (magnitude, direction).
[0000] This information can be used to determine the slippage, i.e., a deviation of the actual movement of the material from the desired movement. In particular, it can be used as a measurement quantity and the controlling of the material transport device.
[0062] acquisition of the positions of individual patterns or features on the material; use of this information in order to control position during embroidery.
[0063] acquisition or measurement of patterns (size, shape). Use of this information to influence pattern formation, for example in the creation of buttonholes,
[0064] acquisition of the brightness or of the illumination of the article being sewn 67 ; use of this measurement quantity as a regulating quantity for regulating the brightness of a sewing light (not shown),
[0065] acquisition and storing of images of the current sewing operation (archiving, documentation),
[0066] acquisition of images for communication to a help desk (e.g., by means of a modem that is integrated in the sewing machine 1 or that can be connected thereto),
[0067] acquisition and imaging of sewing machine elements and/or sewing elements, or parts thereof, on an LCD or on the display unit 10 , e.g. as an auxiliary means during threading, or for the precise positioning of the article being sewn 67 under the needle 17 during embroidery.
[0068] With the device according to the present invention and the method according to the present invention, during operation of the sewing machine 1 safety can be increased, errors can be prevented, operation can be simplified and/or automated, and the quality can be improved. | A method and the device for acquiring and processing measurement quantities in a sewing machine ( 1 ) using at least one camera ( 25 ), situated on a sewing machine ( 1 ), for the acquisition and processing of image data for sewing machine elements and sewing elements. An image processing unit connected downstream from the camera ( 25 ) processes the images supplied by the camera ( 25 ), taking into account data stored in a target quantity memory, and influences the behavior of the machine control unit dependent on the result of the processing. | 3 |
REFERENCE TO RELATED APPLICATIONS
This application claims an invention which was disclosed in Provisional Application No. 60/754,106, filed Dec. 27, 2005, entitled “OVERFLOW DOWNDRAW GLASS FORMING METHOD AND APPARATUS”. The benefit under 35 USC §119(e) of the U.S. provisional application is hereby claimed, and the aforementioned application is hereby incorporated herein by reference.
BACKGROUND OF THE INVENTION
This invention relates generally to the manufacture of glass sheet and, more particularly, to glass sheet used for the production of TFT/LCD display devices that are widely used for computer displays and for flat panel television.
DESCRIPTION OF RELATED ART
The glass that is used for semiconductor powered display applications must have very high surface quality to allow the successful application of semiconductor type material. Sheet glass made using the apparatus of U.S. Pat. No. 3,338,696 assigned to Corning, Inc. makes the highest quality glass as formed and does not require post-processing. The Corning patent makes glass by a manufacturing process termed “The Overflow Process”. Glass made using other processes requires grinding and/or polishing and thus does not have as fine a surface finish. The glass sheet must also conform to stringent thickness variation and warp specifications.
FIGS. 1A through 1D illustrate the principle parts of a typical “Overflow Process” manufacturing system. The molten glass ( 2 ) from the melting furnace and forehearth, which must be of substantially uniform temperature and chemical composition, enters the forming apparatus from the downcomer pipe ( 7 ) at the downcomer pipe bottom end ( 17 ) into the inflow pipe ( 8 ) (also called an inlet pipe) and flows into the sheet forming structure ( 1 ). Examples of the glass sheet forming apparatus are found in U.S. Pat. Nos. 3,338,696 and 3,451,798. The glass sheet forming apparatus is also described in detail in U.S. Pat. Nos. 6,748,765, 6,889,526, 6,895,782, 6,990,834, and 6,997,017 and U.S. patent application Ser. Nos. 11/006,251, 11/060,139, 11/184,212, and 11/553,198 which are hereby incorporated herein by reference. The glass sheet forming apparatus includes a shallow trough on the top of a wedge shaped forming structure ( 1 ). Straight sloped weirs ( 4 ) substantially parallel with the pointed edge of the wedge, herein termed the root ( 5 ), form each side of the trough in the forming structure ( 1 ). The trough bottom ( 6 ) and the sides of the trough are contoured in a manner to provide even distribution of the glass ( 2 ) to the top of each side weir ( 4 ). The molten glass ( 2 ) then flows through the trough, over the top of each side weir ( 4 ), down each side of the wedge shaped sheet forming structure ( 1 ), and joins at the root ( 5 ) to form a sheet of molten glass. The molten glass is then cooled as it is pulled off the root ( 5 ) to form a solid glass sheet ( 10 ) of substantially uniform thickness.
The refractory materials from which the forming structure and its support structure are made have high strength in compression and low strength in tension. Like most structural materials they also change shape when stressed at high temperature by a phenomenon termed “thermal creep”.
FIGS. 2A through 2D illustrate the typical effects of thermal creep on the shape of the forming structure when the end support and compression blocks impart different compression stress in the bottom of the forming structure ( 1 ) near the root ( 5 ). FIG. 2A shows that with no compression loading, the forming structure ( 1 ) sags in the middle such that the top of the weirs ( 4 ) and the root ( 5 ) are now curved ( 21 ) and the trough bottom ( 6 ) has a change in curvature ( 21 ). This longitudinal curvature ( 21 ) causes the molten glass ( 2 ) to no longer flow with constant thickness ( 22 ) over the weirs ( 4 ). More specifically, the longitudinal curvature ( 21 ) allows more glass to flow over the middle of the weirs resulting in an uneven sheet thickness distribution. The forming structure ( 1 ) has an initial longitudinal length ( 20 ) as defined by the phantom lines ( 24 ) and ( 29 ). With no external loading the weirs ( 4 ) get shorter and the root ( 5 ) gets longer.
FIG. 2B shows that sagging of the forming structure is minimized under the optimum longitudinal compression loading ( 26 ) of the lower section of the forming structure ( 1 ) near the root ( 5 ). With optimal loading both the weirs ( 4 ) and the root ( 5 ) shorten equally to longitudinal length ( 27 ). FIG. 2C shows that if too great a longitudinal compression load ( 25 ) is applied to the lower section of the trough ( 1 ) near the root ( 5 ), the root ( 5 ) is compressed excessively, thus producing a convex longitudinal curvature ( 23 ) to the trough weirs ( 4 ), the trough bottom ( 6 ), and the root ( 5 ). The root ( 5 ) shortens considerably more than the weirs ( 4 ) as can be seen by the movement relative to the phantom lines ( 24 ) and ( 29 ). FIGS. 2A through 2C represent the effect of thermal creep over the same time period. FIG. 2D shows a forming structure ( 1 ), which has shortened a greater amount to longitudinal length ( 28 ). This increased shortening is caused by imparting the correct longitudinal load ( 26 ) for the increased time of a substantially longer production campaign. This increased shortening has an adverse effect on the width of the manufactured sheet.
U.S. Pat. No. 3,451,798 teaches that a sheet glass edge control device, termed “edge director” herein, must be installed at each end of the trough to prevent narrowing of the formed sheet as a result of surface tension. FIGS. 3A through 3D show the prior art edge director assemblies ( 41 ) and ( 42 ) shown in FIGS. 4A through 4F attached to the ends of the trough forming structure ( 1 ). The flanges ( 47 ) of the inflow edge director assembly ( 41 ) are compressed against the forming structure ( 1 ) by the inflow support and compression block ( 31 ). The inflow support and compression block ( 31 ) rests on the inflow end support structure ( 33 ) and is held in position by the adjustment bolt ( 34 ). The flanges ( 48 ) of the far end edge director assembly ( 42 ) are compressed against the forming structure ( 1 ) by the far end support and compression block ( 32 ). The far end support and compression block ( 32 ) rests on the far end structure ( 35 ) and is held in position by the force motor ( 38 ). A force motor ( 38 ) is a device that generates a substantially constant linear force ( 26 ), in a longitudinal direction ( 36 ). The energy required to maintain this force ( 26 ) may be supplied by gravitational, pneumatic, hydraulic, or mechanical means. Some examples of force motors include, but are not limited to, an adjustable spring assembly, a mechanical adjustment device that is constantly or periodically monitored and adjusted, an air cylinder, an air powered motor, a hydraulic cylinder, a hydraulic powered motor, a solenoid, an electric motor, or a weight and lever system.
FIGS. 4A through 4C are side, end, and top views of the inflow end edge director ( 41 ) as used in the prior art. The inflow end edge director ( 41 ) has a fence ( 43 ) to which the glass attaches such that the width is maintained. The edge director ( 41 ) also has symmetrical edge director surfaces ( 45 ) that provide for gravity to assist the flowing glass to attach to the fence, and flanges ( 47 ) that are used to secure the edge director to the inflow end of the forming structure ( 1 ).
FIGS. 4D through 4F are side, end, and top views of the far end edge director ( 42 ) as used in the prior art. The far end edge director ( 42 ) has a fence ( 44 ) to which the glass attaches such that the width is maintained. The edge director ( 42 ) also has symmetrical edge director surfaces ( 46 ) that provide for gravity to assist the flowing glass to attach to the fence, and flanges ( 48 ) that are used to secure the edge director to the far end of the forming structure ( 1 ). Attached to the outlet edge director ( 42 ) is a wedge shaped protrusion, herein termed a plow ( 49 ), which aids in the control of the glass flow over the weirs ( 4 ) near the far end edge director ( 42 ).
The edge directors are normally fabricated via welding from platinum sheet or platinum alloy sheet (platinum herein). In the prior art, the edge directors are fixed to each end of the forming structure. Thus, as the campaign progresses and the forming structure becomes shorter via thermal creep, the manufactured sheet becomes narrower. This results in fewer square feet of production, and required process changes.
The forming structure of the prior art is made from a single block of refractory material which is isostatically pressed. The size capability of presently available equipment for isostatic pressing limits the dimensions of the forming structure.
A major drawback of the apparatus of “The Overflow Process” is that the forming apparatus deforms during a manufacturing campaign in a manner such that the glass sheet no longer meets the thickness and width specifications. This is a primary cause for premature termination of the production run.
Another drawback is that the edge directors are required because the glass does not flow over the ends of the forming structure.
Another drawback of the apparatus is that the production rate is limited by the size forming structure.
SUMMARY OF THE INVENTION
The present invention is a significant modification of “The Overflow Process” that embodies design features that support the forming apparatus in a manner such that the deformation that results from thermal creep has a minimum effect on the thickness variation of the glass sheet.
The glass “Sheet Forming Apparatus” normally designed for use in “The Overflow Process” (U.S. Pat. No. 3,338,696) relies on a specifically shaped forming structure to distribute the glass in a manner to form sheet of a uniform thickness. The basic shape of this forming trough is described in detail in U.S. Pat. No. 3,338,696. Structurally the forming structure is a beam, which is supported at each end. The sheet glass forming process is conducted at elevated temperatures, typically between 1100° C. and 1350° C. At these temperatures the materials used for construction of the forming structure exhibit a property called thermal creep, which is deformation of the material caused by applied stress at elevated temperatures. Thus, the forming structure deforms under the stress caused by own weight.
Embodiments of this invention suspend the forming structure from the top in a manner such that the thermal creep, which inevitably occurs, has a minimum impact on the glass flow characteristics of the forming structure. In these embodiments there are no externally applied compression loads on the forming structure and any moments that produce sagging of the forming structure are minimized. Thus sheet glass may be manufactured for a longer time without requiring changing of the forming structure.
In other embodiments of this invention the glass flows over the ends of the forming structure, thus completely enveloping the forming structure.
Other embodiments of this invention also allow for the doubling of the length of the forming structure, thus proportionally increasing the production rate.
Like the present overflow process, this invention forms the sheet glass surfaces from virgin glass from the center of the glass flow stream.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A is a side view of the prior art overflow downdraw sheet glass forming apparatus.
FIG. 1B is a cross-section of the forming structure shown in FIG. 1A across lines B-B.
FIG. 1C is a top view of the prior art overflow downdraw sheet glass forming apparatus.
FIG. 1D is a cross-section of the forming structure shown in FIG. 1A across lines D-D.
FIG. 2A is an illustration of the thermal creep deformation of the glass forming structure under the load of its own weight.
FIG. 2B is an illustration of the thermal creep deformation of the glass forming structure under an applied load that minimizes vertical deformation.
FIG. 2C is an illustration of the thermal creep deformation of the glass forming structure under excessive applied load.
FIG. 2D is an illustration of the thermal creep deformation of the glass forming structure under an applied load that minimizes vertical deformation over the extended period of a production campaign.
FIG. 3A is a side view of the prior art overflow downdraw sheet glass forming apparatus showing the edge directors, the support and compression blocks, and the end support structures for both the inflow end and the far end of the forming structure.
FIG. 3B is a cross-section of the forming structure shown in FIG. 3A across lines B-B.
FIG. 3C is a partial top view of the prior art overflow downdraw sheet glass forming apparatus shown in FIG. 3A .
FIG. 3D is a cross-section of the forming structure shown in FIG. 3A across lines D-D.
FIG. 4A is a side view of the prior art inflow end edge director.
FIG. 4B is an end view of the prior art inflow end edge director.
FIG. 4C is a top view of the prior art inflow end edge director.
FIG. 4D is a side view of the prior art far end edge director.
FIG. 4E is an end view of the prior art far end edge director.
FIG. 4F is a top view of the prior art far end edge director.
FIG. 5A is a side view of an embodiment of the present invention schematically illustrating a center support web that provides for the support of the forming structure from the top.
FIG. 5B is a cross-section of the forming structure shown in FIG. 5A across lines B-B.
FIG. 5C is a partial top view of the embodiment of this invention shown in FIG. 5A .
FIG. 5D is a cross-section of the forming structure shown in FIG. 5A across lines D-D.
FIG. 6A is a side view of an embodiment of the present invention schematically illustrating the components and assembly for the forming structure that is shown in FIGS. 5A through 5D .
FIG. 6B is a cross-section of the forming structure shown in FIG. 6A across lines B-B.
FIG. 6C is a partial top view of the embodiment of this invention shown in FIG. 6A .
FIG. 6D is a cross-section of the forming structure shown in FIG. 6A across lines D-D.
FIG. 7A is a side view of an embodiment of the present invention schematically illustrating a center support web that provides for the support of the forming structure from the top and has no end support structure.
FIG. 7B is a cross-section of the forming structure shown in FIG. 7A across lines B-B.
FIG. 7C is a partial top view of the embodiment of this invention shown in FIG. 7A .
FIG. 7D is a cross-section of the forming structure shown in FIG. 7A across lines D-D.
FIG. 8A is a side view of an embodiment of the present invention schematically illustrating the components and assembly for the forming structure that is shown in FIGS. 7A through 7D .
FIG. 8B is a cross-section of the forming structure shown in FIG. 8A across lines B-B.
FIG. 8C is a partial top view of the embodiment of this invention shown in FIG. 8A .
FIG. 8D is a cross-section of the forming structure shown in FIG. 8A across lines D-D.
FIG. 9A is a side view of an embodiment of the present invention schematically illustrating the center support web that provides for the support of the forming structure from the top, has no end support structure, and has a shape that requires no edge directors.
FIG. 9B is a cross-section of the forming structure shown in FIG. 9A across lines B-B.
FIG. 9C is a partial top view of the embodiment of this invention shown in FIG. 9A .
FIG. 10A is a side view of an embodiment of the present invention schematically illustrating the components and assembly for the forming structure that is shown in FIGS. 9A through 9C .
FIG. 10B is a cross-section of the forming structure shown in FIG. 10A across lines B-B.
FIG. 10C is a partial top view of the embodiment of this invention shown in FIG. 10A .
FIG. 11A is a side view of an embodiment of the present invention showing the forming structure supported by end mounts.
FIG. 11B is a cross-section of the forming structure shown in FIG. 11A across lines B-B.
FIG. 11C is a partial top view of the embodiment of this invention shown in FIG. 11A .
FIG. 11D is a cross-section of the forming structure shown in FIG. 11A across lines D-D.
FIG. 11E is a cross-section of the mounting block shown in FIG. 11A across lines E-E.
FIG. 12A is a side view of an embodiment of the present invention showing the forming structure supported by end mounts.
FIG. 12B is a cross-section of the forming structure shown in FIG. 12A across lines B-B.
FIG. 12C is a partial top view of the embodiment of this invention shown in FIG. 12A .
FIG. 13A is a side view of an embodiment of the present invention showing a forming structure that produces glass sheet with substantially twice the width of the prior art sheet.
FIG. 13B is a cross-section of the forming structure shown in FIG. 13A across lines B-B.
FIG. 13C is a partial top view of the embodiment of this invention shown in FIG. 13A .
FIG. 14A is a side view of an embodiment of the present invention showing a forming structure which produces two sheets of substantially the same width as the prior art sheet.
FIG. 14B is a cross-section of the forming structure shown in FIG. 14A across lines B-B.
FIG. 14C is a partial top view of the embodiment of this invention shown in FIG. 14A .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The refractory materials from which the forming trough and its support structure are made have high strength in compression and low strength in tension. Like most structural materials they also change shape when stressed at high temperature by a process termed “Thermal Creep”. These material characteristics and how these characteristics affect the manufacturing process are the reason for this invention.
FIGS. 5A through 5D illustrate a forming structure ( 51 ) which is supported from the top at surface ( 59 ) by a center support web ( 57 ). The support web ( 57 ) is attached to the bottom ( 56 ) of the trough in the forming structure ( 51 ). For clarity of illustration the support web ( 57 ) is shown as being rectangular in cross section and having a longitudinal length less than that of the weirs ( 54 ) on the forming structure ( 51 ). In practice the longitudinal length of the support web ( 57 ) is optionally the full length of the weirs ( 54 ) and could even extend back into the inflow pipe ( 68 ). The cross section would be streamlined to facilitate smooth flow of the glass. Because the support web ( 57 ) is attached on the centerline of the forming structure ( 51 ) it produces a restriction to the glass flow. The width of the forming structure ( 53 ) between the weirs ( 54 ) will be greater than the forming structure width in the prior art. Attached to the support web ( 57 ) is a flow control web ( 58 ) which guides flow to the far end unusable edge of the formed glass sheet.
FIGS. 6A through 6D show the forming structure ( 51 ) as part of the assembled sheet glass forming apparatus. The glass ( 2 ) is fed to a downcomer pipe ( 7 ), which feeds an inflow pipe ( 68 ) similar to the prior art inflow pipe ( 8 ) that is adapted to fit the wider forming structure ( 51 ). The edge directors ( 61 ) and ( 62 ) are similar to the prior art edge directors ( 41 ) and ( 42 ), but adapted to fit the wider forming structure ( 51 ). The glass ( 2 ) flows down the two parallel troughs past the support web ( 57 ) and the flow control web ( 58 ), flows over the weirs ( 54 ), down the inverted wedge surfaces to the root ( 55 ) of the forming structure ( 51 ) and forms the glass sheet ( 10 ).
The shape and size of the flow control web ( 58 ), the cross-section and length of the support web ( 57 ) where it is submerged in the glass ( 2 ), and the width ( 53 ) between the weirs ( 54 ) in combination with the shape of the trough bottom ( 56 ) and of the weirs ( 54 ), would be determined using the simulation technologies of Computational Fluid Dynamics (CFD) and Oil Modeling.
FIGS. 7A through 7D illustrate another embodiment of this invention whereby the forming structure ( 71 ), which is supported from the top at surface ( 59 ) by a center support web ( 77 ), has a weir ( 74 ) encircling the top of the forming structure, and has rounded ends ( 70 ) and ( 72 ). The center support web ( 77 ) is attached to the bottom ( 76 ) of the trough in the forming structure ( 71 ). The glass flows over the weir ( 74 ) and down all sides of the forming structure ( 71 ) joining at the root ( 75 ) of the forming structure ( 71 ) such that the glass completely envelopes the forming structure ( 71 ).
FIGS. 8A through 8D show the forming structure ( 71 ) as part of the assembled sheet glass forming apparatus. The glass ( 2 ) is fed to a downcomer pipe ( 87 ) similar to that in the prior art, which discharges the glass directly onto the top surface of the glass in the forming structure. No edge directors are shown, but some type of flow control apparatus would be required at each end ( 70 ) and ( 72 ). The glass ( 2 ) flows down the two parallel troughs past the support web ( 77 ) and flow control web ( 78 ), flows over the weir ( 74 ) on each side and each end ( 70 ) and ( 72 ), down the inverted wedge surfaces to the root ( 75 ) and forms the glass sheet ( 10 ). The shape of the bottom and the location of the bottom of the downcomer pipe ( 87 ) are both critical to maintaining uniform flow over the weir ( 74 ). The bottom of the downcomer pipe ( 87 ) may be below the glass surface as shown in FIG. 10A .
The shape and location of the bottom of the downcomer pipe ( 87 ), the shape and size of the flow control web ( 78 ), the cross section and length of the support web ( 77 ) where it is submerged in the glass ( 2 ), the shape of the ends ( 70 ) and ( 72 ), and the width ( 73 ) between the weirs ( 74 ), in combination with the shape of the trough bottom ( 76 ) and of the weirs ( 74 ), would be determined using the simulation technologies of Computational Fluid Dynamics (CFD) and Oil Modeling and would be periodically improved based on manufacturing experience.
FIGS. 9A through 9C illustrate a forming structure ( 91 ) which is supported from the top at surface ( 99 ) by two support webs ( 97 ). The support webs ( 97 ) are attached to the bottom ( 96 ) of the trough in the forming structure ( 91 ). The cross section of the support webs ( 97 ) is streamlined to facilitate smooth flow of the glass. The weirs ( 94 ) completely encircle the top of the forming structure ( 91 ). The forming structure has a shape in the horizontal plane that is substantially an ellipse. This somewhat elliptical shape is such that edge directors are not required at the ends ( 90 ) and ( 92 ). The angle ( 98 ) of the inverted slope varies in the longitudinal direction such that the increase in the gravitational force in the longitudinal direction on the vertically flowing glass ( 2 ) is such to counteract the effect of the surface tension of the glass ( 2 ) as it flows to the root ( 95 ) of the forming structure ( 91 ).
FIGS. 10A through 10C show the forming structure ( 91 ) as part of the assembled sheet glass forming apparatus. The glass ( 2 ) is fed to a downcomer pipe ( 107 ), similar to that in the prior art, which discharges the glass under the top surface of the glass ( 2 ) in the forming structure. The glass ( 2 ) flows in the parallel troughs past the support web, flows over the weir ( 94 ) on each side and each end ( 90 ) and ( 92 ), down the inverted wedge surfaces to the root ( 95 ) of the forming structure ( 91 ) and forms the glass sheet ( 10 ). The shape of the bottom and the location of the bottom of the downcomer pipe ( 107 ) are both critical to maintaining uniform flow over the weir ( 94 ). The bottom of the downcomer pipe ( 107 ) may be above the glass surface as shown in FIG. 8A .
The shape and location of the bottom of the downcomer pipe ( 107 ), the horizontal cross section of the forming structure ( 91 ), the variation of the inverted slope angle ( 98 ), the cross section and length of the support webs ( 97 ) where they are submerged in the glass ( 2 ), and the width ( 93 ) between the weirs ( 94 ), in combination with the shape of the trough bottom ( 96 ) and of the weirs ( 94 ), would be determined using the simulation technologies of Computational Fluid Dynamics (CFD) and Oil Modeling and would be periodically improved based on manufacturing experience.
The somewhat elliptical horizontal shape of forming structure ( 91 ) in FIGS. 9A through 9C can also be incorporated as a feature in the shape of the ends ( 70 ) and ( 72 ) of the forming structure ( 71 ) in FIGS. 7A through 7D . In the embodiment shown in FIGS. 9A through 9C , the somewhat elliptical horizontal shape is shown as encompassing the entire periphery of the forming structure. In additional embodiments the somewhat elliptical horizontal shape may be limited to the end portions ( 90 ) and ( 92 ) of the forming structure.
The support webs ( 57 ), ( 77 ), and ( 97 ), which support the weight of the forming structure and the glass ( 2 ) in and on the forming structure are loaded in tension. The refractory materials, Zircon and Alumina, normally used to construct the forming structure would not be suitable for this part of the forming apparatus assembly. A refractory metal, such as molybdenum, would be preferable for the construction of the support webs ( 57 ), ( 77 ), and ( 97 ). The molybdenum would preferably be clad in platinum or platinum alloy to protect it from oxidation. The refractory material of the forming structure, such as Zircon, would then be attached to the support webs ( 57 ), ( 77 ), and ( 97 ).
FIGS. 11A through 11E show a forming structure ( 117 ) similar in shape to forming structure ( 71 ) of FIG. 7A through 7D supported from the ends by mounting blocks ( 117 ) at each end. The mounting blocks ( 117 ) have a thin streamlined profile as shown by the section in FIG. 11E such as to have minimum interference with the molten glass ( 2 ) flowing over the ends (( 110 ) and ( 112 )) of the forming structure ( 111 ) and down each side of the mounting blocks ( 117 ). The vertical flow of the glass ( 2 ) at each end ( 110 ) and ( 112 ) is on a substantially vertical surface at angle ( 18 ). The range of angle ( 18 ) is 0 to 20 degrees. The glass ( 2 ) flows over the weir ( 114 ) on each side and each end ( 110 ) and ( 112 ), down the wedge surfaces to the root ( 115 ) and forms the glass sheet ( 10 ). The shape of the bottom and the location of the bottom of the downcomer pipe ( 87 ) are both critical to maintaining uniform flow over the weir ( 114 ). The bottom of the downcomer pipe ( 87 ) may be below the glass surface as shown in FIG. 10A .
The shape and location of the bottom of the downcomer pipe ( 87 ), the shape and angle ( 118 ) of the ends ( 110 ) and ( 112 ), and the width ( 113 ) between the weirs ( 114 ), in combination with the shape of the trough bottom ( 116 ) and of the weirs ( 114 ), would be determined using the simulation technologies of Computational Fluid Dynamics (CFD) and Oil Modeling and would be periodically improved based on manufacturing experience.
FIGS. 12A through 12C show a forming structure ( 121 ) similar in shape to forming structure ( 91 ) of FIGS. 9A through 9C supported from the ends by mounting blocks ( 127 ) at each end ( 120 ) and ( 122 ). The mounting blocks ( 127 ) have a thin streamlined profile similar to that shown by the section in FIG. 11E so that there is minimum interference with the molten glass flowing over the ends (( 120 ) and ( 122 )) of the forming structure ( 121 ) and down each side of the mounting blocks ( 127 ). The vertical flow of the glass ( 2 ) at each end ( 120 ) and ( 122 ) is on a substantially vertical surface at angle ( 128 ). The range of angle ( 128 ) is preferably 0 to 20 degrees. The glass ( 2 ) flows over the weir ( 124 ) on each side and each end ( 120 ) and ( 122 ), down the inverted wedge surfaces to the root ( 125 ) and forms the glass sheet ( 10 ). The shape of the bottom and the location of the bottom of the downcomer pipe ( 107 ) are both critical to maintaining uniform flow over the weir ( 124 ).
The shape and location of the bottom of the downcomer pipe ( 87 ), the shape and angle ( 128 ) of the ends ( 120 ) and ( 122 ), and the width ( 123 ) between the weirs ( 124 ), in combination with the shape of the trough bottom ( 126 ) and of the weirs ( 124 ), would be determined using the simulation technologies of Computational Fluid Dynamics (CFD) and Oil Modeling and would be periodically improved based on manufacturing experience.
Either the angle ( 118 ) or ( 128 ), which are shown in FIGS. 11A and 12A respectively, may be optionally incorporated in the shape of the ends of the embodiments of forming structures ( 71 ), ( 91 ), ( 111 ), and ( 121 ).
A refractory metal, such as molybdenum, would be preferable for the construction of the mounting blocks (( 117 ) and ( 127 )) because the thin profile implies high loading which would result in substantial thermal creep. The molybdenum would preferably be clad in platinum or platinum alloy to protect it from oxidation.
Another method of protecting the refractory metal, such as molybdenum, from oxidation is to operate the process in a reducing atmosphere.
FIGS. 13A through 13C show an embodiment of this invention whereby the production rate of the forming apparatus may be substantially increased. This embodiment comprises two forming structure blocks ( 139 ) of length ( 136 ) placed end to end such that the combined length of the forming structure ( 131 ) is length ( 133 ). Length ( 136 ) is the maximum length isostatically pressed refractory that can be procured. Combining two blocks end to end produces a forming structure ( 131 ) with twice the width ( 133 ), which in turn makes a glass sheet ( 130 ) that is substantially twice as wide as prior art sheet. The forming structure blocks ( 139 ) are compressed together by the mounting blocks ( 137 ) and join at the plane ( 135 ). A keying mechanism, not shown, would be required at plane ( 135 ) to insure correct alignment of the two forming structure blocks ( 139 ).
In the embodiments of this invention shown in FIGS. 10A through 10C , FIGS. 12A through 12C , and FIGS. 13A through 13C the most challenging technical development is controlling the glass flow over the weirs ( 94 ), ( 124 ), and ( 134 ) in the center of the forming apparatus near the bottom of the downcomer pipe ( 107 ). If the glass ( 2 ) flow control is not accurate in this region of the sheet ( 130 ), the quality in area ( 132 ) in the center of the sheet ( 130 ) will not meet specification. The two useable width ( 138 ) sections of the sheet ( 130 ) will be substantially the same sheet width as made with an apparatus that uses a single piece forming structure.
FIGS. 14A through 14C show an embodiment of this invention which produces two strips of sheet ( 140 a ) and ( 140 b ). Two forming structure blocks ( 149 ) of length ( 146 ) are compressed together at plane ( 145 ) by the mounting blocks ( 137 ) to make the forming structure ( 141 ). A flow divider ( 142 ) is provided at the center plane of the forming structure ( 141 ) to separate the glass flow such that two separate sheets ( 140 a ) and ( 140 b ) are formed. The sheets each have useable widths ( 148 ) which are substantially the same sheet width as made with an apparatus that uses a single piece forming structure.
The forming structures ( 71 ), ( 91 ), ( 111 ), and ( 121 ) are normally made from refractory materials such as Zircon and Alumina. An additional feature of the embodiments of this invention that use forming structures ( 71 ), ( 91 ), ( 111 ), and ( 121 ) is that the forming structure is completely enveloped in glass during glass sheet forming operations. The forming structure material would then optionally be a refractory metal such as molybdenum. The glass, which encases the molybdenum forming structure structure, would protect the molybdenum from oxidation.
Accordingly, it is to be understood that the embodiments of the invention herein described are merely illustrative of the application of the principles of the invention. Reference herein to details of the illustrated embodiments is not intended to limit the scope of the claims, which themselves recite those features regarded as essential to the invention. | The present invention discloses improved apparatuses for forming sheet glass. In one embodiment, the invention introduces a structural web that supports the forming structure in a manner such that the thermal creep which inevitably occurs has a minimum impact on the glass flow characteristics of the forming structure. | 2 |
BACKGROUND OF THE INVENTION
This invention relates to the problem of preparing support materials useful as components of olefin polymerization catalysts, and the process used to prepare them. In particular, it relates to the preparation of insoluble catalyst support materials containing magnesium, halide and hydrocarbyloxide in well defined ratios. Most particularly, this invention concerns the preparation of substantially pure solid halomagnesium hydrocarbyloxide catalyst support materials with well defined and uniform composition.
The term "hydrocarbyloxide" is intended to cover structures of the formula --OR where R is "hydrocarbyl", i.e., a moiety formed by the removal of hydrogen from a hydrocarbon, e.g. alkyl, aryl and alkylaryl. There are many examples in the prior art of olefin polymerization catalysts obtained by combining a component comprising magnesium halide and a titanium halide with an activating organoaluminum compound. The polymerization activity, stereospecificity, and comonomer incorporation characteristics of such compounds may be manipulated in various ways. In some cases this is accomplished by controlling the particular composition of the magnesium halide, for instance, by including some alkoxy ligands in the magnesium halide compound, or by halogenating a particular magnesium dialkoxide to prepare the magnesium halide. Magnesium halide-supported catalysts for the polymerization of olefins prepared by halogenating a magnesium alkoxide are described in U.S. Pat. Nos. 4,400,302 and 4,414,132 to Goodall, et. al., for example. Since the morphology of the polymer is generally controlled by that of the catalyst, much effort has been expended in attempting to control the morphology of such catalysts.
Examples of catalyst components that are prepared in processes employing materials containing magnesium, halide and hydrocarbyloxide can be found in European Patent Publication No. 301,894. This patent document illustrates the preparation of catalyst components with specific useful polymerization characteristics (co-monomer incorporation, polymer crystallinity, etc.) by employing these materials.
In view of the above considerations, the nature of the magnesium-containing component of a polymerization catalyst composition, and the process used to prepare it are very important. The prior art includes many strategies for the preparation of magnesium, halide and hydrocarbyloxide containing polymerization catalyst support materials. Most of these strategies are based on the work of Turova and Turevskaya (Journal of Organometallic Chemistry, vol. 42, (1972), pp 9-17). Turova et al. suggested thermolysis of Mg(OR) 2 and MgX 2 mixtures (X=halogen; R, R'=alkyl, aryl, etc), eq. (1), or the alcoholysis of Grignard reagents, eq. (2): ##STR1## Subsequent work has varied from this earlier work in certain details, such as in U.S. Pat. Nos. 4,814,313 to Murata et. al. and 4,220,554 to Scata et. al. where Grignard reagents were formed in situ and then reacted with alkoxy ligand sources, eq. (3). ##STR2## Another minor variation can be found in U.S. Pat. No. 4,820,879 to Mehta, who uses HX (eq. (4)) as the halogen ligand source, rather than MgX 2 as in eq. (1).
Mg(OR).sub.2 +HX→XMgOR+HOR (4)
In the method of eq. (3), halide is present before the hydrocarbyloxide is formed, and may or may not be present in the desired ratio to magnesium because of the Schlenk equilibrium. In the method of eq. (4), the halogen ligand source must react with only part of the hydrocarbyloxy ligands present, in order to get the desired product stoichiometry, and the extent of reaction is difficult to control.
Common concerns in the preparation of insoluble solid materials are the issues of uniformity, purity, and composition. Catalyst support materials are substances that may be categorized as either "ionic structures" or "covalent infinite arrays". In these cases it is not always a simple matter to establish the uniformity and purity of a material. Although the above strategies (eq. (1) through eq. (4)) purport to prepare solid compounds such as "XMgOR", they are not supported by examples where the chemical and spectroscopic characterization of the product demonstrates that it is a uniform solid of well defined composition with established purity. (Terminology taken from Advanced Inorganic Chemistry, 5th edition, by F. A. Cotton, and G. Wilkinson: John Wiley and Sons; New York, 1988). In many cases it is possible, and even likely, that the product was actually a mixture, e.g. of MgX 2 and Mg(OR) 2 , that merely had the correct average composition. In all cases where there was spectroscopic characterization sufficient to differentiate between a solid of uniform composition and purity, and a mixture (e.g. U.S. Pat. Nos. 4,820,879 and 4,792,640 to Mehta), mixtures were found.
DESCRIPTION OF THE INVENTION
This invention employs a novel, selective, step-wise, process that exploits a) the high reactivity of magnesium hydrocarbyl groups toward hydrocarbyloxy ligand sources, and b) the difference in reactivity between magnesium hydrocarbyl ligands and magnesium hydrocarbyloxy ligands in reactions with halogen ligand sources to prepare solids of uniform composition and purity with empirical formulae such as XMgOR where, X is halogen and OR is a hydrocarbyloxy group containing from 1 to 20 carbon atoms. Furthermore, this novel process permits the preparation of novel solids of uniform composition and purity having empirical formulae: X 2-z Mg(OR) z where 0≦z<2; or X N (2-z) Mg N (OR) Nz where 0≦z<2 and N is a conveniently chosen multiplier to reduce rational numbers to integers, where the ratios of halide to magnesium (N(2-z):N) and alkoxide to magnesium (Nz:N) are not always 1:1.
The strategy used in regard to the present process is to start with a magnesium compound containing two very reactive groups bound to magnesium, such as hydrocarbyl groups, and introduce the hydrocarbyloxy ligand first. A controlled amount of hydrocarbyloxy ligand is bound to the magnesium by introducing an oxygen-containing compound which can react with the reactive groups on the magnesium to produce the desired magnesium hydrocarbyloxy ligand. This reaction should be chosen so that the oxygen compound is completely consumed, which will insure that the amount of magnesium hydrocarbyloxy bonds can be precisely controlled. The product from this reaction thus contains an amount of a reactive group bound to magnesium, and an amount of less reactive hydrocarbyloxy ligands bound to magnesium. For example: ##STR3## R, R', R"=same or different hydrocarbyls; x+y=z;
0≦x<1;
0≦y<1.
Because the magnesium-hydrocarbyloxy ligand bond is relatively less reactive than the remaining reactive group, the product from this reaction can, with or without isolation, be combined with a halogen ligand source that reacts preferentially with the remaining reactive groups: ##STR4## X=halogen; Y=e.g. halogen, pseudohalogen, X 3 Si, or similar moiety bound to halogen;
other groups and terms as in eq. (5)
A more specific example of the foregoing is supplied by the following two equations:
BuMgEt+HOEt→Bu.sub.l-x Et.sub.l-y Mg(OEt)+xBuH+yEtH (7)
x+y=1
0≦x<1
0≦y<1.
Bu.sub.l-x Et.sub.l-y Mg(OEt)+0.5 SiCl.sub.4 →ClMgOEt+0.5 SiCl.sub.2 Bu.sub.2-2x Et.sub.2-2y (8)
Note that in this case, since each silicon can supply two halogen ligands, 1/2 mole of halogenating reagent is required, instead of 1 mole.
If the reactivity of the halogen ligand source is such that it also reacts to some extent with the less reactive hydrocarbyloxy ligand, a controlled excess of the hydrocarbyloxy ligand may be added in the first step, eqs. (5), (7), as well as a controlled excess of halogenating agent in the second step, eq. (6), (8).
Examples of reactive groups useful in the initial magnesium compound include C 1-20 saturated alkyl groups, C 6-20 aryl groups, or C 7-20 alkylaryl groups. Examples of hydrocarbyloxy groups that could be formed on magnesium include C 1-20 alkylalkoxides, C 6-20 arylalkoxides, and C 7-20 alkylarylalkoxides. Examples of compounds suitable for use as the hydrocarbyloxy ligand source include C 1-20 saturated alcohols, C 6-20 arylalcohols, or C 7-20 alkylaryl alcohols. Other oxygen-containing organic molecules could also be used, including epoxides, ketones, aldehydes, acetals, carbonates, or orthoformates. Inorganic or organometallic hydrocarbyloxide donors, such as M(OR) 4 , where M=Si, Ge, or Sn, or hydrocarbyl-hydrocarbyloxy compounds such as R 4-x M(OR) x with 0<x≦4 might also be employed.
Examples of compounds useful as halogen donors includes the acid halides: HX, elemental halogens: X 2 , and metal halides such as MX x Y 4-x 0<x≦4 where M=C, Si, Ge, or Sn, and Y=any group bound to M through a single bond. Other potential halogen donors include organic acid halides such as RC(O)X, chloroformates such as ROC(0)X, acid halides of main group oxygen acids, such as SOX 2 and POX 3 . Main group halo compounds such as PX 3 , PX 5 , or BX 3 could also be used.
In addition to the features outlined elsewhere in this text, it is important that the reaction between the hydrocarbyloxy ligand source and the dihydrocarbyl magnesium yield a homogenous solution as a reaction product, and it is preferred that any reaction by-products be easily removed, or else inert in subsequent steps. It is desirable, but not mandatory that the reactivity of the halogen source be such that the hydrocarbylmagnesium hydrocarbyloxide and the halogen source can be mixed without obvious reaction at low temperature, and then brought to a temperature where a controlled reaction occurs. By-products from the halogenation step should be easily removed from the product.
In a preferred embodiment of this invention, a soluble dihydrocarbyl magnesium is reacted with alcohol to form hydrocarbyloxy groups and inert saturated or aromatic hydrocarbons to give a soluble product in an inert saturated or aromatic hydrocarbon solvent. This product is then halogenated with a compound R 4-6XKCx compound with R=hydrocarbyl, M=C, Si, Ge or Sn, and 0<x≦4. In the most preferred embodiment of this invention, a primary saturated alcohol and silicon tetrachloride are used.
Some critical aspects of this reaction involve magnesium-ligand reactivity. In the first step, it is critical that the ligands initially bound to magnesium be reactive toward the hydrocarbyloxy ligand source. In the second step, it is critical that the remaining initial ligands be more reactive than the hydrocarbyloxy ligand toward the halogen ligand source. Finally, it is important to know the reactivity of the halogen ligand source so that one will be able to supply the desired amount of halogen ligand. In Eq (8), for instance, it is important to know that SiCl 4 is able to donate about two Cl groups to magnesium hydrocarbyl compounds.
Another critical aspect of this invention, is the ability of the above strategy to produce a material which detailed chemical characterization shows to be a solid, magnesium, halide and hydrocarbyloxide containing material of uniform composition and purity, and not a mixture of, e.g. MgCl 2 and Mg(OR) 2 which would merely have the correct average composition.
Another interesting aspect of this invention is that the selectivity of the reactions, and the flexibility in amounts used, makes it possible to prepare solids of uniform composition and purity with previously unanticipated component ratios: i.e. with Cl:Mg:OEt ratios other than 1:1:1, such as Cl 3 Mg 2 (OEt). Consequently, this strategy makes available a whole range of discrete magnesium compounds, with a variety of compositions, that are useful as catalyst supports.
The Examples shown below demonstrate that it is possible to use selective reactions to prepare substantially pure solids of uniform purity and composition containing chlorine, magnesium and ethoxide. Examples 3 and 5 demonstrate the preparation of substances with empirical formulae: ClMgOEt and Cl 3 Mg 2 (OEt), respectively. Example 6 demonstrates that, when sufficiently selective components are used, intermediate amounts of the components lead to simple mixtures of the possible products. These results are a large improvement over the prior art, where complex mixtures are more typical, substantially pure solids of uniform composition and purity are not obtained.
The purity and compositional uniformity of the products formed by the present invention can be confirmed by solid state 13 C nuclear magnetic resonance spectroscopy. The instant products show no more than one strong, narrow absorption peak for each chemically inequivalent carbon atom in the hydrocarbyloxy ligand therein. For example, FIG. 1 illustrates the spectra for ClMg(OEt) made in accordance with the present invention, whereas FIG. 2 illustrates the distinctly differing spectra, not containing strong narrow absorption peaks, for the type of material claimed to be ClMg(OEt) as made in Example 1 of U.S. Pat. No. 4,820,879.
Example 7A shows that if a physical mixture of MgCl 2 and Mg(OEt) 2 is prepared, 13 C CPMAS NMR can be used to establish that Mg(OEt) 2 is present. Example 7B shows that 13 C CPMAS NMR has sufficient resolution to differentiate between Cl 3 Mg 2 OEt, as prepared in Example 5, and Mg(OEt) 2 .
Examples 8 through 11 demonstrate use of the present invention to prepare materials containing alkoxy groups containing aryl moieties. While the processes of Examples 9 and 11 have not been optimized and the products formed have not been completely analyzed or purified, the results obtained are sufficient to demonstrate successful use of the invention in making the intended product. In both cases, a ClMgOR compound was formed which had spectral characteristics indicative of a single type of ClMgOR product (versus a mixture of many products as in the prior art) which was spectroscopically distinct from the corresponding Mg(OR) 2 compound, thereby ruling out formation of a mixture of MgCl 2 and Mg(OR) 2 .
The present invention is further illustrated by the Examples which follow.
COMPARATIVE EXAMPLE 1
Preparation of Mg(OEt) 2 for Comparison Purposes
A 3-neck round bottom flask equipped with a mechanical stirrer, a reflux condenser and a gas inlet/outlet adapter was charged with butylethylmagnesium (130 g of a 20.2 wt % solution in heptane: 0.24 mole) and heptane (125 g). This solution was stirred (400 rpm) and was heated to reflux with an external oil bath. Heating was discontinued while tetraethyl orthosilicate (49.9 g, 0.24 mole) was added at a rate just sufficient to maintain reflux. Near the end of the addition, precipitates began to form. Heating was resumed, and the solution was refluxed for two additional hours. The solvent and volatiles were removed in vacuo to give colorless solid Mg(OEt) 2 (32.9 g, theory=27.7 g).
Solid state 13 C CPMAS and inverse-gated decoupled MAS NMR spectra of this product are dominated by two resonances corresponding to carbons in the ethoxy groups. These resonances accounted for ca. 85% of the signal intensity in the 13 C inverse-gated decoupled MAS NMR spectrum. The remaining 15% of signal intensity was shared among several peaks that could be assigned to heptane and/or hydrocarbyl groups bound to silicon. 29 Si CPMAS NMR showed the presence of silicon compounds of the type: R x Si(OEt) 4-x 0≦x<4.
The 13 C CPMAS NMR spectrum of this product, and that of a commercial sample of Mg(OEt) 2 (Aldrich Chemical Co.) were both characterized by two resonances: one corresponding to the methylene (δ=58.1 ppm) carbon, and the other to the methyl (δ=21.7 ppm) carbon of the ethoxy group.
The x-ray powder diffraction pattern for this material showed prominent lines at d=8.26 and 4.17 Å, with the lowest angle reflection at d=9.82
COMPARATIVE EXAMPLE 2
Preparation of MgCl 2 for Comparison Purposes
A 3-neck round bottom flask equipped with a mechanical stirrer, a reflux condenser, and a gas inlet/outlet was charged with butylethylmagnesium (104.6 g of 20.2 wt % solution in heptane: 0.19 mole) and heptane (109 g). This solution was cooled to -15° C. and stirred at 200 rpm. Silicon tetrachloride (32.5 g, 0.19 mole) was added. No reaction or exotherm was observed upon addition of SiCl 4 . The solution temperature was increased by about 1° C./minute until refluxing was achieved. After an hour, the reaction mixture was cooled and precipitated solids were allowed to settle. The supernate was decanted, the solids were washed with three 200 ml portions of fresh heptane and were then collected by filtration (17.5 g, 96% of theory).
The product contained less than 0.2% alkanes by headspace GC analysis and showed only traces of carbon and silicon in 13 C and 29 Si CPMAS NMR analyses. Acid-base titration showed no basic components. Elemental analysis showed 25.6% Mg and 72.4% Cl (theory: 25.5% Mg, 74.4% Cl). The X-ray powder diffraction pattern of this material matched the known pattern for MgCl 2 . The product had a surface area of 12 m 2 /g and a median particle size of 12 μ.
The x-ray powder diffraction pattern for this material showed prominent lines at d=4.15 and 2.58 Å, with the lowest angle reflection at 8.26 Å.
EXAMPLE 3
Preparation of High Surface Area ClMg(OEt)
A 1 L, 3-neck, round bottom flask equipped with a mechanical stirrer, a reflux condenser, and a gas inlet/outlet was charged with butylethylmagnesium (208.2 g of 20.2 wt % Mg/Al solution in heptane: 0.38 mole) and heptane (130 g). This solution was stirred rapidly (400 rpm), heated to 60 ° C., and absolute ethanol (22.9 g, 0.50 mole) added slowly, using care to maintain the temperature. External heat was then increased to reflux the solvent. After two and one-half hours 0.38 mole of (Bu,Et) 0 .7 Mg(OEt) 1 .3 was obtained in the form of a homogeneous solution.
The reaction solution was then cooled to -15° C. and stirred at 110 rpm. Silicon tetrachloride (31.6 g, 0.19 mole) was then added. No immediate exotherm or reaction was observed. The solution temperature was increased by about 1° C./minute to 58° C. where it was held for 16 hours. The reaction mixture was cooled, solids allowed to settle, and the supernate decanted. The solids were then washed with 2 300 mL portions of fresh solvent, collected by decantation and vacuum dried. 33.9 g of solid product were obtained (82% recovery of Mg using a Mg content of 22.4%).
13 C CPMAS NMR analysis of this product showed it to have two sharp resonances, corresponding to a single methylene (δ=59.3 ppm) and a single methyl (δ=19.7 ppm) carbon signal characteristic of a material containing only one ethoxy group environment. Some very weak signals, not associated with ethoxy groups bound to magnesium, probably due to residual heptane or silicon hydrocarbyl groups, were also present.
The X-ray powder diffraction pattern for this material showed prominent lines at d=9.30 and 4.17 Å, with the lowest angle reflection at 9.30 Å.
Elemental analysis showed that this product contained 22.4% Mg and 31.9% Cl along with 5.20% H, 24.35% C. The ratio of Cl to Mg was 0.98:1. Acid-base titration of this material shows that it contains 9.4 mmoles base/gram solid. The ratio of (OEt) groups (total base) to Mg was 1.02 to 1. The sum of the Mg, Cl, C and H analyses, added to the amount of oxygen required by the base analysis totals 98.9%.
BET surface area analysis of this product found 233 m 2 /g. The isothermal desorption curve did not show hysteresis. N 2 porosimetry fond a pore volume of 0.33 cc/g at P/P o =0.98. SEM examination of the product showed it to be composed of agglomerates of sub-micron sized globular particles. Particle size analysis of this product showed a median particle size of the agglomerates of 59 μ.
EXAMPLE 4
Preparation of Low Surface Area ClMg(OEt)
A 1 L, 3-neck, round bottom flask equipped with a mechanical stirrer, a reflux condenser, and a gas inlet/outlet was charged with butylethylmagnesium (135.8 g of 20.2 wt % solution in heptane: 0.25 mole) and heptane (149 g). This solution was stirred rapidly (400 rpm), heated to 60 ° C., and absolute ethanol (13.2 g, 0.29 mole) added slowly, using care to maintain the temperature. External heat was then increased to reflux the solvent. After three hours 0.25 mole of (Bu,Et) 0 .85 Mg(OEt) 1 .15 was obtained in the form of a homogeneous solution.
The reaction solution was then cooled to -15° C. and stirred at 110 rpm. Silicon tetrachloride (21.7 g, 0.13 mole) was then added. No immediate exotherm or reaction was observed. The solution temperature was increased by about 1° C./minute to 58° C. where it was held for 15 hours. The reaction mixture was cooled, solids allowed to settle, and the supernate decanted. The solids were then washed with 3 300 mL portions of fresh solvent, collected by filtration and vacuum dried.
13 C CPMAS NMR analysis of this product showed it to have two sharp resonances, corresponding to a single methylene (δ=59.3 ppm) a single methyl (δ=19.7 ppm) carbon signal characteristic of a material containing only one ethoxy group environment. Weak signals corresponding to a low levels of a higher Cl content material (i.e. the product from example 5) are also present.
The X-ray powder diffraction pattern from this product, which was different from that of known materials, showed several lines, the most prominent corresponding to a d-spacing of 9.30 Å. The X-ray powder diffraction pattern of this material showed no evidence of MgCl 2 .
Elemental analysis showed that this product contained 21.6% Mg and 33.4% Cl along with 5.06% H, 23.41% C. The ratio of Cl to Mg was 1.06:1. Acid-base titration of this material shows that it contains 9.2 mmoles base/gram solid. The ratio of (OEt) groups (total base) to Mg was 1.04 to 1. The sum of the Mg, Cl, C and H analyses, added to the amount of oxygen required by the base analysis totals 98.2%.
BET surface area analysis of this product found 6.1 m 2 /g. SEM examination of the product showed it to be composed of irregular smooth surfaced particles from 0.5 to 10 μ in size. Particle size distribution analysis found a median particle size of 14 μ.
EXAMPLE 5
Preparation of Novel, High Surface Area Cl 3 Mg 2 (OEt)
A 1 L 3-neck round bottom flask equipped with a mechanical stirrer, a reflux condenser, and a gas inlet/outlet port, was charged with butylethylmagnesium (159.8 g of a 20.2 wt % solution in heptane: 0.29 mole) and heptane (130 g). The solution was stirred rapidly (400 rpm), heated to 50 ° C., and absolute ethanol (8.1 g, 0.18 mole) added slowly, causing the temperature to rise to 60° C. This temperature was maintained during the ethanol addition. External heat was then applied to reflux the solvent. After two hours 0.29 mole of R 1 .2 Mg(OEt) 0 .8 was obtained in the form of a homogeneous solution.
The reaction solution was then cooled to -15° C. and stirred at 150 rpm. Silicon tetrachloride (39.4 g, 0.23 mole) was then added. No immediate exotherm or reaction was observed. The solution temperature was increased by about 1° C./minute to 60° C. where it was held for 12 hours. The reaction mixture was cooled, solids allowed to settle, and the supernate decanted. The solids were then washed with 5 200 mL portions of fresh solvent, collected by filtration and vacuum dried. The yield of solid product was 25.3 g (80.1% recovery of Mg using a Mg content of 22.0%).
13 C CPMAS NMR analysis of this product showed it to have two sharp resonances, corresponding to a single methylene (δ=63.0 ppm) carbon signal, and a single methyl (δ=18.9 ppm) carbon signal, which is characteristic of a material containing only one ethoxy group environment. Signals from a small amount of residual heptane were also present.
The X-ray powder diffraction pattern for this material showed prominent lines at d=4.17 and 8.66 Å, with the lowest angle reflection at d=9.93 Å.
Elemental analysis showed that this product contained 22.5% Mg and 49.1% Cl along with 3.40% H, 14.88% C. The ratio of Cl to Mg was 1.50:1. Acid-base titration of this material shows that it contains 5.12 mmoles base/gram solid. The ratio of (OEt) groups (total base) to Mg was 0.55 to 1. The sum of the Mg, Cl, C and H analyses, added to the amount of oxygen required by the base analysis totals 98.3%. 5 BET surface area analysis of this product found 299 m 2 /g. N 2 porosimetry found a pore volume of 0.42 cc/g at P/P o =0.98. SEM examination of the product showed it to be composed of irregularly shaped, porous, agglomerates from 5 to 100 μ in size. Particle size distribution analysis found a median particle size of 35.3 μ.
EXAMPLE 6
Preparation of a Mixture of ClMg(OE) and Cl 3 Mg 2 (OEt) 1
A 1 L, 3-neck, round bottom flask equipped with a mechanical stirrer, a reflux condenser, and a gas inlet/outlet Was charged with butylethylmagnesium (162.6 g of 20.2 Wt% solution in heptane: 0.30 mole) and heptane (200 g). This solution was stirred rapidly (400 rpm), and absolute ethanol (14.1 g, 0.31 mole) added slowly, causing a rise in temperature to 60 ° C. External heat was then applied to reflux the solvent. After three hours 0.30 mole of R 1 .0 Mg(OEt) 1 .0 was obtained in the form of a homogeneous solution.
The reaction solution was then cooled to -15° C. and stirred at 110 rpm. Silicon tetrachloride (24.9 g, 0.15 mole) was then added. No immediate exotherm or reaction was observed. The solution temperature was increased by about 1° C./minute to solvent reflux, where it was held for 2 hours. The reaction mixture was cooled, solids allowed to settle, and the supernate decanted. The solids were then washed with 2 300 mL portions of fresh solvent, collected by filtration and vacuum dried. The yield of solid product was 26.4 g (80% recovery of Mg using a Mg content of 22.2%).
13 C CPMAS NMR analysis of this product showed it to be a mixture of the products from Examples 3 (main component) and 5. Some very weak signals, not associated with ethoxy groups bound to magnesium, probably due to residual heptane or silicon hydrocarbyl groups, were also present.
Elemental analysis showed that this product contained 22.2% Mg and 36.8% Cl along with 5.05% H, 22.75% C and 0.14% Si. The ratio of Cl to Mg was 1.14:1. Acid-base titration of this material shows that it contains 7.9 mmoles base/gram solid. The ratio of (OEt) groups (total base) to Mg was 0.87:1. The sum of the Mg, Cl, C, H and Si analyses, added to the amount of oxygen required by the base analysis totals 99.6%.
BET surface area analysis of this product found 60 m 2 /g, with some hysteresis in the isothermal desorption curve characteristic of `ink-bottle` shaped pores present. N 2 porosimetry found a pore volume of 0.84 cc/g at P/P o =0.98. Particle size distribution analysis found a median particle size of 25 μ.
EXAMPLE 7
Mixture A: Equal amounts of MgCl 2 and Mg(OEt) 2 were ground together with a mortar and pestle, to prepare a physical mixture. The 13 C CPMAS NMR spectrum of this mixture had peaks with the same chemical shift and shape as that of pure Mg(OEt) 2 (methyleneδ=58.1 ppm, methyl δ=21.7 ppm).
Mixture B: One part of Mg(OEt) 2 was added to 4 parts Cl 3 Mg 2 OEt as prepared by Example 5 and the resultant mixture ground with a mortar and pestle, to prepare an intimate physical mixture. The 13 C CPMAS NMR spectrum of this mixture showed peaks from both components, having essentially the same chemical shift and shape as that of the pure compounds: Mg(OEt) 2 (methylene δ=58.0 ppm, methylδ=21.8 ppm) and Cl 3 Mg 2 OEt according to Example 3 (methylene δ=63.3 ppm, methyl δ=19.2 ppm).
COMPARATIVE EXAMPLE 8
Preparation of Mg(--OC 6 H 4 CH.sub.) 2 for Comparison Purposes
A 3-neck round bottom flask equipped with a mechanical stirrer, a reflux condenser and a gas inlet/outlet adapter was charged with para-cresol (9.32 g, 0.0862 mole) and heptane (60 g). Butylethylmagnesium (4.65 grams, 0.0421 mole) in n-heptane (124 g) was slowly added to the reaction flask and white precipitates formed immediately. The reaction mixture was then refluxed for 2 hours. The solids were filtered and then dried in vacuo to give 6.0 g of a colorless solid Mg(--OC 6 H 4 CH 3 ) 2 (57% recovery of Mg using a Mg content of 9.8%).
Elemental analysis showed 9.8% Mg. GC analysis after hydrolysis showed 90.4% para-cresol. The ratio of ( -- OC 6 H 4 CH 3 ):MG was 2.1:1.0 and the sum of the magnesium and para-cresol analyses was 100.2%.
The solid state 13 C CPMAS NMR spectrum of this product was characterized by four resonances: three resonances corresponding to aryl (δ 1 =155.6 ppm, δ 2 ≅δ 3 =130.6 ppm, δ 4 =117.1 ppm) carbons, and one resonance corresponding to a methyl (δ 5 =18.1 ppm) carbon.
EXAMPLE 9
Preparation of ClMg(OC 6 H 4 CH 3 )
A 3-neck round bottom indented flask equipped with a mechanical stirrer, a reflux condenser, and a gas inlet/outlet adapter was charged with butylethylmagnesium(292.7 g of 5.4 wt % solution in toluene: 0.143 mole). The solution was stirred rapidly (300 rpm), heated to 60° C., and para-cresol(15.47 g, 0.143 mole) added slowly. External heat was then increased to reflux the solvent. After 17 hours, silicon tetrachloride(12.42 g, 0.073 mole) was added slowly to the reaction mixture. Gelation occurred immediately upon the addition. The mixture was cooled with stirring to room temperature and then filtered. The solids were washed with 3 ×100 ml of n-heptane and vacuum dried. 11.58 g of solid colorless solid product were obtained (45% recovery of Mg using a magnesium content of 13.6%).
Elemental analysis showed 13.6% Mg and 14.2% Cl. GC analysis after hydrolysis showed 58.2% para-cresol. The ratio of ( -- OC 6 H 4 CH 3 ):MG:Cl=0.96:1.0:0.72.
The solid state 13 C CPMAS NMR spectrum of this product was characterized by four resonances: three resonances corresponding to aryl (δ 1 =155.7 ppm, δ 2 ≅δ 3 =130.1 ppm, δ 4 =119.1 ppm) carbons, and one resonance corresponding to a methyl (δ 5 =20.4 ppm) carbon. Some signals, not associated with para-cresoxy groups bound to magnesium, probably due to residual n-heptane, magnesium hydrocarbyl groups, or silicon hydrocarbyl groups, were also present.
COMPARATIVE EXAMPLE 10
Preparation of [Mg(OC 6 H 2 (C 4 H 9 ) 2 CH 3 ) 2 ] 2
A 3-neck round bottom flask equipped with a mechanical stirrer, a reflux condenser and a gas inlet/outlet adapter was charged with 2,6-di-tert-butyl-4-methylphenol (99.5 g of a 49 wt % solution in n-heptane: 0.2201 moles). Butylethylmagnesium (128.4 g of a 9.5 Wt% solution in n-heptane: 0.1104 moles) was slowly added to the reaction flask. The reaction mixture was then refluxed for 2 hours. The soluble mixture was then allowed to cool to room temperature with stirring. The solids were filtered and then dried in vacuo to give 39.1 g of a colorless solid [Mg(OC 6 H 2 (C 4 H 9 ) 2 CH 3 ) 2 ] 2 (83% recovery based on a Mg content of 5.7%).
Elemental analysis showed 5.7% Mg. GC analysis after hydrolysis showed 93.9% 2,6,-di-tert-butyl-4-methylphenol. The ratio of - OC 6 H 2 (C 4 H 9 ) 2 CH 3 :Mg was 1.8:1.0 (the sum of the Mg and 2,6-di-tert-butyl-4-methylphenol analyses was 99.6%.
The solid state 13 C CPMAS NMR spectrum of this product was characterized by fifteen resonances: eight resonances corresponding to aryl (δ 1 =158.9 ppm, δ 2 =153.0 ppm, δ 3 =137.0 ppm, δ 4 =131.1 ppm, δ 5 =128.4 ppm, δ 6 =126.3 ppm, δ 7 =125.3 ppm, δ 8 =122.0 ppm) carbons, and seven resonances corresponding to hydrocarbyl (δ 9 =35.9 ppm, δ 10 =35.2 ppm, δ 11 =34.3 ppm, δ 12 =31.8 ppm, δ 13 =23.2 ppm, δ 14 =21.5 ppm, δ 15 =19.1 ppm) carbons. The resonance pairs are indicative of a dimeric molecular structure, e.g. [Mg(OC 6 H 2 (C 4 H 9 ) 2 CH 3 ) 2 ] 2 , which is typical for sterically crowded bis phenoxy magnesium compounds such as this (Inorganic Chemistry, Vol. 27 (1988), pp. 867-870).
EXAMPLE 11
Preparation of ClMg(OC.sub. H 2 (C 4 H 9 ) 2 CH 3 )
A 3-neck round bottom indented flask equipped with a mechanical stirrer, a reflux condenser, and a gas inlet/outlet adapter was charged with butylethylmagnesium(267 g of 6.55 wt % solution in toluene: 0.159 mole). The solution was stirred rapidly (300 rpm), heated to 60° C., and 2,6-di-tert-butyl-4-methylphenol (188.0 g of 24.2 wt % solution in toluene: 0.206 mole) was added slowly. External heat was then increased to reflux the solvent. The soluble mixture was heated at reflux for 2 hours and then cooled to -15° C. Silicon tetrachloride(13.91 g, 0.082 mole) was added slowly to the reaction mixture. The soluble mixture was heated at reflux for 1 hour and then cooled with stirring (400-500 rpm) to room temperature. The precipitate was filtered, washed with 100 ml of n-heptane and vacuum dried. 12.6 g of solid colorless solid product were obtained (26% recovery of Mg using a magnesium content of 8.0%).
Elemental analysis showed 8.0% Mg and 9.5% Cl. GC analysis after hydrolysis showed 75.5% 2,6-di-tert-butyl-4-methyl-phenol. The molar ratio of ( - OC 6 H 2 (C 4 H 9 ) 2 CH 3 ):Mg:Cl was 1.04:1.0:0.81.
The solid state 13 C CPMAS NMR spectrum of this product was characterized by seven resonances: four resonances corresponding to aryl (δ 1 =153.4 ppm, δ 2 =138.1 ppm, δ 3 =132.8 ppm, δ 4 =127.7 ppm) carbons, and three resonances corresponding to hydrocarbyl (δ 5 =35.7 ppm, δ 6 =31.7 ppm, δ 7 =20.6 ppm) carbons.
The foregoing Examples have been presented for illustrative purposes only and, for that reason, should not be construed in a limiting sense. The scope of protection sought is set forth in the claims which follow. | A substantially pure, chemically distinct halomagnesium alkoxide compound is formed by reaction of a dihydrocarbylmagnesium compound with a compound which will replace an hydrocarbyl functionality thereon with an hydrocarbyloxy functionality and thereafter reacting the resulting product with a compound which replaces the other hydrocarbyl functionality with a halogen functionality, such as chlorine. The 13 C nuclear magnetic resonance spectrum of the product exhibits no more than one strong, narrow absorption peak for each chemically inequivalent carbon atom in the hydrocarbyloxy ligand of the compound. | 2 |
RELATED APPLICATION
This application is a continuation of U.S. patent application Ser. No. 11/416,534 filed on May 3, 2006.
FIELD OF THE INVENTION
The present invention relates to computer systems; more particularly, the present invention relates to regulating voltage in a microprocessor.
BACKGROUND
Growing demand for integrated circuits (ICs), for example microprocessors, with ever higher levels of performance and functionality have driven these devices to circuit densities beyond 100 million transistors per die. This number may soon exceed one billion transistors on a single die. The growth in transistor density has been made possible by the use of MOSFET transistors with gate lengths below 100 nm. As gate length has shortened, power supply voltages have fallen, in some cases, to below 1 V.
Even in a mobile computing environment (laptop), high-speed microprocessors, with clock speeds in excess of 2 GHz, may require in excess of 100 watts of power when operating at maximum load. With operating voltages below 1 V, this translates to power supply currents that reach beyond 100 A. Nevertheless, when used in a mobile environment, the same microprocessor must often draw less than 1 watt of “average power” due to battery considerations.
Integrated circuits are typically powered from one or more DC supply voltages provided by external supplies and converters. The power is provided through pins, leads, lands, or bumps on the integrated circuit package. The traditional method for providing such high power to integrated circuits may involve the use of a high-efficiency, programmable DC-to-DC (switch-mode) power converter located near the IC package.
This type of converter (buck regulator) may use a DC input voltage as high as 48V and provide a DC output voltage below 2 V. Conventional DC-to-DC power converters use switching frequencies in the neighborhood of 200 KHz, with some high-end units in the 1-2 MHz range. Such converters usually require a handful of relatively large components, including a pulse-width modulation (PWM) controller, one or more power transistors, filter and decoupling capacitors, and one or more large inductors and/or transformers.
Typical switch-mode power converters include one or more phases to supply the full output current. However, in many instances it may be inefficient to implement full operation of the converter, especially in applications that have low (e.g., nearly 0) current draw.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is illustrated by way of example and not limitation in the figures of the accompanying drawings, in which like references indicate similar elements, and in which:
FIG. 1 is a block diagram of one embodiment of a computer system;
FIG. 2 illustrates a block diagram of one embodiment of a central processing unit;
FIG. 3 illustrates one embodiment of a power converter; and
FIG. 4 illustrates a block diagram of one embodiment of a power control unit.
DETAILED DESCRIPTION
A voltage regulator having a suspend mode is described. In the following detailed description of the present invention, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one skilled in the art that the present invention may be practiced without these specific details. In other instances, well-known structures and devices are shown in block diagram form, rather than in detail, in order to avoid obscuring the present invention.
Reference in the specification to “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. The appearances of the phrase “in one embodiment” in various places in the specification are not necessarily all referring to the same embodiment.
FIG. 1 is a block diagram of one embodiment of a computer system 100 . Computer system 100 includes a central processing unit (CPU) 102 coupled to interconnect 105 . In one embodiment, CPU 102 is a processor in the Itanium® family of processors including the Itanium® 2 processor available from Intel Corporation of Santa Clara, Calif. Alternatively, other CPUs may be used.
A chipset 107 may also be coupled to bus 105 . Chipset 107 includes a memory control hub (MCH) 110 . MCH 110 may include a memory controller 112 that is coupled to a main system memory 115 . Main system memory 115 stores data and sequences of instructions that are executed by CPU 102 or any other device included in system 100 . In one embodiment, main system memory 115 includes dynamic random access memory (DRAM); however, main system memory 115 may be implemented using other memory types. Additional devices may also be coupled to interconnect 105 , such as multiple CPUs and/or multiple system memories.
MCH 110 is coupled to an input/output control hub (ICH) 140 via a hub interface. ICH 140 provides an interface to input/output (I/O) devices within computer system 100 . In addition, computer system 100 includes a power supply 165 to provide power to CPU 102 and chipset 107 . In one embodiment, power supply 165 is implemented as multiple cascaded supplies, where a first supply converts the AC input from a wall outlet to a set of standard voltage rails, and a set of downstream supplies (often referred to as a point-of-load regulators) convert the standard voltages to the less standardized voltages directly used by advanced logic ICs.
FIG. 2 illustrates one embodiment of CPU 102 coupled to power converter 210 . In one embodiment, power converter 210 is a programmable DC-to-DC (switch-mode) power converter located near the CPU 102 IC package to provide high power to CPU 102 . However in other embodiments, power converter 210 may be located on the CPU 102 package.
FIG. 3 illustrates one embodiment of power converter 210 . Power converter 210 is a 2-phase converter that receives a 12V voltage input at each phase, which is converted to a 1.2V output voltage. According to one embodiment, each phase includes a set of power field effect transistors (FETs) and an inductor. The phases all couple into a shared bank of output filter capacitors, represented in FIG. 3 as a single capacitor C.
Referring back to FIG. 2 , CPU 102 includes processing cores 0 - 3 coupled to receive power from power converter 210 , and a power control unit 250 . Each processing core operates as an independent microprocessor to permit thread-level parallelism. Power control unit 250 regulates the voltage applied to CPU 102 by power converter 210 , based at least in part on the potential of the operational frequency of all or a subset of the operational circuit(s) of CPU 102 .
FIG. 4 illustrates one embodiment of power control unit 250 . Power control unit 250 includes a voltage regulator (VR) microcontroller 410 , a finite state machine (FSM) control block 420 and a VR 430 . VR microcontroller 410 provides voltage control configuration parameters that are implemented to control voltage. According to one embodiment, VR microcontroller 410 provides the configuration parameters via input/output (I/O) writes to addresses to add coefficients that define voltage control functionality.
FSM control block 420 implements various FSMs to control various voltage control parameters. In one embodiment, FSM control block 420 includes ramp rate control, power throttle and loadline adjust current. VR 430 includes a compensator 432 and a pulsewidth modulator 436 . Compensator 432 receives a target voltage from control block and compares the target voltage to an actual voltage received from one or more of the cores 0 - 3 .
In response, compensator 432 generates an error term that is used to drive to zero error using negative feedback. Pulsewidth modulator 436 generates pulse signals to control current based upon the error term received from compensator 432 . The pulse signals are transmitted from pulsewidth modulator 436 to power converter 210 to control the activation of the power FETs at each phase.
In normal operation, CPU 102 components may demand a very high current from power converter 210 , which is generally the motivation for designing a voltage regulator with multiple phases. In normal operation, the current demand is generally high enough that multiple phases can continuously be pulsed, and the energy lost in continuous pulsing is small compared to the total current draw.
However at certain instances (e.g., where CPU 102 goes into a sleep state), it would be inefficient for power converter 210 to continuously pulse even a single phase. According to one embodiment, whenever the CPU 102 cores go into a sleep state, power control unit 250 and power converter 210 go into a suspend mode. In such an embodiment, a clock supplying power control unit 250 is deactivated.
In such an embodiment, the current draw at CPU 102 is sufficiently low so as to enable the charge stored at the output filter capacitors to supply power to CPU for a predetermined period of time. For example, if the CPU 102 sleep state duration is in a range of a few (e.g., 2-4) milliseconds operation at power control unit 250 and power converter 210 may be suspended until CPU 102 is reactivated. Thus, the power FET switches at power converter 210 are deactivated (e.g., no current generated by power converter 210 ) until CPU 102 is reactivated.
In another embodiment, power control unit 250 monitors the CPU 102 voltage whenever it and power converter 210 are in the suspend state. In this embodiment, power converter 210 remains in the suspend state until the voltage falls below a predetermined threshold (e.g., 1.2V). Once the voltage falls below the threshold, VR 430 exits the suspend state and transmits a pulse to activate one or both of the phases at power converter 210 in order to supply current to CPU 102 . In a further embodiment, VR 430 may reenter the suspend state once current is supplied to CPU 102 as long as CPU 102 remains in the sleep state. Subsequently, the CPU 102 is again monitored by power control unit 250 .
In yet another embodiment, whenever CPU 102 is in the suspend state and the CPU 102 voltage is above the threshold voltage, power converter 210 will enter an adaptive diode emulation mode. In such a mode, one phase is repeatedly sequenced through the following states: only upper FET on (UPPER state), only lower FET on (LOWER state), both FETs off (OFF state). Further, the repeated sequencing is performed at a largely fixed frequency, and the portion of time spent in each state is adapted to maintain a desired voltage. In another embodiment, the UPPER state time and the LOWER state time may be largely fixed, while the OFF state time is adapted to maintain a desired voltage.
The above-described power management mechanism yields an increase in battery life in a mobile computer system.
Whereas many alterations and modifications of the present invention will no doubt become apparent to a person of ordinary skill in the art after having read the foregoing description, it is to be understood that any particular embodiment shown and described by way of illustration is in no way intended to be considered limiting. Therefore, references to details of various embodiments are not intended to limit the scope of the claims which in themselves recite only those features regarded as essential to the invention. | A system is disclosed. The system includes a central processing unit (CPU) to operate in one or more low power sleep states, and a power converter. The power converter includes phase inductors; and one or more power switches to drive the phase inductors. The one or more power switches are deactivated during the CPU sleep state. | 7 |
BACKGROUND OF THE INVENTION
Canola oil presently is commercially available which consists of approximately 6 percent saturated fatty acids primarily in the form of stearic acid (C18:0) and palmitic acid (C16:0), approximately 62 percent by weight oleic acid (C18:1) which contains a single double bond per molecule, approximately 22 percent by weight linoleic acid (C18:2) which contains two double bonds per molecule, approximately 10 percent by weight linolenic acid (C18:3) which contains three double bonds per molecule, and less than one percent by weight erucic acid (C22:1) which contains a single double bond per molecule.
Over the years scientists have worked to improve the fatty acid profile for rapeseed oil. Initially the erucic acid (C22:1) composition of rapeseed oil was reduced to produce what is often termed to be “canola” oil. The oxidative stability of the vegetable oil is related to the number of double bonds in its fatty acids. Molecules with several double bonds are recognized to be less stable. Thus, scientists also have worked to reduce the content of linolenic acid (C18:3) in order to improve shelf life and oxidative stability, particularly upon exposure to heat. This has not proved to be possible through the use of naturally occurring germplasm and the reported values for linolenic acid (C18:3) for such germplasm have been greater than 6 percent by weight (e.g., greater than 6 up to approximately 12 percent by weight). As reported by Gerhard Robbelen in Chapter 10 entitled “Changes and Limitations of Breeding for Improved Polyenic Fatty Acids Content in Rapeseed” from “Biotechnology for the Oils and Fats Industry” edited by Colin Ratledge, Peter Dawson, and James Rattray, American Oil Chemists' Society (1984), a mutagenesis experiment was able to achieve lines with less than approximately 3.5 percent by weight of linolenic acid (C18:3) based upon the total fatty acid content. The profiles of these lines indicated that nearly all of the linolenic acid was being directed to linoleic acid (C18:2) and that the levels of oleic acid (C18:1) increased only one or two percent. Nevertheless the oil appeared to offer some advantages over normal canola oil. For instance, the refining process required less hydrogenation than normal canola oil and it exhibited a superior fry life.
Studies have established the value of monounsaturated fatty acids as a dietary constituent. This has led to the popularization of the “Mediterranean Diet,” with its emphasis on olive oil, a naturally occurring high source of oleic acid (C18:1). Such a diet is thought to avoid the problem of arteriosclerosis that results from the consumption of saturated fatty acids. However, even in this diet olive oil is thought to be less than ideal, due to its level of saturates. Canola oil is potentially a superior dietary oil, since it contains approximately one-half the saturated fat content of olive oil.
Mutagenesis techniques have been disclosed in the technical literature for increasing the oleic acid (C18:1) content of endogenously formed canola oil over that typically encountered. See in this regard the teachings of U.S. Pat. Nos. 5,625,130 and 5,638,637; European Patent No. 0323753; and International Publication Nos. WO90/10380 and WO92/03919.
Also, approaches involving genetic engineering have been utilized to modify the fatty acid profile of the oil that is endogenously formed in rapeseeds. See, for instance, International Publication No. WO 93/11245, and the Hitz et al. article appearing in the Proceedings of the Ninth International Rapeseed Congress, Cambridge, UK, Vol. 2, Pages 470 to 472 (1995).
Heretofore, it commonly has been observed that when a rape plant is provided that endogenously forms a vegetable oil having an oleic acid content (C18:1) of at least 80 percent by weight that such plant also exhibits less than optimum agronomic performance. Such reduced agronomic performance often is manifest by reduced plant vigor, a later flowering propensity, a lesser number of seed pods per plant, a lesser number of seeds per pod, a lesser overall plant yield, a smaller number of leaves per plant, a lesser total leaf area per plant, a lesser plant height, and a requirement for more time for the plant to reach full maturity. This reduced agronomic performance must be weighed against the improved character of the endogenously formed vegetable oil with respect to oleic acid production that is made possible by such plants.
It is an object of the present invention to provide an improved plant breeding process for forming Brassica napus F 1 hybrid seed having an enhanced commercial value attributable to a combination of (1) the atypical fatty acid profile of the endogenously formed seeds, and (2) the seed yield.
It is an object of the present invention to provide an improved plant breeding process for forming Brassica napus F 1 hybrid seed which exhibits a highly elevated oleic acid (C18:1) content.
It is a further object of the present invention to provide an improved process for forming Brassica napus F 1 hybrid seeds which exhibit a highly elevated oleic acid (C18:1) content and when planted can be grown to form rape plants associated with high oleic acid production which are free from the agronomic shortcomings commonly encountered in the prior art with rape plants that yield such an elevated oleic acid content.
These and other objects and advantages as well as the scope, nature, and utilization of the claimed invention will be apparent to those skilled in the art from the following detailed description and appended claims.
SUMMARY OF THE INVENTION
It has been found that an improved process for producing seeds capable of forming F 1 hybrid Brassica napus plants comprises:
(a) planting in pollinating proximity in a planting area parent plants (i) and (ii), wherein parent (i) is a Brassica napus plant possessing solely in either the A-genome or the C-genome a homozygous modified FAD-2 (i.e., oleate desaturase) gene pair that causes expression of an elevated oleic acid concentration in the endogenously formed oil of the seeds formed thereon, and further possesses at least one homozygous modified FAD-3 (i.e., linolate desaturase) gene pair that causes the expression of a reduced linolenic acid concentration in the endogenously formed oil of the seeds, and wherein parent (ii) is a Brassica napus plant possessing in each of the A-genome and the C-genome a homozygous modified FAD-2 gene pair that causes the expression of an elevated oleic acid concentration in the endogenously formed oil of the seeds formed thereon whereby oleic acid is formed in the endogenously formed oil of the seeds in a greater concentration than in the seeds of parent (i) under the same growing conditions, and further possesses at least one homozygous modified FAD-3 gene pair that results in a reduced linolenic acid concentration in the endogenously formed oil of the seeds formed thereon;
(b) growing Brassica napus plants resulting from the planting of step (a);
(c) preventing self-pollination of the plants of parent (i);
(d) transferring pollen between parent (ii) and parent (i); and
(e) harvesting F 1 hybrid seeds produced on plants of parent (i) that are capable of forming Brassica napus plants that upon self-pollination form seeds possessing an endogenously formed vegetable oil having an oleic acid concentration of at least 80 percent by weight and which exceeds that of parent (i), a linolenic acid concentration of no more than 3 percent by weight, and wherein the resulting F 1 hybrid seeds when planted are capable of producing a crop in a yield that exceeds that of parent (i) and parent (ii) when each parent is pollinated by a pollen source possessing a genotype substantially the same as that of each parent plant and is grown under the same conditions.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The fatty acid concentrations discussed herein are determined in accordance with a standard procedure wherein the oil is removed from the Brassica napus oilseeds by crushing and is extracted as fatty acid methyl esters following reaction with methanol and sodium methoxide. Next the resulting ester is analyzed for fatty acid content by gas liquid chromatography using a capillary column which allows separation on the basis of the degree of unsaturation and chain length. This analysis procedure is described in the work of J. K. Daun et al, J. Amer. Oil Chem. Soc ., 60:1751-1754 (1983) which is herein incorporated by reference.
It is recognized that Brassica napus is a dibasic allotetraploid formed of two genomes (i.e., the A-genome and C-genome) and has a total of 38 chromosomes. The A-genome component is derived from Brassica campestris and consists of 20 chromosomes. The C-genome component is derived from Brassica oleracea and consists of 18 chromosomes.
When carrying out the process of the present invention, two parent plants described herein are planted in a planting area and are grown in pollinating proximity, self-pollination of the female parent plants (i.e., seed parent plants) is prevented, pollen is transferred from the male parent plants to the female parent plants to achieve fertilization, and F 1 hybrid seeds are formed thereon in a yield that exceeds that of both parent plants having an elevated oleic acid (C18:1) content of at least 80 percent by weight based upon the total fatty acid content in the endogenously formed vegetable oil of the seeds. “Pollinating proximity” is used herein to specify that the parent plants are grown in sufficient closeness to make possible the transfer of pollen while maintaining the viability of such pollen. The high oleic acid concentration of the vegetable oil is achieved through the concept of the present invention without sacrifice in agronomic properties.
The improved plant breeding process of the present invention involves the selection and utilization of specifically-defined Brassica napus parent plants. Such parent plants have been found through empirical research to be capable of yielding the advantageous results with respect to highly elevated oleic acid content and reduced linolenic acid content in the endogenously formed vegetable oil of the seeds combined with good agronomic performance which commonly was lacking in the prior art.
The Brassica napus female parent (i.e., the seed parent) selected for use in the hybridization process of the present invention possesses solely in either the A-genome or the C-genome a homozygous modified FAD-2 (i.e., oleate desaturase) gene pair that causes the expression of an elevated oleic acid (C18:1) concentration in the endogenously formed oil of the seeds combined with at least one homozygous modified FAD-3 (i.e., linolate desaturase) gene pair that causes the expression of a reduced linolenic acid (C18:3) concentration in the endogenously formed oil of the seeds. Such female parent commonly is selected that forms an oleic acid content of approximately 77 to 79 percent by weight based upon the total fatty acid content in the endogenously formed vegetable oil of the seeds. The vegetable oil oleic acid content of the female parent commonly will exceed that of the well-known Profit variety which possesses an unmodified FAD-2 gene pair by at least 14 percent (e.g., by 14 to 17 percent) by weight under the same growing conditions. The reference Profit variety was introduced by Agriculture Canada during 1989 and is known and publicly available. Seeds of the Profit variety can be obtained from Agriculture and Agri-Food Canada, Sakatoon, Saskatchewan, Canada. It has been found to be essential that the modified FAD-2 gene pair be present solely in either the A-genome or the C-genome so as to avoid the impairment of agronomic qualities that otherwise are observed if such modification were present in both genomes. The presence of the modified FAD-2 gene pair in both genomes (i.e., in the A-genome as well as in the C-genome) which leads to an even more highly elevated oleic acid production in the endogenously formed vegetable oil of the seeds commonly has been found to concomitantly impact adversely upon lipid loading throughout the plant including the cell membranes and to result in reduced agronomic performance as previously discussed. The presence of a modified FAD-2 gene pair solely in one genome can be confirmed by a oleic acid (C18:1) in the endogenously formed vegetable oil of the seeds of approximately 76 to 79 percent by weight based upon the total fatty acid content.
The Brassica napus male parent (i.e., the pollen parent) selected for use in the hybridization process of the present invention possesses in each of the A-genome and in the C-genome a homozygous modified FAD-2 gene pair that causes the expression of an elevated oleic acid concentration in the endogenously formed oil of the seeds in a greater concentration than in the seeds of the female parent. Such male parent commonly is selected that forms an oleic acid content of approximately 85 to 89 percent by weight based upon the total fatty acid content in the endogenously formed vegetable oil of the seeds. The vegetable oil oleic acid content of the male parent commonly will exceed that of the well-known Profit variety by at least 20 percent (by 20 to 25 percent) by weight under the same growing conditions. In view of the presence of the modified FAD-2 gene pair in both the A-genome and the C-genome, the overall agronomic qualities of the male parent are lesser than those of the female parent.
Parent plants possessing the modified genomes as discussed above can be formed by genetic engineering or the mutagenesis of conventional Brassic napus germplasm (e.g., existing canola varieties), or can be selected from previously available sources that already incorporate the requisite modified genomes as discussed herein. Once on hand, the requisite genes can be readily transferred by conventional plant breeding into other Brassica napus germplasms.
In a preferred embodiment when carrying out mutagenesis, one selects plant cells capable of regeneration (e.g., seeds, microspores, ovules, pollen, vegetative parts) from any of the oilseed Brassica napus varieties (e.g., canola) which are recognized to have superior agronomic characteristics. The Brassica napus plants may be of either the summer or winter types. The oilseed Brassica napus plant cells are subjected in at least one generation to mutagenesis, and an oilseed Brassica napus plant is regenerated from the cells to produce an oilseed plant and to form an oilseed in at least one subsequent generation that possesses the ability to form the atypical modified FAD-2 gene pair in the female parent and the atypical modified FAD-2 gene pairs in the male parent. Parent oilseed Brassica napus plants possessing the requisite FAD-2 gene pair(s) may be produced following mutagenesis via self-pollination for a sufficient number of generations (2 to 8 generations) to achieve substantial genetic homogeneity. Alternatively, the desired characteristics can be fixed through the formation of a new plant from a haploid microspore cell, causing the haploid to double, and producing a homozygous diploid plant in accordance with known techniques.
The mutagenesis preferably is accomplished by subjecting the plant cells (an oilseed) to a technique selected from the group consisting of contact with a chemical mutagen, gamma irradiation, and a combination of the foregoing, for a sufficient duration to accomplish the desired genetic modification but insufficient to completely destroy the viability of the cells and their ability to be regenerated into a plant. The Brassica napus oilseed preferably possesses a moisture content of approximately 5 to 6 percent by weight at the time of such mutagenesis. The mutagenesis may be accomplished by use of chemical means, such as by contact with ethylmethylsulfonate, ethylnitrosourea, etc., and by the use of physical means, such as x-rays, etc. The mutagenesis also may be carried out by gamma radiation, such as that supplied by a Cesium 137 source. The gamma radiation preferably is supplied to the plant cells (e.g., an oilseed) in a dosage of approximately 60 to 200 Krad., and most preferably in a dosage of approximately 60 to 90 Krad. It should be understood that even when operating at radiation dosages within the ranges specified, some plant cells (e.g., oilseeds) may completely lose their viability and must be discarded. See commonly assigned U.S. Pat. Nos. 5,625,130 and 5,638,637 which are herein incorporated by reference for a further discussion of the mutagenesis treatment.
When a mature Brassica napus halfseed is found to possess a desired mutation(s), the other halfseed, which will be genetically the same as the halfseed which was subjected to halfseed analysis, can next be caused to germinate and an oilseed Brassica napus plant is formed from the same and is allowed to undergo self-pollination. Such planting of the halfseed preferably also is carried out in a greenhouse in which the pollination is carefully controlled and is monitored. The resulting oilseeds formed on a plant resulting from the halfseed are harvested, planted, and are self-pollinated for a sufficient number of generations to achieve substantial genetic homogeneity. The genetic stabilization of the oilseed Brassica napus plant material enables the creation of plants having a reasonably predictable genotype which can be used as breeding or source material.
In accordance with the concept of the present invention, it additionally is essential that each of the female and male parent plants possesses at least one homozygous modified FAD-3 (i.e., linolate desaturase) gene pair that causes the expression of a reduced linolenic acid (i.e., alpha-linolenic acid) concentration in the endogenously formed oil of the seeds. Such modified FAD-3 gene pair can be obtained by genetic engineering or the mutagenesis of conventional Brassica napus germplasm (e.g., existing canola varieties) or can be selected from previously available sources that already incorporate the requisite FAD-3 gene modification. The modified FAD-3 gene pair can be present in either the A-genome or in the C-genome, and preferably is present in each of the these genomes. The modified FAD-3 gene pair likewise preferably is obtainable by mutagenesis. A reduced linolenic acid content of no more than 3 percent by weight based upon the total fatty acid content preferably is exhibited by each of the parent plants in the endogenously formed vegetable oil of the seeds. In a preferred embodiment, both the female parent and the male parent exhibit a linolenic acid (C18:3) content of approximately 1 to 3 percent by weight (e.g., 1 to 2 percent by weight) based upon the total fatty acid content.
Oilseed Brassica napus germplasm containing the requisite homozygous modified FAD-3 gene pair(s) that causes a reduced linolenic acid concentration in the endogenously formed oil of the seeds is known and is publicly available. For instance, rape germplasm possessing this trait has been available in Germany from the mid-1970's, and in North American since 1983. Representative commercially available rape varieties that include the genetic means for the expression of this low linolenic acid trait include STELLAR, and APOLLO. A particularly preferred source for the requisite FAD-3 gene pair for the expression of enhanced linolenic acid in the stated concentration is the STELLAR variety that was developed at the University of Manitoba, Manitoba, Canada, during 1987, following receipt of support from the Western Canola and Rapeseed Recommending Committee. Also, a particularly preferred source for the requisite FAD-3 gene pair for the expression of enhanced linolenic acid in the stated concentration is the APOLLO variety that was developed at the University of Manitoba, and was registered in Canada as No. 3,694 during February, 1992, following the receipt of support from the Western Canola and Rapeseed Recommending Committee.
Brassica napus seeds designated NS1973 and NS2037 and possessing the requisite modified FAD-2 gene pair solely in one genome as well as the modified FAD-3 gene pair suitable for use as the female parent in the process of the present invention were deposited under the terms of the Budapest Treaty at the American Type Culture Collection, 10801 University Boulevard, Manassas, Va., U.S.A. 20110-2209, on Jun. 25, 1998. A 2,500 seed deposit of NS1973 has been assigned ATCC Accession No. 209997. A 2,500 seed deposit of NS2037 has been assigned ATCC Accession No. 209994.
Brassica napus seeds designated 95SN-56605 and 95SN-56634 and possessing the requisite modified FAD-2 gene pair in both the A-genome and the C-genome as well as modified FAD-3 gene pair suitable for use as the male parent in the process of the present invention additionally were deposited under the terms of the Budapest Treaty at the American Type Culture Collection on Jun. 25, 1998. A 2,500 seed deposit of 95SN-56605 has been assigned ATCC Accession No. 209995. A 2,500 seed deposit of 95SN-56634 has been assigned ATCC Accession No. 209996.
When the parent plants are grown within pollinating proximity of each other in accordance with the process of the present invention, it is essential that self-pollination of the female parent plants be precluded. This can be done through the emasculation of the flowers at an early stage of flower development. Such impediment to self-pollination preferably is accomplished through the prevention of pollen formation on the female parent plants through any one of a variety of techniques that is inherent within the plant. Such female parent plants can incorporate some form of male sterility. For instance, male sterility can be cytoplasmic male sterility (i.e., genic-cytoplasmic), nuclear male sterility, molecular male sterility wherein a transgene inhibits microsporogenesis and/or pollen formation, or be produced by self-incompatability. In a particularly preferred embodiment the female parent plants possess cytoplasmic male sterility of the ogura (OGU) type and the male parent plants include a fertility restorer as available from Institut National de Recherche Agricole (INRA) of Rennes, France. See also in this regard the technology of International Publication Nos. WO92/05251 and WO98/027806 which is herein incorporated by reference.
The improved process of the present invention can be used to advantage to form single-cross Brassica napus F 1 hybrids. During such single-cross embodiment the parent plants can be grown as substantially homogeneous adjoining populations so as to well facilitate natural cross-pollination from the male parent plants to the female parent plants. The F 1 seed formed on the female parent plants next is selectively harvested by conventional means. One also has the option of growing the two parent plants during the formation of a single-cross hybrid in bulk and harvesting a composite seed blend of high oleic acid content consisting of F 1 hybrid seed, formed on the female parent and seed formed upon the male parent as the result of self-pollination. Alternatively, three-way crosses can be carried out wherein a single-cross F 1 hybrid is used as a female parent and is crossed with a different male parent that satisfies the fatty acid parameters for the female parent of the first cross. Here, assuming a bulk planting, the overall oleic acid content of the vegetable oil will be reduced over that of a simple single-cross hybrid; however, the seed yield will be further enhanced in view of the good agronomic performance of both parents when making the second cross. Also, the formation of double-cross hybrids can be carried out wherein the products of two different single-crosses are combined. Self-incompatibility can be used to particular advantage to prevent self-pollination of female parents when forming a double-cross hybrid. Here the final seed product will be a composite of more than one genotype wherein the overall oleic acid content is at least 80 percent by weight based upon the total fatty acid content.
The F 1 hybrid seeds made possible by the use of the technology of the present invention commonly exhibit an oleic acid concentration of approximately 80 to 86 percent by weight and a linolenic acid content of approximately 1 to 3 percent by weight based upon the total fatty acid content, and are capable of forming plants which following self-pollination and seed set yield a seed harvest bearing a vegetable oil having average oleic acid and linolenic acid concentrations within the specified ranges.
The improved process of the present invention makes possible the formation of Brassica napus F 1 hybrid seeds which when planted are capable of producing a crop in a yield that exceeds that of each parent used in the formation of the F 1 hybrid when each parent is pollinated by a pollen source possessing a genotype substantially the same as that of each parent and is grown under the same conditions. Additive gene action with respect to oleic acid production is achieved without sacrifice of agronomic characteristics. This good yield is made possible while making possible an oleic acid content in the vegetable oil of at least 80 percent (e.g., 80 to 86 percent) by weight based upon the total fatty acid content. Commonly, seed yields of equal to or greater than those of widely grown canola varieties which lack the modified fatty acid profile are made possible. In a preferred embodiment the yield exceeds that of the well-known Legend variety under the same growing conditions. The reference Legend variety was introduced by Svalöf AB during 1988 and is known and publicly available. Seeds of the Legend variety can be obtained from Svalöf-Weibull Canada Ltd., of Lindsay, Ontario, Canada.
The following Examples are presented as specific illustrations of the claimed invention. It should be understood, however, that the invention is not limited to the specific details set forth in the Examples.
EXAMPLE I
A Brassica napus line designated NS1973 was selected for use as the female parent. Such line was derived through crossing and pedigree selection in progeny generations from FA677M5-132 (ATCC Accession No. 40523). In the endogenously formed vegetable oil of NS1973 there was exhibited an average oleic acid (C18:1) content of 79.02 percent by weight and an average linolenic acid (C18:3) content of 1.65 percent by weight based upon the total fatty acid content. In this female parent the elevated oleic acid content was created through the presence of a homozygous modified FAD-2 gene pair solely in one genome that was formed through mutagenesis and the reduced linolenic acid content was created through the presence of at least one homozygous modified FAD-3 gene pair that was formed through mutagenesis. Seeds of NS1973 bear ATCC Accession No. 209997 as earlier discussed.
A Brassica napus line designated 95SN56605 was selected for use as the male parent. Such line was derived through crossing and pedigree selection in progeny generations from FA677M5-132 (ATCC Accession No. 40523). In the endogenously formed vegetable oil of 95SN56605 there was exhibited an average oleic acid (C18:1) content of 87.09 percent by weight and an average linolenic acid (C18:3) content of 1.64 percent by weight based upon the total fatty acid content. In this male parent the highly elevated oleic acid content was created through the presence of a homozygous modified FAD-2 gene pair in both the A-genome and the C-genome that was formed through mutagenesis and the reduced linolenic acid content was created through the presence of at least one homozygous modified FAD-3 gene pair that was formed through mutagenesis. Seeds of 95SN56605 bear ATCC Accession No. 209995 as previously discussed.
In order to determine parent yield potential, the parent lines were grown as a plot of twenty plants each in a replicated yield trial at Acton, Ontario, Canada, and were bagged to ensure self-pollination. The bags were removed at the end of flowering so that the fatty acid composition of the selfed seed would not be affected by an artificial bagged environment during the final portion of the seed filling when most of the lipid accumulation takes place. At maturity the selfed plants were harvested individually. Fatty acid and yield determinations were made. When determining yield the total weight of harvested seed was adjusted to 8.5 percent moisture. A value of 100 was assigned to the seed yield of the NS1973 female parent. On this scale, a seed yield of only 43 percent that of the female parent was found to form on the 95SN56605 male parent.
F 1 hybrid seeds and F 2 seeds were produced in a common field environment at the same location and were evaluated for yield and fatty acid composition. More specifically, the flowers of the NS1973 female parent were hand emasculated at an early stage of flower development according to the procedure described in Chapter 35 entitled “Rapeseed and Mustard” by R. K. Downey et al appearing at Pages 495 to 509 of “Hybridization of Crop Plants” edited by Walter R. Fehr and Henry H. Hadley (1980) in order to prevent the self-pollination of the female parent plants. At the appropriate stage in flower maturity, pollen was transferred by hand from the 95SN56605 male parent plants to the NS1973 female parent plants to accomplish fertilization. F 1 hybrid seeds were next produced on the fertilized NS1973 female parent plants which were selectively harvested and were analyzed for the fatty acid composition of the endogenously formed vegetable oil of the seeds.
The resulting F 1 hybrid seeds were found to exhibit an average elevated oleic acid content of 82.36 percent by weight and a reduced linolenic acid content of 1.59 percent by weight based upon the total fatty acid content. Also, the F 1 hybrid seed yield was found to be 127 percent of the female parent and exceeded that of each of the parent plants. Also, when the F 1 hybrid seeds were planted, they were found to exhibit good agronomic characteristics unlike the male parent plants.
EXAMPLE II
Example I was repeated with the exception that Brassica napus 95SN56634 (ATCC Accession No. 209996) was substituted for male parent 95SN56605. Such 95SN56634 line was derived through crossing and pedigree selection in progeny generations from FA677M5-132 (ATCC Accession No. 40523). In the endogenously formed vegetable oil of 95SN56634 there was exhibited an average oleic acid (C18:1) content of 86.57 percent by weight and an average linolenic acid (C18:3) content of 1.42 percent by weight based upon the total fatty acid content. The seed yield of the 95SN56634 male parent was found to be only 50 percent that of the female parent. The highly elevated average oleic acid content of the male parent was created through the presence of a homozygous modified FAD-2 gene pair in both the A-genome and the C-genome that was formed through mutagenesis and the reduced linolenic acid content was created through the presence of at least one homozygous modified FAD-3 gene pair that was formed through mutagenesis. The resulting F 1 hybrid seeds were found to exhibit an average elevated oleic acid content of 82.6 percent by weight and an average reduced linolenic acid content of 1.69 percent by weight based upon the total fatty acid content. Also, the F 1 hybrid seed yield was found to be 108 percent that of the female parent. When the F 1 hybrid seeds were planted, the resulting plants were found to exhibit good agronomic characteristics unlike the male parent plants.
EXAMPLE III
Example I was repeated with the exception that Brassica napus line NS2037 (ATCC Accession No. 209994) was substituted for female parent line NS1973 and Brassica napus line 95SN56634 was substituted for male parent line 95SN56605. Such NS2037 line was derived through crossing and pedigree selection in progeny generations from FA677M5-132 (ATCC Accession No. 40523). In the endogenously formed vegetable oil of NS2037 there was exhibited an average oleic acid (C18:1) content of 78.64 percent by weight and an average linolenic acid (C18:3) content of 1.52 percent by weight based upon the total fatty acid content. In such female parent the elevated oleic acid content was created through the presence of a homozygous modified FAD-2 gene pair solely in one genome that was formed through mutagenesis and the reduced linolenic acid content was created through the presence of at least one homozygous modified FAD-3 gene pair that was formed through mutagenesis. The F 1 hybrid seed was found to exhibit an average elevated oleic acid content of 82.3 percent by weight and an average reduced linolenic acid content of 1.51 percent by weight based upon the total fatty acid content. Also, the F 1 hybrid seed yield was found to be 150 percent that of the female parent and exceeded that of each of the parent plants. Also, when the F 1 hybrid plants were planted, the resulting plants were found to exhibit good agronomic characteristics unlike the male parent plants.
EXAMPLE IV
Example I was repeated with the exception that Brassica napus line NS2037(ATCC Accession No. 20994) utilized in Example III was substituted for female parent line NS1973. The F 1 hybrid seed was found to exhibit an average elevated oleic acid (C18:1) content of 82.69 percent by weight and an average reduced linolenic acid (C18:3) content of 1.46 percent by weight based upon the total fatty acid content. Also, the F 1 hybrid seed yield was found to be 119 percent that of the female parent. When F 1 hybrid plants were planted, the resulting plants were found to exhibit good agronomic characteristics unlike the male parent plants.
The homozygous modified FAD-2 and FAD-3 gene pairs present in the Brassica napus parent plants of all Examples can be readily transferred by conventional plant breeding to other Brassica napus germplasms which can likewise be used to carry out the process of the present invention. Also, the prevention of the self-pollination of the female parent plants when carrying out the process of the present invention can be expeditiously carried out on a larger scale by the use of various types of male sterility, etc., as previously discussed. Such techniques to preclude self-pollination of the female parent plants are already known and available to those skilled in plant breeding.
Although the invention has been described with preferred embodiments, it is to be understood that variations and modifications may be resorted to as will be apparent to those skilled in the art. Such variations and modifications are to be considered within the purview and scope of the claims appended hereto. | An improved route is provided for producing seeds capable of forming a Brassica napus F 1 hybrid via plant breeding wherein the vegetable oil of the seeds exhibits a highly elevated oleic acid (C18:1) content of at least 80 percent by weight (e.g. 80 to 86 percent by weight) and a reduced linolenic acid (C18:3) content of no more than 3 percent by weight (e.g. 1 to 3 percent by weight) based upon the total fatty acid content. The female parent plant (i.e., the seed parent) possesses a homozygous modified FAD-2 gene pair for elevated oleic acid production solely in either the A-genome or the C-genome, and the male parent (i.e, the pollen parent) possesses a homozygous modified FAD-2 gene pair for highly elevated oleic acid production in both the A-genome and the C-genome. Both parent plants also include at least one homozygous modified FAD-3 gene pair for reduced linolenic acid production. The seed yield depression commonly observed in the past in Brassica napus plants exhibiting a comparable highly elevated oleic acid concentration effectively is ameliorated in an efficient manner. The grower of the resulting seeds can produce a Brassica napus crop in improved yields wherein the endogenously formed oil of the seed harvest contains on average the desired elevated oleic acid content and reduced linolenic acid content. An endogenously formed Brassica napus oil is provided that is particularly well suited for use in frying applications. Such oil exhibits further stability in view of the low concentration of linolenic acid that concomitantly is produced within the seeds. | 0 |
FIELD OF THE INVENTION
[0001] The present invention relates to a new process for large-scale production of 3-{4-methyl-5-[(1R)-1-(2-(3-methylphenyl-2H-tetrazol-5-yl)-ethoxy]-4H-[1,2,4]triazol-3-yl}-pyridine, which is a pharmacologically useful mGluR5 antagonist. The present invention also provides new processes for large-scale production of 3-(5-methanesulfonyl-4-methyl-4H-1,2,4-triazol-3-yl)-pyridine as well as (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol, which compounds are intermediates in the process of producing 3-{4-methyl-5-[(1R)-1-(2-(3-methylphenyl-2H-tetrazol-5-yl)-ethoxy]-4H-[1,2,4]triazol-3-yl}-pyridine.
TECHNICAL BACKGROUND
[0002] 3-{4-Methyl-5-[(1R)-1-(2-(3-methylphenyl-2H-tetrazol-5-yl)-ethoxy]-4H-[1,2,4]triazol-3-yl}-pyridine is an antagonist of the mGluR5 receptor. Accordingly, this compound is expected to be well suited for treatment of mGluR5 receptor-mediated disorders, such as neurological disorders, psychiatric disorders, gastrointestinal disorders, and chronic and acute pain disorders. This and similar compounds are disclosed in WO2009/051556 and WO2005/080356. Furthermore, WO2005/080356 describes a three-step process of producing 3-(5-methanesulfonyl-4-methyl-4H-1,2,4-triazol-3-yl)-pyridine. WO2009/051556 discloses a six-step process of manufacturing (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol as well as synthesis of the final product 3-{4-methyl-5-[(1R)-1-(2-(3-methylphenyl-2H-tetrazol-5-yl)-ethoxy]-4H-[1,2,4]triazol-3-yl}-pyridine.
[0003] The processes of WO2009/051556 and WO2005/080356 are complicated multi-step processes that are suitable for laboratory scale. Accordingly, there is a need for an improved process, which is possible to carry out in larger scale, and which ideally is simple, cost effective, and without harmful impact on the environment.
SUMMARY OF THE INVENTION
[0004] In a first aspect, the invention provides a process for the manufacture of the compound 3-{4-methyl-5-[(1R)-1-(2-(3-methylphenyl-2H-tetrazol-5-yl)-ethoxy]-4H-[1,2,4]triazol-3-yl}-pyridine of formula 14
[0000]
[0000] wherein
a) the compound 3-(5-methanesulfonyl-4-methyl-4H-1,2,4-triazol-3-yl)-pyridine of formula 6
[0000]
[0000] and the compound (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol of formula 13
[0000]
[0000] are dissolved in an aprotic solvent, whereafter a base is added, providing the compound of formula 14.
[0005] Examples of an aprotic solvent that may be useful in accordance with the invention, is tetrahydrofuran, 2-methyltetrahydrofuran, DMSO, acetonitrile, sulfolan or isopropyl acetate.
[0006] Examples of a base that may be useful in accordance with the invention is an alkoxide base such as lithium-, sodium- or potassium tert-butoxide, lithium-, sodium- or potassium tert-amylate, or a hydride base such as sodium or potassium hydride.
[0007] Preferably, 3-{4-methyl-5-[(1R)-1-(2-(3-methylphenyl-2H-tetrazol-5-yl)-ethoxy]-4H-[1,2,4]triazol-3-yl}-pyridine is purified by crystallization from isopropyl acetate.
[0008] In a second aspect, the invention provides a process for the manufacture of the compound 4-methyl-3-methylthio-5-(3-pyridyl)-1,2,4-triazole of formula 5
[0000]
[0000] comprising the steps of:
i) dissolving nicotinic acid hydrazide in a first solvent;
ii) adding an isocyanate to the solution of step i) until complete conversion is obtained;
iii) adding a base to the resulting mixture of step ii), providing the compound 4-methyl-5-pyridin-3-yl-2,4-dihydro-3H-1,2,4-triazole-3-thione of formula 4
[0000]
[0000] iv) charging methyl iodide to the reaction mixture of step iii);
wherein steps i)-v) are carried out without intermediate isolation;
providing the compound 4-methyl-3-methylthio-5-(3-pyridyl)-1,2,4-triazole of formula 5.
[0009] Preferably, the first solvent is chosen from the group of n-butanol and water.
[0010] Preferably, the isocyanate is methyl isocyanate.
[0011] Preferably, the base is chosen from the group of sodium hydroxide, potassium hydroxide and tributylamine.
[0012] In a particularly preferred embodiment, the first solvent is n-butanol, the isocyanate is methyl isocyanate and the base is tributylamine.
[0013] In a preferred embodiment, the following steps are carried out after step v) above:
[0000] vi) dissolving the compound 4-methyl-3-methylthio-5-(3-pyridyl)-1,2,4-triazole of formula 5 in an acid aqueous solution;
vii) adding a tungstate such as sodium tungstate dihydrate and allowing said tungstate to react with said 4-methyl-3-methylthio-5-(3-pyridyl)-1,2,4-triazole of formula 5;
viii) increasing pH of the reaction resulting in precipitation of the compound 3-(5-methanesulfonyl-4-methyl-4H-1,2,4-triazol-3-yl)-pyridine of formula 4; which is thereafter recovered.
[0014] In a preferred embodiment, said acid aqueous solution is a diluted sulphuric acid solution.
[0015] Preferably step vii) is carried out in presence of hydrogen peroxide. It is also preferred to add a sulphite, such as sodium sulphite, when the reaction has reached completion in order to quench excess peroxide. It is also preferred to increase pH in step viii) by adding a strong base such as sodium hydroxide or potassium hydroxide. It is also preferred to recover 3-(5-methanesulfonyl-4-methyl-4H-1,2,4-triazol-3-yl)-pyridine in step ix) by filtration or centrifugation.
[0016] In a third aspect, the invention provides a process for the manufacture of the compound (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol of formula 13
[0000]
[0000] wherein
aa) (S)-2-methyl-CBS-oxaborolidine and borane or a borane complex, are dissolved in a suitable solvent; whereafter bb) the compound 1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanone of formula 12 is added to the mixture, providing the compound (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol of formula 13.
[0017] Preferably, the borane or borane complex in step aa)) is borane dimethylsulfide. Alternative borane sources such as borane tetrahydrofuran, borane trimethylamine and borane N,N-diethylaniline complexes may be used in the process. Preferably, said suitable solvent is tetrahydrofuran or 2-methyl tetrahydrofuran.
[0018] It is preferred that an excess of borane is quenched by adding an alcohol, such as methanol, after completion of formation of (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol.
[0019] Preferably, the compound (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol is recovered by extracting the reaction with an aqueous solution. Preferably, said aqueous solution is an aqueous solution of hydrochloric acid.
[0020] Alternatively, the compound (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol may be produced enzymatically by using an alcohol dehydrogenase and a co-factor selected from the group of NADH and NADPH, said co-factor being suitable for said alcohol dehydrogenase, comprising the steps of
[0000] AA) providing 1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanone and a suitable co-factor selected from the group of NADH and NADPH;
BB) dissolving said 1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanone and said suitable co-factor in a suspension of a lower alcohol and an aqueous buffer solution;
CC) adding a preparation of a suitable alcohol dehydrogenase and maintaining pH of the resulting mixture within the range 4.9-8.0;
DD) adding an organic solvent such as tert-butyl methylether; and
EE) recovering (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol from the organic phase.
[0021] In a preferred embodiment, said lower alcohol is isopropanol. It is also preferred that the buffer solution is an aqueous solution containing triethanolamine hydrochloride and magnesium chloride.
[0022] In a preferred embodiment, said alcohol dehydrogenase is an alcohol dehydrogenase referred to as IEP Ox58, manufactured by IEP GmbH, DE, and obtainable from DSM pharmaceutical products, Geleen, NL. However, any alcohol dehydrogenase (EC 1.1.1.1, CAS 9031-72-5) having NADH or NADPH as a co-factor and an ability to produce the (R) isomer of 1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol could be used. Preferably, the enzyme should also be able to regenerate the co-factor that is consumed during reduction of 1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanone, by oxidizing isopropanol toacetone.
[0023] The organic solvent in step dd) is preferably tert-butyl-methylether but other ethers such as tetrahydrofuran, methyl tetrahydrofuran and diethyl ether can also be used.
[0024] Alternatively, (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol may be prepared by a asymmetric hydrogenation comprising the steps of:
[0025] 1) adding said 1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanone to a suitable reaction medium containing a solvent and a catalytic amount of a transition metal based catalyst such as benzeneruthenium (II) chloride dimer in combination with S-Xyl-BINAP and S-DAIPEN or S-Xyl-Segphos in combination with S-DAIPEN or RR-Cyl-C*-Thunefos in combination with S-DAIPEN in the presence of a strong base such as potassium tert-butoxide in 2-propanol.
[0000] 2) reacting 1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanon with hydrogen at an increased pressure.
DETAILED DESCRIPTION OF THE INVENTION
[0026] Accordingly, the present invention provides a process of producing 3-{4-methyl-5-[(1R)-1-(2-(3-methylphenyl-2H-tetrazol-5-yl)-ethoxy]-4H-[1,2,4]triazol-3-yl}-pyridine. The process is divided into two separate branches leading to intermediates 3-(5-methanesulfonyl-4-methyl-4H-1,2,4-triazol-3-yl)-pyridine and (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol, respectively. In the final steps of the process these intermediates are allowed to react with each other leading to formation of 3-{4-methyl-5-[(1R)-1-(2-(3-methylphenyl-2H-tetrazol-5-yl)-ethoxy]-4H-[1,2,4]triazol-3-yl}-pyridine.
[0027] The synthesis of 3-(5-methanesulfonyl-4-methyl-4H-1,2,4-triazol-3-yl)-pyridine is outlined in Scheme 1 below:
[0000]
[0028] The process starts by adding nicotinic acid hydrazide (1) and an isothiocyanate such as methyl isothiocyanate (2) to a solvent selected from the group of water and a lower alcohol, such as n-butanol. When the reaction is completed, the resulting carbazide (3) is exposed to alkaline conditions without intermediate isolation leading to formation of 4-methyl-5-pyridin-3-yl-2,4-dihydro-3H-1,2,4-triazole-3-thione (4). Methyl iodide is then added to the resulting reaction without intermediate isolation and 3-[4-methyl-5-(methylthio)-4H-1,2,4-triazol-3-yl]-pyridine (5) is formed and isolated before next step.
[0029] In case water is used as solvent, sodium hydroxide is added to the reaction mixture containing carbazide (3) in order to increase pH. Sulfide (5) is isolated and purified by extraction with dichloromethane and subsequent precipitation in n-heptane. In a more preferred embodiment, n-butanol is used as solvent. In this case, pH of the carbazide (3)-containing reaction mixture is increased by adding tributylamine. Moreover, sulfide (5) is precipitated directly from the reaction mixture without addition of any anti-solvents and can be isolated by filtration.
[0030] Sulfide (5) is added to an aqueous sulfuric acid solution, where it reacts with a tungstate, such as sodium tungstate dihydrate. Preferably, the solution also contains hydrogen peroxide. When the reaction is completed, excess hydrogen peroxide is quenched by adding a bisulfite, such as sodium bisulfite. Then, pH of the resulting reaction medium is adjusted to pH 3-4 by adding an alkaline agent such as NaOH. The pH adjustment induces precipitation of 3-(5-methanesulfonyl-4-methyl-4H-1,2,4-triazol-3-yl)-pyridine (6).
[0031] The process for preparing (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol is disclosed in Scheme 2, below:
[0000]
[0032] The first process steps up to formation of 1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]-ethanone (12) have been disclosed in U.S. provisional application 60/981,294. m-Toluidine (7), sodium nitrite and sodium acetate is dissolved in a mixture of ethanol, water and hydrochloric acid at a temperature below 5° C. Ethyl 2-chloro-acetoacetate (8) is then added and allowed to react with m-toluidine (7) at room temperature. Resulting ethyl (2Z)-chloro-[(3-methylphenyl)-hydrazono]acetate (9) is obtained by extraction with 2-methyl tetrahydrofuran, and the methyl tetrahydrofuran phase is used as such in next step without intermediate isolation. An aqueous solution of ammonium hydroxide is brought into contact with the 2-methyl tetrahydrofuran phase leading to formation of ethyl (2Z)-amino-[(3-methylphenyl)-hydrazono]-acetate (10). The aqueous phase is discarded and intermediate compound (10) is precipitated from the 2-methyl tetrahydrofuran phase using n-heptane as an anti-solvent. Said ethyl (2Z)-amino-[(3-methylphenyl)-hydrazono]-acetate (10) is dissolved in a mixture of 2-methyl tetrahydrofuran and acetic acid and the resulting mixture is contacted with an aqueous solution of sodium nitrite, leading to formation of ethyl 2-(3-methylphenyl)-2H-tetrazole-5-carboxylate (11). The aqueous phase is discarded and a mixture of methyl magnesium bromide and triethylamine in toluene/tetrahydrofuran is added to the organic phase leading to formation of 1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]-ethanone (12). The reaction mixture is quenched with acetic acid in 2-methyl tetrahydrofuran, and then washed with water and aqueous potassium carbonate solution. The water phase is discarded, the organic phase is concentrated and intermediate compound (12) is precipitated. Intermediate compound (12) is then added to a mixture of (S)-2-methyl-CBS oxaborolidine and borane or a borane complex and (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol (13) is recovered from the reaction.
[0033] Alternatively, 1-[2-(3-Methylphenyl)-2H-tetrazol-5-yl]-ethanone (12) and NADH are added to a mixture of a lower alcohol, such as isopropanol, and an aqueous buffer solution capable of maintaining pH in the range of 4.9-8.0. A preparation of an alcohol dehydrogenase (EC1.1.1.1, CAS 9031-72-5), preferably the preparation referred to as IEP Ox58, manufactured by IEP GmbH, DE and obtainable from DSM pharmaceutical products, Geleen, NL, is added and (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol (13) is formed. The product is recovered by extraction with an organic solvent, such as tert-butyl methyl ether or a similar ether, the aqueous phase is discarded and finally, the organic solvent is removed by evaporation.
[0034] The process of manufacturing 3-{4-methyl-5-[(1R)-1-(2-(3-methylphenyl-2H-tetrazol-5-yl)-ethoxy]-4H-[1,2,4]triazol-3-yl}-pyridine is illustrated in Scheme 3, below:
[0000]
[0035] In the final step, 3-(5-methanesulfonyl-4-methyl-4H-1,2,4-triazol-3-yl)-pyridine and (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol is dissolved in tetrahydrofuran. Potassium tert-butoxide dissolved in tetrahydrofuran is added and the final product 3-{4-methyl-5-[(1R)-1-(2-(3-methylphenyl-2H-tetrazol-5-yl)-ethoxy]-4H-[1,2,4]triazol-3-yl}-pyridine (14) is formed. It is normally further purified, for instance by re-crystallization. A suitable solvent in this regard is isopropyl acetate.
EXPERIMENTAL PART
[0036] The invention will now be disclosed with reference to the following examples. These examples are enclosed for information purposes and are not intended to restrict the scope of the invention.
Reference Example 1
Preparation of 1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]-ethanone (compound 12)
[0037] m-Toluidine (6.86 g, 63.38 mmol) (7) was dissolved in ethanol (20 ml), water (7 ml) and 37% hydrochloric acid (13 ml, 158 mmol) and the solution was cooled to −5° C. A solution of sodium nitrite (4.96 g, 69.72 mmol) in water (14 ml) was added to the reaction mixture while keeping the reaction temperature below 5° C., then a solution of sodium acetate (15.60 g, 190.14 mmol) in water (31 ml) was added while keeping the reaction temperature below 0° C. Ethyl 2-chloroacetoacetate (10.87 g, 63.38 mmol) (8) was added and the reaction mixture was stirred overnight at 27° C. 2-Methyltetrahydrofuran (27 ml) was added and the temperature was adjusted to 40° C., the lower aqueous layer was discarded and the solution of ethyl (2Z)-chloro-[(3-methylphenyl)-hydrazono]acetate (9) was used as such in the next step.
[0038] Ammonium hydroxide (25% solution in water, 29 ml, 393 mmol) was added at 0° C. whereupon the mixture was warmed to 17° C. for 2 hours. The aqueous layer was discarded and 2-Methyltetrahydrofuran (14 ml) was added. The same volume solvent was distilled of at 50° C. under reduced pressure. The procedure was repeated using 21 ml 2-methyltetrahydrofuran and the solution was concentrated to 27 ml. The temperature was adjusted to 30° C. after which n-heptane (27 ml) was added and the solution was cooled to 5° C. during 4 hours whereon another portion of n-heptane (27 ml) was added to the resulting slurry. The product was isolated by filtration, washed with n-heptane (27 ml) and was dried at 40° C. under reduced pressure giving ethyl (2Z)-amino-[(3-methylphenyl)-hydrazono]-acetate (10), 11.19 g as a brown yellow powder in 72% yield over two steps.
[0039] A solution of Sodium Nitrite (3.94 g, 46.17 mmol) in water (22 ml) was added drop wise over 1 hour to a solution of ethyl (2Z)-amino-[(3-methylphenyl)-hydrazono]-acetate (10) (11.19 g, 48.70 mmol) in 2-methyltetrahydrofuran (112 ml) and acetic acid (11 ml, 185 mmol) held at 70° C. The solution was cooled to 35° C. and the aqueous phase was discarded. The organic phase was washed with water (22 ml) followed by potassium carbonate (15.95 g, 115.44 mmol) dissolved in water (45 ml). The organic phase was concentrated by 50% under reduced pressure at 50° C. The solution containing ethyl 2-(3-methylphenyl)-2H-tetrazole-5-carboxylate (11) was used as such in the following step.
[0040] To methyl magnesium bromide 1.4M in toluene/THF (3/1) (59.4 ml, 83.11 mmol) was added triethylamine (35 ml, 249 mmol) at ambient temperature. The mixture was cooled to −20° C. and was added drop wise while keeping the inner temp below −10° C. to the above solution of ethyl 2-(3-methylphenyl)-2H-tetrazole-5-carboxylate (11). The reaction mixture was quenched by adding the mixture to acetic acid (26 ml, 462 mmol) in 2-methyltetrahydrofuran (45 ml) while keeping the reaction temperature below 0° C. After complete addition, the mixture was warmed to 50° C. and the aqueous phase was discarded. The organic phase was washed with water (45 ml) followed by potassium carbonate (10.2 g, 73.9 mmol) dissolved in water (45 ml). The organic phase was concentrated to 20 ml under reduced pressure at 50° C. and isopropanol (60 ml) was added and the then cooled to 5° C. over 4 hours. The product was isolated by filtration, washed with cooled isopropanol (22 ml) and dried under reduced pressure at 40° C. giving 1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]-ethanone (12), 5.46 g in 57% yield over two steps.
Example 2
Enzymatic reduction of 1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]-ethanone to give (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol (compound 13)
[0041] A buffer solution was prepared comprising 100 mM triethanolamine and 2 mM magnesium chloride in water and pH was adjusted to 8.0 with aqueous NaOH.
[0042] 20 g 1-[2-(3-Methylphenyl)-2H-tetrazol-5-yl]ethanone (12) and 12 mg NADH were mixed in 40 ml isopropanol and 50 ml buffer solution (see above) was added. 5 ml of enzyme preparation IEP Ox58 (manufactured by IEP GmbH and obtainable from DSM pharmaceutical products, Geleen, NL) was then added and the pH of the formed suspension is adjusted to 8.0 by addition of 1M NaOH. The suspension was stirred over night at 25° C. until complete conversion is obtained. The mixture is diluted with 375 mL of tert-butyl methylether and 125 mL of water are added. The mixture is stirred and the aqueous phase is discarded. The organic phase is washed 4 times with 125 mL 3 wt % NaCl in water. The organic phase is filtered through a bed of Hyflo and washed with 50 mL of tert-butyl methylether. The organic phase is concentrated in vacuum and 19.9 g, 99% of the wanted product is isolated as a brown oil.
Example 3
Preparation of 4-methyl-3-methylthio-5-(3-pyridyl)-1,2,4-triazole in water (compound 5)
[0043] Nicotinic acid hydrazid (900 g, 6.56 moles, 1 eq), Methyl isothiocyanate (480 g, 6.56 moles, 1 eq) and water (4.15 L, 5 rel. vol.) were charged to a 10 L reactor and the mixture was agitated at 60° C. until complete conversion was obtained. Sodium hydroxide (45% w/w) (700 g, 7.88 moles, 500 ml, 1.2 eq) was added during 30 min and the formed slurry went into solution, the solution was held at 60° C. for 2 h and was then cooled to 20 h. Methyl iodide (1123 g, 7.91 mol, 1.21 eq) was charged to the reaction mixture and full conversion was obtained after 1 h reaction time. Dichloromethan (2.7 L, 3 rel. vol.) was then charged and the mixture was agitated for 30 min. The organic layer was separated and the aqueous layer was washed twice with dichloromethane (2×2.7 L). The organic layers were combined and the aqueous layer was discarded. The organic phase was concentrated under reduce pressure at 40° C. to a total volume of 4 L and the temperature was adjusted to 0° C. n-Heptane (1.8 L, 2 rel. vol.) was charged during 2 h and the slurry was agitated for 8 h and a second portion of n-heptane (2.7 L, 3 rel. vol.) was charged. The slurry was aged for 1 h whereupon the product was isolated by filtration. The filter cake was washed twice with heptane (2×1 L) and the product was dried under reduced pressure at 40° C. giving 820 g, 64% with 95.8% w/w strength and a chromatographic purity of 98%.
Example 4
Preparation of 4-methyl-3-methylthio-5-(3-pyridyl)-1,2,4-triazole in n-butanol (compound 5)
[0044] To a warm solution of nicotinic acid hydrazide (80 g, 583 mmol) in n-Butanol (280 ml) was slowly added a solution of methyl isothiocyanate (43.5 g, 583 mmol) in n-Butanol (120 ml). The reaction mixture was held at 80° C. for 3 h for full conversion to the thiocarbazide. To the reaction mixture was tributylamine (171 ml, 700 mmol) added and the reaction mixture was held at 80° C. for 9 hours until full conversion to the thione was seen. The reaction mixture was cooled to 20° C. and methyl iodide was slowly added and the mixture was stirred for 1 hour. After full conversion to the sulfide the slurry was cooled to 0° C. over 4 hours and the precipitate was isolated by filtration, washed with isopropyl acetate (2*320 ml) and dried under reduced pressure to give 4-methyl-3-methylthio-5-(3-pyridyl)-1,2,4-triazole (91.6 g, 76% yield) as a white solid.
Example 5
Preparation of 4-methyl-3-methylsulfonyl-5-(3-pyridyl)-1,2,4-triazole (compound 6)
[0045] 4-methyl-3-methylthio-5-(3-pyridyl)-1,2,4-triazole (10 g, 48.48 mmol) was mixed with sodium tungstate dihydrate (0.31 g, 0.97 mmol), water (40 mL) and sulfuric acid (2.63 mL, 48.48 mmol). The mixture was warmed to 50° C. and hydrogen peroxide (9.13 mL, 106.66 mmol) was added over 5 h. The solution was kept under stirring until completion when 39% sodium bisulfate in water (1.93 mL, 9.7 mmol) was added to quench excess peroxide. Water (40 mL) and methanol (10 mL) were added followed by the addition of 45% NaOH (4.33 mL, 82.42 mmol) during 30 minutes. The resulting clear solution was seeded with 4-methyl-3-methylsulfonyl-5-(3-pyridyl)-1,2,4-triazole (100 mg) and was held at 50° C. for 1 hour when 45% sodium hydroxide (0.39 mL, 7.27 mmol) was charged over 30 minutes. The mixture was held at 50° C. for further 5 hours and was then cooled to 10° C. over 10 hours. The product was isolated and was washed with water (20 mL) followed by isopropanol (20 mL) giving 4-methyl-3-methylsulfonyl-5-(3-pyridyl)-1,2,4-triazole (8.16 g, 70% yield) as a white solid.
Example 6
Preparation of 3-{4-methyl-5-[(1R)-1-(2-(3-methylphenyl-2H-tetrazol-5-yl)-ethoxy]-4H-[1,2,4]triazol-3-yl}-pyridine (compound 14)
[0046] To 4-methyl-3-methylsulfonyl-5-(3-pyridyl)-1,2,4-triazole (12.2 g, 51.0 mmol) and (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol (10.0 g, 48.6 mmol) mixed in tetrahydrofuran (40 mL) at 25° C., was added a solution of 1M potassium tert-butoxide in tetrahydrofuran (51 mL, 48.6 mmol) over 1 hour. The reaction mixture was held until consumption of starting materials is complete and the mixture was quenched by the addition of a solution of sodium chloride (6.0 g) and 37% hydrochloric acid (0.4 mL) dissolved in water (30 mL). The aqueous phase was discarded and the organic phase was washed two times with further NaCl-solution (6.0 g in 30 ml water). The organic phase was concentrated to ca 3 relative volumes and isopropyl acetate (80 mL) was added and the solution was concentrated to ca 3 relative volumes. Isopropyl acetate (70 mL) was added, the temperature adjusted to 70° C. and the solution was filtered to remove solid impurities. The solution was cooled to 50° C. and was seeded with the title compound (10mg 0.1w/w %). The solution was held at 50° C. for 1 hour and then cooled to 10° C. over 5 hours. The product was isolated and washed with isopropyl acetate (20 mL) and dried under reduced pressure at 40° C. to give 3-{4-methyl-5-[(1R)-1-(2-(3-methylphenyl-2H-tetrazol-5-yl)-ethoxy]-4H-[1,2,4]triazol-3-yl}-pyridine (14.4 g, 80% yield).
Example 7
Non-enzymatic preparation of (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol) (compound 13)
[0047] (S)-2-Methyl-CBS-oxaborolidine (16.3 mL (16.3 mmol, 1M solution in toluene) and borane dimethylsulfide (9.25 mL 97.5 mmol) were mixed and diluted with 18 mL 2-is methyltetrahydrofuran. The resulting solution was heated to 45° C. A solution of 1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]-ethanone, (32.8 g, 162.3 mmol) dissolved in 395 mL 2-methyltetrahydrofurane was added to the CBS-borane solution over approximately 3.5 h. The reaction had reached complete conversion after the addition of the ketone solution. The inner temperature was then set to 15° C. and 41 mL methanol was added to quench excess borane. The quenched reaction mixture was then extracted with 42 mL 6M HCl. The temperature was adjusted to 25° C. after which 115 ml water was added, the phases was separated and the aqueous phase was discarded. The organic phase was extracted with 120 ml water, the phases allowed to separate and the aqueous phase was discarded and the organic phase concentrated under reduced pressure, giving 31.7 g of the wanted product (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol) with 84% ee.
Example 8
Preparation of 1-[2-(3-methylphenyl)-2H-tetrazol-5-yl)]-ethanone (compound 12) using a flow reactor
[0048] The reaction was performed in an ART PR37 equipped with a PL37/3-12 plate from Alfa Laval.
[0049] FIG. 1 shows how each of the solutions 1, 2 and 3 respectively as described below, are fed into the ART PR37 equipped with a PL37/3-12 plate. P1, and N1-N8 are inlet ports. The final product is collected at the outlet “collection”.
[0050] Three starting solutions were used:
Solution 1:
[0051] Ethyl 2-(3-methylphenyl)-2H-tetrazole-5-carboxylate (27.0 g, 115.0 mmol, 12.4 wt %), triethylamine (56.1 ml, 402.5 mmol, 18.9 wt %) and 2-methyltetrahydrofuran (68.7 wt %) was injected at Port P1 at a flow rate of 15.2 g/min.
Solution 2
[0052] 1.4 M Methyl magnesium bromide solution (98.6 ml, 138.0 eq) was injected at Port N1 at a flow rate of 7.1 g/min
Solution 3:
[0053] Acetic acid (308 ml, 1.79 mol, 36.1 wt %), 2-methyltetrahydrofuran (29.5 wt %), water (34.4 wt %) was injected at Port N8 at a flow rate of 21.6 g/min
[0054] The pressure was set at 17 bar and the mantle temperature was at 0° C. This provided a temperature at port N2 of 10° C. The reaction solution was collected during approximately 5 minutes where ca 9.6 g, 41.2 mmol Ethyl 2-(3-methylphenyl)-2H-tetrazole-5-carboxylate had been reacted. The reaction solution was analyzed by HPLC at 254 nm and provided the following results:
[0055] 1-[2-(3-methylphenyl)-2H-tetrazol-5-yl)]-ethanone 84.3 area %, tert-alcohol by-product 13 area % and aldol by-product 2.4 area %.
[0056] The aqueous phase was discarded and the organic phase was washed with water (50 ml) followed pH adjustment to pH 7 with saturated potassium carbonate solution. The aqueous phase was discarded and the organic phase was concentrated to 28 g under reduced pressure. To the concentrate was added isopropanol (74 ml) and the mixture was warmed to 55° C. resulting in a clear solution, which was cooled to 20° C. during 3 hours. The product was isolated by filtration, washed with isopropanol (25 ml) and dried under reduced pressure at 40° C., providing 1-[2-(3-methylphenyl)-2H-tetrazol-5-yl)]-ethanone 6.45 g, 76% yield.
Example 9
Catalytic enantioselective hydrogenation of 1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]-ethanon to give (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]-ethanol
[0057] Under an inert atmosphere 8 mM benzeneruthenium (II) chloride dimer (65 μl, 0.5 μmol) in dimethylformamide was mixed with 27.5 mM 1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]-ethanon (43 μl) in toluene/tetrahydrofuran (10:6), R-Xyl-BINAP (0.7 mg, 1.0 μmol) and dimethylformamide (100 μl). The mixture was agitated at 100° C. for 1 hour and was then cooled to 30° C. To the mixture was added 22 mM R-DAIPEN (45.5 μl, 1.0 μmol) in toluene. The mixture was agitated at 30° C. for 1 hour when potassium tert-butoxide in isopropanol (450 μl, 5 mg/ml) was added. After 2 minutes 1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]-ethanon (20.0 mg, 98.9 μmol) was added and the reaction mixture was pressurized to 50 bar hydrogen pressure and was agitated for 1 hour. The reaction was sampled showing formation of (1S)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]-ethanol in 99% enantioselectivity.
[0058] The combination of R-Xyl-Segphos and R-DAIPEN provided 99% enantioselectivity of (1S)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]-ethanol.
[0059] The combination of R ax, SS-Xyl-C*-Thunefos and R-DAIPEN provided 99% enentioselectivity of (1S)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]-ethanol.
[0060] The combination of CTH-C3-Thunefos and R,R-DACH provided 98% enentioselectivity of (1S)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]-ethanol.
[0061] The combination of R-Xyl-BINAP and R-DPEN provided 97% enentioselectivity of (1S)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]-ethanol.
[0062] The combination of R-Xyl-BINAP and R,R-DACH provided 97% enentioselectivity of (1S)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]-ethanol.
[0063] The combination of R-Xyl-Segphos and R-DPEN provided 97% enentioselectivity of (1S)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]-ethanol.
[0064] The use of the other enantiomer of the catalysts will provide (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]-ethanol. | The present invention provides a process for the manufacture of the compound 3-{4-methyl-5-[(1R)-1-(2-(3-methylphenyl-2H-tetrazol-5-yl)-ethoxy]-4H-[1,2,4]triazol-3-yl}-pyridine of formula 14 wherein a) the compound 3-(5-methane-sulfonyl-4-methyl-4H-1,2,4-triazol-3-yl)-pyridine of formula 6 and the compound (1R)-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol of formula 13 are dissolved in an aprotic solvent, whereafter an alkoxide base is added, providing the compound of formula 14. The invention also provides methods for manufacturing 3-(5-methanesulfonyl-4-methyl-4H-1,2,4-triazol-3-yl)-pyridine and (1R)-1-[2-(3-methylphenyl)-2H-tetrazol-5-yl]ethanol. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present utility patent application claims the benefit of provisional application No. 61/459,895 filed Dec. 20, 2010.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT Not Applicable.
THE NAMES OF THE PARTIES TO A JOINT RESEARCH OR DEVELOPMENT
[0002] Not Applicable.
BACKGROUND OF THE INVENTION
[0003] Field of the Invention
[0004] The present invention relates to disaster prevention system for offshore oil wells and in particular to a supplemental disaster preventive system to provide means to insure human, equipment and environmental safety and associated cost avoidance during the offshore well drilling process under all conceived/feasible accidents/failures conditions. The overall system design concept, related procedures/processes and many associated system components to provide major cost reduction benefits for the entire life cycle (drilling, completion, production and abandonment) for both accident/failure and normal/uneventful operations.
[0005] Description of Related Art Including Information Disclosed Under 37 CFR 1.97 and 1.98 Shortly after the 2010 offshore oil well catastrophe in the Gulf of Mexico, it became obvious that British Petroleum (BP), the entire oil industry, and/or the US Government were unprepared to effectively stop the gushing oil or the means to clean it up. Throughout the first two plus months of the disaster numerous re-sealing, capturing, clogging, killing and capping techniques were unsuccessfully attempted and several high risk/cost ‘normal’ well drilling processes were brought to light.
[0006] The successful 20 July re-seal, capture and cap ‘Rube Goldberg’/‘Kluge’ (said with admiration) was a simplistic but effective temporary solution for the catastrophic symptoms of the problem—where the primary operative phrase is ‘temporary solution for the catastrophic symptoms’.
[0007] The enormous somewhat/sometimes unquantifiable costs of the (or of a future) incident includes:
[0008] Human life,
[0009] Environment,
[0010] Drilling platform,
[0011] Well (the equipment and the associated labor and its potential production),
[0012] Equipment and labor associated with the numerous re-seal, capture, and cap ‘quick fixes’,
[0013] Equipment and labor associated with the relief/kill wells,
[0014] Gulf clean-up,
[0015] Tourist and fishing industry,
[0016] Local community,
[0017] Public opinion relating to the oil industry & the government and
[0018] Nation and international financial markets
[0019] The prior art ‘blowout prevender’ (BOP) is intended to close off the well in case of an uncontrolled/emergency condition (blowout). It's a multi mega-buck, multi-ton device installed on the seafloor having various means/methods, with the design intent of closing a well. The most technically difficult is if/when a pipe and/or pipes (drill, casing, etc.) are within the well. The BOP must ‘ram’ through the pipe(s) and close off the well. That seems difficult, but add the extreme water pressure and low temperatures, the more extreme oil pressure and high temperatures and the prior art BOP is likely not going to work. After the Macondo's well was finally closed, the BOP was pulled up and evaluated—it was functional but did not do the job.
[0020] As offshore oil drilling/production continues in the future it seems only rational that the government as well as oil industry itself would demand, as a prime priority the development of improved equipment/systems and processes.
[0021] Whatever the cause(s) (human neglect/error, equipment failure, etc.) of the 2010 oil well disaster and whatever means are developed to insure no such similar failure and/or related impacts reoccurs, there are potentially more likely and more damaging events—specifically natural disasters and (accidental or deliberate) human intervention that must also be addressed.
[0022] The focus of the ‘quick fix’ was to stop/control the symptoms of the immediate catastrophe—the gushing oil.
[0023] What is needed is an overall systems design and implementation approach that provides the means to reduce/eliminate the causes and impacts of any conceived/realistic threats to oil wells in the future and further provides more reliable, practical and cost effective means to accomplish the oil well drilling task.
BRIEF SUMMARY OF THE INVENTION
[0024] The primary design objective of the present invention was to provide an offshore oil well improvement system using an overall systems design and implementation approach that provides the means to reduce/eliminate the causes and impacts of any conceived/realistic threats to oil wells in the future and further provide more reliable, practical and cost effective means to accomplish oil well drilling.
[0025] As the present invention design evolved it became apparent that many related procedures/processes and many associated system components provide major cost reduction benefits for the oil well's entire life cycle (drilling, completion, production and abandonment) in either problem or normal operations.
[0026] The present invention is composed of two functional and physically integrated subsystems, the Multi-Function Well Subsystem (MFWS) and the Intrusion Detection and Response Subsystem (ID&RS).
[0027] The MFWS is presented in two basic configurations, the ‘Fundamental’ & the ‘Advanced’. Both configurations modify the sea-floor and in-well equipment to provide maintenance access and unique tools to provide the means to: cap the well, seal/re-seal the well, drill/re-drill the well, kill the well from the top, improve BOP reliability, add BOP functional redundancy, improve the cementing process, incorporate a sea-floor pressure relief/diversion function and improves the well's life cycle safety.
[0028] The Advanced MFWS includes a unique dome top cylindrical sidewall structure enclosing the well's sea-floor equipment providing improved structural strength as well as passive protection from natural/human induced disasters.
[0029] The ID&RS provides the means to detect, track and classify the 3D aspects of air/surface/sub-surface objects about a specific oil well or group of oil wells and provides the means to evaluate and eliminate threats.
[0030] As all elements are based on existing simplistic proven technology, the development cost risk is minimum.
[0031] As the system design includes a major focus on the physical implementation and operation, the implementation and operational cost risk is minimum
[0032] Considering the pure human and environmental safety, the pure dollar and cents (or multi-million/billion dollar) cost avoidance and/or the potential cost savings/reductions (for any or all such reasons) it is a significant understatement to suggest that features of the present invention should be integrated with other planned improvements, and incorporated on all oil wells.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0033] These and other details of the present invention will be described in connection with the accompanying drawings, which are furnished only by way of illustration and not in limitation of the invention.
[0034] The drawings are intended to provide an introductory overview of major system/system elements that along with other unique system supporting devices are comprehensively defined in the ‘Detailed Description Of The Invention’.
[0035] FIG. 1 is a diagrammatic cross-sectional view of the Fundamental Multi-Function Well Subsystem (MFWS) showing a typical oil well's sea-floor equipment of a Stud ( 3 ), Marine Riser ( 4 ), BOP ( 5 ), Production Valve Assembly ( 6 ) and Well Pipe/Casing ( 2 ) sitting on the Sea-Floor ( 1 ). Connected to this ‘typical’ equipment is a ‘Normal’ Capture Valve & Associated pipe ( 11 ) going to a surface capture platform and a well drill & return pipe ( 9 ) ‘typically connected to ( 6 ) going to a surface drilling platform. The drawing further depicts the addition of two additional items, an Adjunctive BOP/Valve Assembly (AVA) ( 7 ) and a Platform to Well Interface Assembly (P-WIA) ( 8 ) in series with the ‘typical’ well's interface of ( 6 ) & ( 9 ). These two units are further shown on FIGS. 3A & 3B and FIG. 4 . These units provide functional redundancy of the BOP (using alternative, simplistic technology) to seal/close the well. Unit ( 8 ) provides the means to seal the drill pipe's exterior wall return flow path while unit ( 7 ) closes the entire well's flow path when there no obstruction (drill pipes, casings etc.) within the valve area of unit ( 7 ). Note the drawing does not depict the drill pipe, drill bit or various casings that may be going into the well from the drill platform during the drilling stage. When in use these would be feed through items ( 9 , 8 , 7 , 6 , 5 , 4 , 3 & 2 ). It is further noted that the full ‘functional redundancy of the BOP’ is not yet complete in that the BOP can (by intent but with poor reliability) ram through an obstruction and close the well. The full ‘functional redundancy’ is provided by one of two alternate means. The first is the Enclosed Pipe Cutter within ( 7 ) and the second is the remote Pipe Coupling/De-Coupling device as shown on FIG. 6 . In either case the cut or de-coupled pipe must be extracted from the valve area of unit ( 7 ). Such would be accomplished via the drill platform or a Remote Operated Vehicle (ROV) lifting the pipe/casing or the addition of an internal pipe lifting device (not shown). FIG. 1 further shows a Pressure Relief/Diversion Valve & Pipe/Tube ( 10 ) on a parallel well output port of unit 6 . This provides an input to the Pressure Relief/Diversion Assemble as shown on FIG. 5 . This provides the means to safely protect a problem well & platform, the means to safely capture the well output and the means to safely reduce/eliminate the disastrous effects on the environment.
[0036] FIG. 2 is a diagrammatic cross-sectional view of the Advanced Multi-Function Well Subsystem (MFWS) in a similar fashion to FIG. 1 . FIG. 1 begins showing a ‘typical’ oil well's sea-floor equipment of a Stud ( 3 ), Marine Riser ( 4 ), BOP ( 5 ) & Sea-Floor ( 1 ) (as identified on FIGS. 1 as 1 , 2 , 3 , 4 , & 5 ).
[0037] The Advanced MFWS differs by replacement the Production Valve Assembly with a unique manifold Domed Assembly (DA) structurally enclosing—reinforcing the well's sea-floor equipment. The DA consists of a Dome Cylindrical Sidewall ( 21 ), a Dome Top ( 22 ), and the Dome Interior Plate ( 23 ). The DA's lower section further includes Leveling Devices ( 24 ), Floor/Footing ( 25 ), & Vent Pipes ( 26 ). The Dome Top ( 22 ) includes parallel well outputs for the Normal Capture Valve & Pipe ( 11 ) & the Pressure Relief/Diversion Valve & Pipe ( 10 ) (functionally identical to 11 & 10 on FIG. 1 ). The DA upper section further includes a large ROV Access Port ( 27 ) that can be converted to the smaller port size of a normal BOP feed thru access by installing the Access Port Adaptor (APA) ( 28 ). Two sets of AVA's ( 8 ) & P-WIA' s ( 7 ) are provided in series with the Normal Well Drill & Return Pipe ( 9 ). One set is connected to the BPO ( 5 ) via the BOP Output Adaptor (OPA) ( 32 ) and a Pipe Mounting Adaptor (PMA) ( 31 ). The other set is connected to the APA ( 28 ). The Dome Interior Plate ( 23 ) includes a Cable/Tube Access Hole and an associated Cable/Hole Sealer ( 29 ) (further shown on FIG. 3A ). The interior area between the Dome Top ( 22 ) & Dome Interior Plate ( 23 ) and further enclosed by 28 , 29 , 31 , 32 , 10 & 11 is the Reservoir Area ( 30 ) sealed form the exterior sea water and is capable of holding well pressure.
[0038] FIG. 3A is a diagrammatic cross-sectional view of the Adjunctive BOP/Access Valve Assembly (AVA)-Housing with an Enclosed Pipe Cutter (EPC).
[0039] The Housing ( 41 ) includes a physical area ( 42 ) below the Access Valve ( 43 ) that incorporates the EPC. The mechanical aspects of the EPC are shown on FIG. 3B . As a general reference the BOP Access Area ( 44 ) is shown as dashed lines. As a specific reference to the Advanced MFWS relating to the lower (ref. FIG. 2 ) AVA ( 7 ) & P-WIA ( 8 ), the Dome Interior Plate ( 23 ), PMA ( 31 ), OPA ( 32 ), Cable/Tube Access Hole & associated sealer ( 29 ) and AVA, P-WIA & DA control & monitor cables/tubes ( 45 ) are shown. In the case of the Fundamental MFWS the AVA ( 7 ) is directly connected to the Production Valve Assembly ( 6 ) and the upper set of AVA ( 7 ) & P-WIA ( 8 ) of the Advanced MFWS directly connects to the APA ( 28 ) (ref. FIG. 2 ).
[0040] FIG. 3B is diagrammatic cross-sectional top view, at the EPC elevation depicting the mechanical aspects of the Adjunctive BOP/Access Valve Assembly (AVA) with EPC. Item 51 is a flat circular/donut shaped turn-table connected to the AVA housing via ball bearings. Item 52 (in dashed lines) reference the BOP's access area depicting the required centered opening of item 51 . Item 53 is the turn-table motor assembly consisting of a motor, gearing, encoder & associated housing. The motor housing is attached to the AVA housing. The motor shaft, gearing & encoder interface with the turn-table. An item 54 (in dashed lines) represents the AVA housing under the turn-table.
[0041] Item 55 ′s are six Lateral Drive Devices.
[0042] Items 56 are three circular saw blades each including a motor & tachometer. Items 57 are three wedges. Items 58 & 59 are details of items 55 . Item 58 is the fixed member of item 55 . It is affixed to the turn-table and includes a lateral drive motor, an encoder, slides & gearing. Item 59 is the lateral sliding member of item 55 and includes slides & gearing. The dashed lines at item 59 indicate this member at its extended position.
[0043] FIG. 4 is a diagrammatic cross-sectional view of the Platform to Well Interface Assembly (P-WIA).
[0044] Item 61 depicts the housing. Item 62 depicts the return flow opening/path. Item 63 is the remotely controlled by-pass valve allowing (return) flow around a sealed pipe outer wall to return. Items 64 are remotely controlled expandable ‘o’ ring gaskets capable of closing the area between the interior pipes outer sidewall and the AVA's housing (the return path). The dashed lines at items 64 show the said gasket expanded. Item 65 is a sample pipe within the P-WIA. Item 66 is a reference to the Normal Well Return Pipe going to the drill platform. This reference is applicable to the Fundamental MFWS & the upper P-WIA of the Advanced MFWS. The lower P-WIA of the Advanced MFWS is opened to the Reservoir. Item 67 (in dashed lines) is a reference to the BOP's access feed-thru area. FIG. 5 is a diagrammatic cross-sectional view of the Pressure Relief/Diversion Assembly. Item 71 is the Containment/Separator Tank. Although not shown it is assumed internal elements would provide enhanced oil-water-mud-gas separation beyond that obtained by a simplistic internally opened tank. Item 72 is the Ballast required to stabilize the tank to the Sea-Floor ( 1 ) as the tank takes on different elements (initially filled with sea water and latter replaced with mud, oil & gas). Items 10 & 11 are references to the Pressure Relief/Diversion Valve and the pipe/tubing coming from the well as seen on FIGS. 1 & 2 . This pipe/tube extends horizontal from the well's sea-floor equipment to a safe area where any possible release of oil/gas from the well will not impact the safety of the surface equipment or personnel. Item 73 is a composite of numerous controls and internal tank monitoring/sensors interfacing with the surface equipment. Items 77 are pipes/tubes to further divert and/or capture the tank's separated holdings. It is assumed the different separated outputs would go to different places (such as oil to a surface containment area or capture vehicle while the gas may be diverted to a further safer area father away from the oil containment/capture area). Items 74 , 75 & 76 are remotely controlled valves. Item 74 is the Sea Water/Mud Valve and would initially be opened in conjunction with the Pressure Relief/Diversion Valve to allow the tank to extract its initial sea water and accept the wells output. As sensors indicate the tank no longer contains sea water/mud the valve would be closed. Item 75 is the Gas Valve. If gas is sensed within the tank this valve would be opened. Item 76 is the Oil Release Valve. As oil is sensed within the tank this valve would be opened.
[0045] FIG. 6 is diagrammatic perspective & cross-sectional views of a matching/mating pair of the Coupling/De-Coupling Pipes.
[0046] Items 81 are the upper end & lower end of the upper & lower coupling pipes. These ends have standard pipe to pipe coupling means. Item 82 (in dashed lines) indicates the inside wall. Item 84 is the smaller diameter upper pipe coupling surface that fits within the lower coupling pipe as indicated by the dashed lines of Item ( 90 ). Item 89 depicts a tapered the bottom portion of item 84 allowing it to initially align/fit into the lower section. Item 83 is the upper pipe's mounting flange & gasket that mates to the lower pipes mounting flange item 91 . Item 92 is a unique threaded element in the interior sidewall of the lower pipe. The ‘unique’ threads have a stepping characteristic as shown on Detail ‘B’ item 93 . The widths of the individual steps are slightly larger than the width of the remote controlled Spring Loaded Grabbing Device (SLGD), item 85 . Items 85 are installed on the upper coupling pipe via Pivots ( 87 ) and normally extend out from the sidewall via its internal spring. When compressed the SLGD fits into the pipe's sidewall per item 88 . Detail ‘A’, item 94 indicates a sloped mating (mating the slope of item 93 ) of the SLGP. As the upper & lower sections are joined the SLGDs compress into the sidewall and springs in & out of the different levels of the stepped threaded element. When the mounting flanges bottom-out the upper pipe is turned clockwise (where it ratchet into, further tightens and locks into the threaded-stepped element. The pipes de-couple via energizing the SLGD remote control mechanism, item 86 where the SLGD is pulled into its sidewall unlatching/freeing the two pipe sections.
DETAILED DESCRIPTION OF THE INVENTION
[0047] The system of the present invention comprises two functional and physically integrated subsystems, the Multi-Function Well Subsystem (MFWS) and the Intrusion Detection and Response Subsystem (ID&RS).
[0048] Both MFWS configurations (Fundamental and Advanced) utilize ‘other’ (not shown on Figures) unique support devices including: Production Hard Cap (PHC) Remote Monitor and Control Unit (RM&CU) Re-Case End Pipe (R-CEP) Re-Case Pipe (R-CP) Bottom Kill End Pipe (BKEP) Kill Pipe (KP) Modified Conversion Float Valve (MCFV) Modified Casing (MC) Modified Reamer Shoe/Drill Shaft (MRS/DS) Modified Drill Bit (MDB)
[0049] The Production Hard Cap (PHC) is a simplistic device. It is round as viewed from the top and has a mounting surface compatible with both the Production Valves and the Production Ports. The PHC is utilized to provide means to cap each individual unused Production Port and/or Valve.
[0050] The Remote Monitor and Control Unit (RM&CU) is a platform mounted specialized device associated with the Multi-Function Well Subsystem (MFWS).
[0051] The RM&CU will provide the surface platform to sea-floor and in-well equipment man-machine monitor & control interface. The RM&CU will include processing capability to provide operator recommendations and warnings, as well as an automatic mode to control the sea-floor and in-well equipment for critical/emergency situations. Although specific operational displays, modes, functions or controls are not specified in detail at this time, it is assumed the RM&CU equipment (such as monitors, computers and interface devices) matching/exceeding the system requirements are commercially/off-the-shelf available. The Re-Case End Pipe (R-CEP) is a pipe section smaller in diameter than the installed well pipe/casing in need of repair when the drill pipe is not in the well. It will have a remotely controlled initially closed bottom end valve, a remotely controlled expandable ‘o-ring’/gasket around its outer circumference near the closed end. It will further have a remotely controlled sidewall gate valve located slightly above the said gasket. Prior to installing the R-CEP the number of sections of Re-Casing Pipe (R-CP) required to repair the well must be determined. At a point above where the existing well pipe is in need of repair but below the BOP, a pair of remotely controlled Coupling/De-Coupling Pipes shall be joined, followed by additional sections of R-CP from above the bottom of the BPO to the surface platform. The R-CEP and R-CP would be lowered through the ‘normal outer/return drill pipe’ to the desired location. The R-CEP gasket would be energized sealing/closing/choking the pipe to pipe area. The sidewall remotely controlled gate valve will be opened and mud followed by concrete would be pumped directly into the re-casing pipe. The mud/concrete flows through the opened gate valve and into the pipe/casing in need of repair to seal the pipe to pipe/casing area. The concrete will flow through said area until cement is detected in the pipe to pipe area above the last (highest) section of well pipe that needed repair. The concrete pumping will stop, the sidewall gate valve will be closed and the concrete will be removed from the interior of the Re-Case Pipe. The bottom remotely controlled closed end valve will then be opened. The concrete is let to set between the pipe to pipe areas. The Re-Case Pipe (below the BOP and above the well pipe that require repair) will be uncoupled via the Coupling/De-Coupling Pipe (or will be cut and extracted).
[0052] The Re-Case Pipe (R-CP) is similar to the lowest section of the installed faulty well pipe/casing except: [ 0051 ] Smaller in diameter. Selected sections (the uppermost as a minimum) shall incorporate remotely monitored exterior pressure, oil, water, mud and concrete sensors.
[0053] The Bottom Kill End Pipe (BKEP) is similar to the R-CEP except: The ‘initially’ closed bottom end will also have a permanently closed section above it. The volume between the initially and permanently closed portions will contain pre-loaded ‘junk’, along with a remotely controlled means to open the bottom and release the ‘junk’. The ‘junk’ will be of various size material, flexible, buoyant (in oil) and capable of withstanding well pressures and temperatures, will not include the remotely controlled circular hydraulic controlled gasket around its outer circumference near the closed end, but instead will include a large expandable remotely controlled end plug (similar to an expandable pipe plug). The ‘large’ plug will be capable of expanding to the diameter of the well bore. The large plug will be set below the well casing and the plug would be expanded. The initially closed bottom end will be opened releasing the junk further sealing/clogging/choking the well. Mud followed by concrete would be pumped through KP in a similar manner as the Re-Case Pipe except the concrete will also flow into the well bore and the concrete will not be evacuated from the pipes interior. The upper sections of pipe will be removed in a similar manner as the Re-Case Pipe.
[0054] The Kill Pipe (KP) is similar to the R-CP except the ‘selected sections’(the uppermost as a minimum) shall incorporate remotely monitored interior (as well as exterior) pressure, oil, water, mud and cement sensors.
[0055] The Modified Conversion Float Valve (MCFV) changes the release method/mechanism from the present dropped ball, semi obstructing the flow through a pipe holding the valve opened causing a delta pressure. When/if the delta pressure and flow meet a pre-selected criterion, the said pipe releases and converts the device to a one-way valve.
[0056] The modification converts the valve to an electrical remote controlled device—activating a solenoid. The opening valve will further be spring loaded and its opening will be sensed and reported and remotely monitored as flow-rate.
[0057] The Modified Casing (MC) incorporates remote controlled sidewall gate valves near the top of the casing. Although the MC is primarily intended for the lower most casing, it could be desirable for other casing sections as well. The said valves would be initially being held closed. Upon command the valves will allow one-way flow, from the pipe into the well-bore. This will allow cementing from the top of the casing to the bottom, reducing the required pressure and further provides a more positive void/bore fill.
[0058] The Modified Reamer Shoe/Drill Shaft (MRS/DS) modifications combine the functional elements of the R-CEP and the BKEP with the following alterations: The ‘large’ ‘plug’ element of the BKEP is incorporated on the lower part of the shaft/collar slightly above the shoe or drill bit to seal/clog/choke the well bore to drill shaft/collar incorporates a remotely controlled gate valve device internal to the pipe, just above the drill bit to restrict flow through the drill bit. The remotely controlled ‘o-ring’ pipe to pipe sealing gasket around the pipes circumference incorporated on the R-CEP shall be re-located to above the controlled gate valve. The intent of the MRS/DS is: Similar to the BKEP by providing the means to kill the well below the last pipe in the well bore, but with the reamer/drill shaft in the well. Similar to the R-CEP by providing reliable means to re-case (specifically the pipe to pipe cementing process), but with the drill shaft/collar and/or the Reamer Shoe in the well to provide improved reliable means to cement the last pipe to the well bore.
[0059] The ‘Fundamental’ MFWS provides maintenance access, redundancy, sea-floor pressure relief/diversion means and utilizing common unique and in-use apparatus and tools, used in conjunction with a newly devised oil well access to provide the means to: Cap the well, Seal/re-seal the well, Drill/re-drill the well, Kill the well (at the bottom from the top), Improve BOP(s) reliability and Improve means to end casing
[0060] The ‘Advanced’ MFWS includes all the features of the above, and further includes a unique dome top, cylindrical sidewall assembly/structure enclosing the well's sea-floor equipment providing improved structural strength and protection from natural/human induced disasters.
[0061] Either the Fundamental or Advanced MFWS configurations could be modified to include an additional Adjunctive BOP/Access Valve Assembly (AVA) installed below the BOP providing further redundancy.
[0062] MFWS Detail Design Notes/Information
[0063] The dome's size is determined by the wells characteristics. The primary factor is the height of the wells above sea-floor equipment (Marine Riser and BOP and newly installed adaptors/assemblies—OPA, PMA, and AVA and P-WIA) followed by the margin of safety associated with the: lateral stability of the DA (diameter to height ratio), sidewall strength beyond that required to support the top members—where the ‘beyond’ is the strength to compensate for falling objects/underwater blasts, height and width of the required maintenance area (ROV workspace). The overall ‘Dome Assembly’ size shall be as small as possible but its sidewall height shall be greater than the existing wells sea-floor equipment (Marine Riser and BOP)—(generic/ball-park height >60′). The sidewall diameter will provide lateral stability of the Dome Assembly and have a surface area compatible with all required dome top ports. (>two third the height, generic/ball-park diameter >40′) The initial (pre-cementing) weight of the Dome Assembly shall be slightly greater than the weight to sink it to the sea-floor, But if prior to its installation, the well head is opened and under pressure and can not be controlled/stopped, then weight must be added to overcome the well pressure. The added weight shall be determined assuming all top ports/valves opened (the said ports/valves would be opened during the normal installation/setting process). The top domed member (dome top and interior plate forming the reservoir) shall be made of material and joined in a manner to withstand greater than two times the wells' anticipated pressure. The cylindrical sidewall of the dome is fabricated with material and supporting braces capable of supporting the top (domed) structure and act as a concrete form to structurally connect the dome top section to a concrete floor pad. The center interior will include installation positioning/guide braces about the locations of Marine Riser, BOP and BOP Output Pipe Adaptor. The sidewall may be made of two or more vertical separable sections enabling sea-floor equipment changes for the completion-production phases (if/as desired). The exterior of the sidewalls will include a minimum of three horizontally extending ‘L’ brackets. The brackets will support remotely controlled leveling jacks capable of lifting/leveling the pre cemented Dome Assembly. The dome top to sidewall mechanical interface shall include lifting hooks/eye-bolts and shall be capable of supporting the DA's initial (pre-cemented) weight. After the DA is set (positioned and leveled) on the sea-floor, pressure relief vent pipes (approximately 3-4 feet long) will be vertically set in the sea-floor having the vent pipes be semi-evenly spaced in the floor and encompassing an area approximately five percent of the total sea-floor area, and a concrete floor (approximately 3 feet deep) will be poured (structurally connecting the Well Stud to the sidewall). The cylindrical sidewall will include an opening the size compatible with passing through a ‘typical’ off-shore oil well's ROV. The opening will be enclosed by a door. The door will include pressure relief/venting means allowing higher internal pressure to be released, while sealing the interior from higher external pressure. The center of the dome top will house a large access port. ‘Large’ is defined as the area capable of passing through a device the size of an ROV. The port will be initially used to access the interior of the dome during installation and latter for repair/replacement on assemblies within the dome. The exterior of this port area will include guide-pins and bolt studs to mechanically secure an Access Port Adaptor (APA). The APA reduces the port size and is used to connect various assemblies/adaptors for well pipe drilling, sealing repair and abandonment processes (killing), Off-center of the access port will include several production sized ports. The exterior of these ports will include the means to secure a Pressure Relief/Diversion Valve, Production Valves or Production Hard Caps. These mounting elements (pins and bolt studs) shall be identical (size, spacing and pattern) on all Production Ports. These ports/valves will be initially opened (as well as the Access Port) during the Dome Assembly (DA) installation (lowering and positioning). The ports/valves are initially used for pressure relief/venting and latter used for production—or will be capped. The Dome Assembly will include numerous standard (non-unique) remotely monitored/controlled equipment such as: Levels, Internal and external closed circuit T.V. (s) and associated lights, Pressure sensors, Oil, water and gas detectors All assemblies/adaptors/tools shall include the following where applicable: Be made of material capable of withstanding greater than twice the well's pressure Supporting means compatible with lifting, lowering and positioning the unit from the surface platform and ROV(s) Top and bottom mounting surfaces' compatible (size and shape) with the units they physically interface with Top and bottom mounting hardware (bolt studs, guide-pins) and compatible (size and pattern) holes and captivated securing components with the units they physically interface with:
[0064] Mounted gaskets compatible with the size and shape of the unit and the unit it physically interface with the means to remotely remove and replace all internal functional elements by a ROV(s). Remotely controllable devices shall be designed using electrical, fiber-optics, mechanical, hydraulic and/or pneumatic means with connections compatible with a ROV(s) capability to install/remove. There are many different ‘working’ pipe sizes and the expandable seals of the P-WIA will likely not be capable of handling, therefore different sized P-WIA s′ or inserts must be provided. Varying levels of pressure could be applied to the P-WIA's seals allowing for a fully opened, to fully a hard sealed, as well as intermediate levels allowing for rotating and vertical pipe movement as well as sequencing the said pressure from the upper & lower seals as the pipe joints pass thru the unit. The functionally/performance of numerous MFWS unique equipment/tools require or would be enhanced with the addition of an ‘in-well’ monitoring & control interface. Numerous interface structures could be employed to provide this function. Although the intent of this document is to provided a ‘system level’ design the following is provided as design information/specifications/requirements for this interface as follows:
[0065] Design.
[0066] Embedded Fiber-Optic (FO) cable within the drill pipe sidewall, Compression pipe to pipe FO connections, directly connect sensors and controlled devices attached to the drill pipe to the said cable. Sensors and controlled devices not directly attached to the drill pipe interface via non-physical contact means of coded Light/IR/RF and/or acoustic interface devices (such as a garage door opener or ‘Easy-Pass’ type device). Sensor and controlled devices powered by batteries. Controlled devices using hydraulics would use battery power to activate (in-well) pumps with initial pressure equalization means. Notes/Requirements: The FO bandwidth is orders of magnitude greater than required (but provides a convenient bi-directional capability). The sensors will include addresses (digital/frequency codes) capable of any future conceivable need. The following define the minimum required simultaneous functionally, which basically defines/limits the requirements of the controlling/monitoring unit. 25 discretes—yes/no (such as sensed gas), 15 levels indicators with ten to the 5.sup.th dynamic range (such as well pressure), 15 controls (such as turn on/off), 15 control status/feedback.
[0067] The sequence of operations of the Pipe Cutter Mechanism will be initiated by an operator at the Remote Monitor and Control Unit (RM&CU). In the automatic operational mode, after being ‘initiated’, an embedded micro-processor and program in the RM&CU will control and perform the cutting process described below. In a manual mode the operator will perform the steps below: 1. An operator at the RM&CU will initiate a pipe cut defining a given size pipe. 2. The Circular Saws and Lateral Drive Devices drives, with minimum torque contacts the pipe to confirm the designated pipe size. If different informs the operator. 3. If the pipe designated is confirmed the proper size, the saw motors are turned on and laterally driven into the pipe until either the thickness of the pipe-wall is penetrated or the saw motor speed decreases greater than 20%. If the latter occurs see * (below). 4. When the pipe-wall is penetrated, the Turn-Table Motor turns on and continues to cut the pipe until either the Turn-Table turns to where the pipe is cut by each saw 110 degrees or the saw motor speed decreases greater than 20%. If the latter occurs see * (below). 5. When three saws have cut the pipe 110 degrees, Circular Saws and Lateral Drive Devices retract the saw blades and: The Turn-Table is positioned at 120 degrees. 6. The Wedges' Lateral Drive Devices is activated pressing the wedges into the pipe cut. 7. The Circular Saws' Lateral Drive Devices is again activated to drive the saw blade towards the pipe until either the thickness of the pipe-wall is penetrated and the pipe is fully cut or the saw motor speed decreases greater than 20%. If the latter occurs see * (below). 8. Once the pipe is fully cut it must be extracted. If another pipe needs to be cut, the first pipe must be pulled clear of the pipe cutting lateral drive mechanism.
[0068] *If any of the saws speed decreases greater than 20% from its unloaded speed, the appropriate drives will be backed-off until the no-load speed is obtained. The drives will then proceed to the continuing cutting process.
[0069] The heart the pressure relief, diversion, capture and recovery subsystem is the unique seabed containment/separator tank supported with its primary interfaces devices (manifold, remote controlled valves and offset/diversion piping) providing the means to vent and/or capture oil/gas.
[0070] This continuation-in-part application incorporates a new capture device (a Containment Balloon) as an additional option to venting into the sea or capturing in a surface containment device (floating opened top -closed sidewall area or tanker(s)).
[0071] This continuation-in-part subsystem description further identifies various means (pipe/tank thermal insulation, heaters and/or anti-freeze chemical injection) incorporated in the pressure relief, diversion, capture and recovery flow path to guard against potential freezing—blocking gases.
[0072] The objective of the Intrusion Detection and Response Subsystem (ID&RS) is to protect the surface and underwater oil well elements from deliberate human intervention. It is assumed a 3D restrictive zone will be established about an individual or group of oil wells.
[0073] The ID&RS provides the means to detect, track and classify the 3D aspects (bearing, range, and depth) of air/surface/sub-surface objects about a specific oil well or group of oil wells. It also provides the means to evaluate potential threats and ‘Hard and/or Soft Kill’ threats.
[0074] The ID&RS elements are identified in four categories as follows:
[0075] 1. Major existing military type platform equipment that provides short range AAW, ASUW and ASW capability including such items as: Radars (search and fire control), IFF, ESM, Sonar, Active and Passive Decoys (Acoustic, RF and IR), Hard Kill Weapons (guns, missiles, torpedoes and depth charges). 2. Major existing military/commercial type equipment such as: LAMPS Helicopter and ROV s. 3. Unique equipment such as:
[0076] Array(s) of sea surface tethered remotely controlled RF and IR generators/decoys, Array(s) of below sea tethered remotely monitored Passive Acoustic Sensors (PAS) and a platform mounted PAS, Remotely controlled acoustic generators/decoys and remotely controlled acoustic corner reflectors, Interface, Processing and Display Monitor and Controls 4. Trained Operator(s).
[0077] Many of the terms such as ‘short range’ and ‘weapons’ are quite subjective and since the primary threat is considered to be quite rudimentary the following are identified as design guidance: A Radar (search, fire control and integrated IFF) capability such as the MK92 CAS, Weapons such as the Standard Missile, Harpoon and Mk46 Torpedoes would work but have a significant over kill for the anticipated threat, Hard Kill weapons could include such items as a MK15 CIWS, a 3 ″ gun, SUBROC and Helicopter launched depth charges and shoulder type fire and forget anti-air and anti-surface missiles.
[0078] ID&RS Detail Design Notes/Information
[0079] The acoustic sensors and arrays are conceptually based on USN ASUW and ASW detection and processing techniques. The subsurface piggy-back depth angle sensor and the related arrays depth determination is unique but based on the triangular processing of the bearing and range. It is anticipated the sensed ‘depth angle’ will be compromised by sea-floor and surface reflections/bounce, but it is assumed that integrating over time and averaging the three differently located sensors data will provide tangible results. The tracking, classification, threat analysis and threat response recommendations are also based on USN processing.
[0080] The RF, IR and acoustic generators and corner reflector(s), and their associated array, are conceptually based on USAF and USN air tactical counter-measures (stand-off jammers and gate stealers) and USN submarine counter-measures (decoys).
[0081] The Light Airborne Multi-Purpose System (LAMPS) operations are based on the USN LAMPS MK111 ASW and ASUW techniques.
[0082] The following describe a single well installation utilizing a USN or USCG Ship for the ‘Major existing military type platform equipment that provides short range AAW, ASUW and ASW capability’.
[0083] It is assumed alternative interfaces, operations and array configurations could be derived for well platform based equipment and/or multiple well implementations.
[0084] The Radar and associated IFF and Electromagnet (passive detection) Sensor (EMS) are the ‘eyes’ for above the surface, while the passive acoustic sensors are the ‘eyes’ for below the surface.
[0085] The acoustic sensor array provides subsurface and surface detection data and the means required to triangulate the sensors detections to determine Bearing, Range and Depth. The outputs of the acoustic sensors* and control signals for all generators (RF, IR and acoustical) interface with (via cable) an Array Distribution Unit (ADU). The ADU (data/controls) interfaces (via cable) with to the Data and Signal Formatter (D&SF). D&/SF on a (oil well) platform digitizes and serializes the signals. The digitized and serialized signal is sent to the platforms RF Data Link and then the ship's RF Data Link. The data is then sent to the Processor where is processed for display monitoring and display interface, detection support (bearing, range and depth determination for acoustic contacts) and tracking, classification, threat analysis and related recommendations, as well as historical storage for air, surface and subsurface contacts.
[0086] The processed data and information is then sent to the Display Monitor and Control Unit. A trained Operator views/reviews the data and information and determines and initiates appropriate actions.
[0087] The processing will include an operator selectable auto threat-quick reaction ‘soft-kill’/decoy mode, allowing the program to automatically control the RF, IR, acoustical generators and corner reflectors.
[0088] The controls are sent to the appropriate selected unit(s) (specific sensor and/or generator) via the Processor, RF Data Link, Data Formatter, Array Distribution Unit and then to the appropriate unit. LAMPS Helicopter interfaces via its own data link.
[0089] If ROV actions are required, a stand alone interface, monitor and control system identical to the existing ROV's will be used.
[0090] If the Ship has a sonobuoy receiver system compatible with the number and type of sonobuoys in the array the sensors could directly (via RF) interface with the ship.
[0091] It is assumed the sensor (RADAR, IFF, and ESM etc.) and weapons on a USN or USCG Ship identified as short range AAW, ASUW and ASW capable would well serve this mission, particularly as supplemented.
[0092] The RF and IR Generators/Decoys are standard simplistic active noise or repeater source similar to numerous such devices used by the USN and USAF. The device shall be externally stimulated and controlled by the Processor to produce outputs capable of:
[0093] Being totally silent, Producing broadband continuous wave frequencies over the entire spectrum of anticipated homing devices, at power levels greater than the anticipated homing device's transmitter, Producing a controlled variable delayed pulsed repeater outputs compatible with the pulse-width and spectrum of an anticipated active pulsed homing device. The controlled variable delay shall have a minimum range from; <1 us to greater than 10 ms. The repeater will further have controlled power levels from a maximum equaling the anticipated power of a homing device's transmitter, to minimum power level of zero.
[0094] The Passive Acoustic Sensor (PAS) is derived from a modification of the standard AN/SSQ 53 Directional Frequency Analysis and Recording (DIFAR) Sonobuoy.
[0095] The low-tech modifications include: Providing an external power source via cable (vs. internal battery power), Removing the antenna output interface and utilize output via cable interface format, Mounting two unit's piggy back on different axis (one producing bearing angle and the other depth angle),Increase buoyancy to insure unit with attached cable (and attached Acoustic Generator has significant positive buoyancy.
[0096] The Acoustic Generator (AG) is a simplistic active acoustic noise source similar to numerous such devices used by the USN.
[0097] The device shall be externally stimulated and controlled by the Processor to produce outputs capable of: Being totally silent, Emulating the acoustic signature of an oil well's sea-floor and platform, with power levels equal to ten times the said well, Producing broadband continuous wave acoustic frequencies over the entire spectrum of anticipated homing devices, at power levels greater than an anticipated homing device's transmitter, Producing a controlled variable delayed pulsed repeater output compatible with the pulse-width and spectrum of an anticipated active pulsed homing device. The controlled variable delay shall have a minimum range from; less than 10 us to greater than 10 ms. The repeater will further have controlled power levels from a maximum equaling the anticipated power of a homing device's transmitter, to a minimum power level of zero. The Acoustic Corner Reflector (ACR) is a simplistic passive decoy type device. It is basically composed of two flat acoustical reflective crossing plains (crossing in the center) at 90 degrees that reflects an acoustical signal back in the same angle it was received. The ACR further includes a remote controlled element that rotates (from the center) one of the plains to form a dual flat surface. The ACR is deployed with weighs on the sea-floor and/or tethered at different depths.
[0098] The PAS and AG units will be connected (via cable or be physically joined) and typically deployed in functional sets of three or four typically @ equal distance from each other and equal distance about a specific well (or in other functional sets about a group of wells).
[0099] Each of the PAS, AG and/or ACR units will be tethered from the sea-floor to pre-determined depths. The RF & IR generators will be tethered to the sea surface.
[0100] The said tethered cables could include various combinations of sensors/decoys. The sea-floor will hold the tethered cable with weights capable of insuring it does not change its position (depth, lat. and long.). The cable length from the tethered weight to the sea-floor to platform shall be the planned distance plus about one and a half times the sea depth (for future recovery/maintenance). A single (non-joined) AG will be mounted on the underside of the surface platform providing the means to calculate (via the processor) the exact position and aspect of the joined PAS and AG devices.
[0101] The ROV(s) is identical to such devices used by the oil industry for deep off-shore drilling but this unit's interface cables will be lengthened so it can travel greater than two miles from the platform. The ROV(s) provide the means to view, evaluate and move delayed fused under-sea explosives.
[0102] The Array Distribution Unit (ADU) function only acts as a convenient physical wire/cable distribution center.
[0103] The Data and Signal Formatter (D&SF) is an active electronic data and signal formatting device located on the platform.
[0104] The ‘formatting includes: Analogue to Digital conversion, Digital to Analogue conversion, Multiplexing and De-multiplexing into and from a single serial digital data interface cable. The D& SF will have the minimum through-put capacity (bandwidth) to simultaneously handle: From Sensors: Acoustic outputs of eight type AN/SSQ-53 Sonobuoys. Plus 50% (control, feedback, status, etc.). To Sensors and Generators: Approximately 25% of the ‘from sensors’ bandwidth
[0105] It is assumed devices matching/exceeding these requirements are available ‘off-the shelf’ (from Industry/US Government). The RF Data Link is a common device used by industry and the government. The device converts serial (cable media) electronic data/signals to RF for transmission to another location via an antenna and likewise receives RF and converts it to serial electronic data/signals.
[0106] The capacity (bandwidth) must be compatible with the required data/signals of the system, as identified for the D&SF.
[0107] It is assumed devices matching/exceeding these requirements are available ‘off-the shelf’ (from Industry/US Government).
[0108] *The above assumes a separate in-place ship to helicopter (LAMPS) data link.
[0109] The Processor includes a computer and specialized computer programs. The Processor provides critical functions related to the surface/sub-subsurface objects: Detection, Position, Tracking, Classification, Threat Analysis and related recommendations The processor also provides interface for the Display Monitor and Control Unit. The processor further provides for sensor position and aspect calibration, operator training via simulation and historical operational recording.
[0110] It is assumed the computers are in-place on the ship, or a computer matching/exceeding the required process capacity and speed are available ‘off-the shelf’ commercially. The ‘specialized computer programs would have to be developed, but the USN utilizes similar functional software for their AAW, ASUW and ASW mission. If such were made available the development (time, cost and risk) would be reduced by an order of magnitude.
[0111] The Display Monitor and Control Unit (DM&CU) provides for the operator to system interface.
[0112] The Light Airborne Multi-Purpose System (LAMPS) is identical to that used by the USN for surface and sub-surface detection, localization and engagements.
[0113] Although specific operational displays, modes, functions or controls are not specified in detail at this time, it is assumed the DM&CU is in-place on the ship or a unit matching/exceeding the requirements is commercially available—large touch-screen monitor would well serve the all requirements.
[0114] It is understood that the preceding description is given merely by way of illustration and not in limitation of the invention and that various modifications may be made thereto without departing from the spirit of the invention as claimed. | The parent patent—The Oil Well Improvement System—incorporates and integrates several different unique assemblies and subsystems that provides a cost effective disaster preventive system for offshore oil wells while concurrently providing the means to reduce the cost of the drilling processes.
The system modifies the sea-floor, in-well and platform equipment and processes.
This divisional patent—The Pressure Relief, Diversion Capture & Recovery Subsystem—acts in concert with the Oil Well Improvement System to provide an additional and/or interim means to control a blown out well by providing an alternate/safe low resistance flow path along with the means to capture and recovery oils/gases. | 4 |
BACKGROUND
[0001] 1. Field of the Invention
[0002] This invention relates to exercising equipment and, more particularly, to an apparatus for the exercise of leg muscles to increase blood flow in the legs while seated on a transport vehicle.
[0003] 2. Related Art
[0004] Currently, there are limited options for exercising on an airplane. On very long flights passengers are seated for long periods of time, which can cause their legs to become numb due to reduced circulation. The ability to stand up and walk around in an airplane is not always practical and the attempt to do so may disturb other passengers.
[0005] Some air carriers are considering exercise rooms on board airplanes. However, this requires that the number of seats or cargo space be reduced.
[0006] Other exercise options can include exercise-friendly power bands used to provide resistance to the movement of a user's limbs. While others choose to brace themselves against walls, typically near the galley or lavatories, to perform stretching exercises for legs, calves, back, and arms. With increased security concerns on airplanes, the congregation of passengers near the galley or lavatories is discouraged and often prohibited.
SUMMARY
[0007] The invention provides exercise equipment that allows for movement of the legs while offering resistance to that movement. The exercise equipment is for use on an airplane while in a seated position. The exercise equipment includes two pedals, which can be alternatively compressed with the feet to exercise the legs and stimulate circulation.
[0008] As described below, the exercise apparatus rides on a telescoping track mounted below a seat in front of the exercising passenger. The exercise equipment can be moved from a stowed position to an exercise position. The resistance is provided through any means of mechanical or pneumatic actuation and the like. The loads experienced by the compression of the pedals are absorbed in the seat tracks of the seat in front of the exercising passenger to prevent disturbance of other passengers. The exercise equipment stows under the seat in front of the exercising passenger when not in use.
[0009] Beneficially, the present invention inhibits deep vein thrombosis, which can cause blood clots, triggered by long periods of inactivity while seated. The present invention enables movement of the leg muscles, which increases blood flow in the legs and inhibits the formation of blood clots.
[0010] Additional advantages, objects, and features of the invention will be set forth in part in the detailed description which follows. It is to be understood that both the foregoing general description and the following detailed description are merely exemplary of the invention, and are intended to provide an overview or framework for understanding the nature and character of the invention as it is claimed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The accompanying drawings are included to provide further understanding of the invention, illustrate various embodiments of the invention, and together with the description serve to explain the principles and operation of the invention. In the drawings, the same components have the same reference numerals. The illustrated embodiment is intended to illustrate, but not to limit the invention. The drawings include the following Figures:
[0012] FIGS. 1A and 1B are simplified side and top views of the exercise apparatus in accordance with an embodiment of the present invention; and
[0013] FIG. 2 is a simplified side view of the exercise apparatus of FIG. 1A mounted to a seat in accordance with an embodiment of the present invention.
DETAILED DESCRIPTION
[0014] The present invention allows for exercise of a user's leg muscles while the user is seated.
[0015] FIGS. 1A and 1B are side and top views of exercise apparatus 100 according to an embodiment of the present invention. Exercise apparatus 100 includes a glide assembly 102 including two telescoping tracks 104 and 106 . The telescoping feature of tracks 104 and 106 allows for track 106 to moveably extend from track 104 in a linear path, generally free of lateral motion.
[0016] At the extended end of track 106 is mounted a pair of foot pads 108 and 110 . The overall width of foot pads 108 and 110 should provide for travel in a linear path within glide assembly 102 , also free of lateral motion. In one embodiment, foot pads 108 and 110 are made slightly narrower then the distance between tracks 104 and 106 of glide assembly 102 .
[0017] At least one roller wheel 112 is positioned on the extended end of track 106 to evenly distribute the weight and increase the stability of exercise apparatus 100 during use. One skilled in the art will recognize that the number and location of roller wheel 112 is not limited to that which is shown in FIG. 1 . Various bracing structures can be used to enhance structural rigidity of tracks 108 and 110 as would be recognized by those of ordinary skill in the art.
[0018] Foot pads 108 and 110 permit simultaneous exercise of two legs. Foot pads 108 and 110 may be formed of a variety of materials, such as plastic, metal, or other material that is lightweight, durable and sturdy to minimize flexing when in use. Glide assembly 102 are also formed of plastic, metal or other material that is lightweight, durable and sturdy to avoid flexing when in use. By way of example glide assembly 102 may be formed of aluminum.
[0019] In one embodiment, a joint or hinge 114 may be provided to allow the ability to fold foot pads 108 and 110 down toward tracks 108 and 110 for convenient storage. Optionally, a second joint or hinge 116 can be provided near foot pads 108 and 110 to allow foot pads 108 and 110 to be folded along tracks 104 and 106 and lay flat there along.
[0020] Foot pads 108 and 110 are sized in width to fit between tracks 104 and 106 of tracks 108 and 110 . Such a width would then easily allow exercise apparatus 100 to fit between the legs of a stationary chair. Exercise apparatus 100 located under a chair allows the path of travel of the user's feet while exercising to be natural. In one embodiment, foot pad travel may be sized in length to provide about a 0.5 inch to about 8 inches of travel, although it is known that shorter lengths may be sufficient for increasing blood flow. Foot pads 108 and 110 may be sized to accommodate any user's feet. Foot pads 108 and 110 are made generally longer and wider than a user's foot to avoid the ends of a user's foot from approaching the ends of the foot pads and be in danger of colliding with surrounding structures. It should be understood that the present invention is not limited to any specific dimensions.
[0021] In one embodiment, the top surfaces of foot pads 108 and 110 can be texturized to inhibit the user's foot from sliding relative to the texturized foot pads.
[0022] In one embodiment, the resistance mechanism is provided by a mechanical spring within a pneumatic cylinder. The mechanical spring is a coil spring providing a minimal amount of resistance for exercise and the pedal return force. The pneumatic cylinder is a cylinder within a cylinder having sliding surfaces that are pneumatically sealed. An internal guide keeps the internal cylinder aligned with the external cylinder. A simple valve connected to the cylinder is opened for less resistance and closed for greater resistance.
[0023] In one embodiment, the internal cylinder can be welded or similarly attached to a foot pad, while the external cylinder is welded or similarly attached to an attachment block. The attachment block is welded or similarly attached to the track. The attachment between the external cylinder and the attachment block is made so as to angle the pneumatic cylinder toward the user's foot.
[0024] FIG. 2 . illustrates exercise apparatus 100 for use as part of a seating configuration in a transport vehicle, such as an airplane seating arrangement. Exercise apparatus 100 is mounted close to the floor and oriented below a seat in front of the user. The user is seated in a chair located at the other end of exercise apparatus 100 , such that the chair and the user are facing exercise apparatus 100 . The user places one foot on each foot pad 108 and 110 . Alternatively or in addition, a user may place her foot on the texturized surface of the foot pads.
[0025] In operation, the user moves both feet fore and aft so as to move foot pads 108 and 110 40 in a bicycling motion.
[0026] It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit and scope of the invention. Thus it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. | A leg exerciser having first and second foot pads coupled to a glide assembly having longitudinally extending first and second tracks for moving the first and second foot pads between a stored position and an exercising position. The foots pads are coupled to a resistance means to provide resistance to the movement of the foot pads. The leg exerciser is configured to be mounted to a seat. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to multi-stage acrylic polymeric compositions, to a process of producing films and sheets by calendering the multi-stage acrylic polymeric compositions, to composites of coated textile materials and other substrates wherein the coating is a film or sheet of the calendered multi-stage acrylic polymer composition, and to a process of treating a textile material or other substrate with sheets of films of the calendered multi-stage acrylic polymeric compositions. The use of the compositions according to the invention provides improvement of various properties of textile materials treated therewith, such as flexibility and a leather-like hand while retaining good low-temperature properties.
2. Prior Art And Related Applications
The use of calenders for processing synthetic thermoplastic materials to produce films or sheets is well-known. The state of the art of calendering synthetic thermoplastic materials is described in the following: "Calendering," Eberhart Meinicke, pages 802-819 in Herman F. Mark, Norman G. Gaylord, and Norman M. Bikales, eds., Encyclopedia of Polymer Science and Technology, Volume 2, Interscience Division, John Wiley & Sons, New York, 1965; "Calendering," G. W. Eighmy, Jr., pages 237-238 in Modern Plastics Encyclopedia, 1978-1979; "Calendering Today Isn't Just Vinyls," pages 61-63 in Modern Plastics, June 1974; and "Calendering," G. W. Eighmy, page 451 in Modern Plastics Encyclopedia, 1970-1971.
The bulk of thermoplastic materials processed on calenders is poly(vinyl chloride), sometimes referred to hereafter as PVC. Other thermoplastic materials more recently used in calendering operations include acrylonitrile-butadiene-styrene polymer-modified PVC and polyethylene-modified PVC, cellulose acetate, polyolefins including polyethylene, chlorinated polyethylene and polypropylene, and polyurethane elastomers. Interest in the use of non-PVC synthetic thermoplastic materials has been increasing due to environmental and ecological considerations which favor decreasing the use of PVC and of plasticizers normally used with PVC. Although many synthetic thermoplastic materials have been used heretofore in place of PVC in calendering operations, the use of soft and flexible acrylic polymeric materials as the predominant thermoplastic material is not known for the production of films and sheets by calendering, the films and sheets thereby produced being useful for coating fabrics and textiles or other substrates to produce composites having applications such as home furniture upholstery, automotive upholstery, clothing fabric, luggage, wall covering, and the like.
Applicant's copending application, U.S. Ser. No. 945,733, filed Sept. 25, 1978, discloses a textile treating composition and an article comprising a textile material treated therewith, wherein the textile treating composition comprises an acrylic latex, the particles of which comprise about 30-60% by weight of polymeric core and about 70-40% by weight of a polymeric shell, wherein said core is formed by emulsion polymerization of a first monomer composition consisting essentially of:
70-95% by weight of C 1 -C 8 alkyl acrylate,
0-15% by weight of a C 1 -C 8 alkyl methacrylate,
4-10% by weight of acrylamide or methacrylamide,
0-0.3% by weight of allyl methacrylate, and
0-2% by weight of itaconic acid;
and wherein said shell is formed on said core by emulsion polymerization of a second monomer composition in the presence of said core, said second monomer composition consisting essentially of:
40-70% by weight of a C 1 -C 8 alkyl acrylate,
20-50% by weight of a C 1 -C 8 alkyl methacrylate,
2-10% by weight of N-methylolacrylamide, N-methylol methacrylamide, or a mixture of methacrylamide and N-methylolacrylamide,
and 0-2% by weight of itaconic acid.
Commonly assigned U.S. Pat. No. 4,107,120 and U.S. Pat. No. 4,181,769 to Plamondon, the later being a division of the former (U.S. Pat. No. 4,107,120), disclose a textile treating composition and an article comprising a textile material treated therewith, wherein the textile treating composition consists essentially of an acrylic latex, the particles of which comprise about 30-60% by weight of a polymeric core and about 70-40% by weight of a polymeric shell, wherein the core is formed by emulsion polymerization of a first monomer composition consisting of:
(a) a major amount of a principal monomer system, and
(b) a minor amount of a crosslinking monomer system comprising:
(i) about 0.5% to 6% by weight on the total first monomer composition of a graftlinking monomer or an active crosslinking monomer, and
(ii) about 4% to 10% by weight on the total first monomer composition of a latent crosslinking monomer; and wherein said shell is formed on said core by emulsion polymerization of a second monomer composition in the presence of said core, said second monomer composition consisting essentially of:
(a) a major amount of a principal monomer system; and
(b) about 2% to 10% on the total second monomer composition of a latent crosslinking monomer; the monomers of said first monomer composition being selected to provide a T g in said core of -20° C. or lower, and the monomers of said second monomer composition being selected to provide a T g in said shell of about 60° C. to about -10° C.
Carty, U.S. Pat. No. 4,086,296, discloses a blend of a thermoplastic polymer (e.g. ABS resins, polystyrene, polypropylene, polyesters such as polyethylene terephthalate, polyamides such as poly[caprolactam] and polyurethanes which are mentioned in column 6, lines 23 to 60) with a multiphase acrylic composite polymer, the latter functioning as a lubricant and/or processing aid in the above-mentioned thermoplastic polymers.
Lane et al, U.S. Pat. No. 3,745,196, disclose a polystage elastomer having a first stage polymer having a glass temperature below about -35° C. comprising at least 50% by weight of an alkyl acrylate and, optionally, 0 to 5% by weight of a polyethylenically unsaturated crosslinking comonomer, 0 to 10% by weight of a curing site-containing monomer, and from 0 to 50% by weight of at least one monomer selected from alkoxyalkyl acrylates, alkylthioalkyl acrylates, cyanoalkoxyalkyl acrylates, and nitrile substituted alkyl acrylates. The final stage of the elastomer comprises at least 60% by weight of ethyl acrylate and/or methyl acrylate and, optionally, 0 to 40% by weight of comonomers such as acrylonitrile, lower (C 1 -C 4 ) alkyl esters of acrylic acid and curing--site monomers.
Griffin, U.S. Pat. No. 3,458,603 discloses a three-stage granular polymerization process for the production of thermoplastic polymer materials suitable for injection molding to manufacture various molded articles.
Dickie, U.S. Pat. No. 3,787,522, discloses a particulate thermoplastic material having at least two stages formed by emulsion polymerization and having a rubber-like core of a major amount of an alkyl acrylate and a minor amount of a polyethylenically unsaturated compound as a crosslinking agent and a glass-like outer shell of about 30 to 99 molar parts of methyl methacrylate and about 1 to 70 molar parts of monomers copolymerizable with methyl methacrylate. The polymers are useful as modifiers of thermoset polymers and as intermediates for forming other rubber-like and/or rubber-modified materials suitable for molding with each other and with other thermoplastic materials.
Myers, U.S. Pat. No. 3,971,835, discloses a three-stage, sequentially produced graft copolymer comprising a non-rubbery, hard first stage polymer of 50 to 100 weight percent of a vinyl aromatic compound, 0 to 50 weight % of a different monovinylidene monomer and 0 to 10 weight % of a polyfunctional crosslinking monomer; a second stage rubbery polymer of 50 to 100 weight % of butadiene, isoprene, chloroprene, and an alkyl acrylate or mixtures thereof wherein the alkyl group has about 3 to 8 carbon atoms, 0 to 50 weight % of a monovinylidene monomer and 0 to 10 weight % of a polyfunctional crosslinking agent; and a third stage polymer of 50 to 100 weight % of an alkyl methacrylate wherein the alkyl group has 1 to 4 carbon atoms, 0 to 50 weight % of a vinylidene monomer, and 0 to 10 weight % of a polyfunctional crosslinking monomer. The 3-stage graft polymer is used as a modifier for vinyl halide polymers.
Owens, U.S. Pat. No. 3,793,402 and 3,843,753, discloses broadly acrylic heteropolymers having two or more stages.
Although the polymer compositions mentioned above generally provide excellent properties when used as latex coatings on fabrics or as processing aids for handling other polymers such as poly(vinyl chloride), they possess deficiencies which do not permit their use as thermoplastic materials for calendering into films or sheets.
SUMMARY OF THE INVENTION
It has now been discovered that a certain class of acrylic polymers is particularly suited for use as the thermoplastic material in calendering operations to produce films and sheets which can be used to produce coated fabrics or other substrates.
For a polymer to be calenderable, it must have a high degree of thermoplasticity. Under the stress of calendering rolls a polymer requires a balance between softening point, heat stability and flow. A softened polymer must be able to flow adequately to give the desired film, but it must still have sufficient integrity to be transferred from one roll to another, a property called "nerve" in the art. A polymer must have some degree of "pseudo-crosslinking" or internal interaction to give its mass some integrity. Such interaction can arise from entanglement of the polymer mass, some degree of crystallinity (as occurs in the case of PVC) or low degree of crosslinking, or combinations of the above. In addition to these basic inherent polymer responses, other properties, such as low tack, fluxing characteristics, degradation, and the like, can be controlled by the use of various additives to formulations of the polymers, as is known in the art. Ideally, the use of such additives should be minimized.
It is an object of the invention to provide a calenderable acrylic composition, to provide a calendered acrylic film or sheet, to provide textile materials treated with the calendered acrylic film or sheet, and to provide processes for producing the film or sheet by calendering the acrylic composition and for producing the treated textile materials.
These objects, and others as will become apparent, are achieved by the present invention which comprises, in one aspect, a calenderable, soft, three-stage acrylic polymeric composition, said composition having a calculated T g of from about (-) 40° C. to about (+) 20° C., the isolated and dried particles of which comprise about 30-60% by weight of a polymeric first stage, about 30-60% by weight of a polymeric second stage, and about 5-20% by weight of a polymeric third stage, wherein
(1) said first stage is formed by emulsion polymerization of a first monomer composition having a T g of about (-) 10° C. or lower consisting essentially of:
(a) about 70-95% by weight of at least one (C 1 -C 8 ) alkyl acrylate,
(b) about 0-15% by weight of at least one (C 1 -C 8 ) alkyl methacrylate,
(c) about 4-10% by weight of a latent cross-linking monomer selected from acrylamide or methacrylamide, and
(d) about 0.5-4% by weight of at least one alpha, beta-ethylenically unsaturated carboxylic acid selected from acrylic acid, methacrylic acid, and itaconic acid;
(2) said second stage is formed by emulsion polymerization, in the presence of said first stage, of a second monomer composition having a T g of about (-) 10° to (+) 60° C. consisting essentially of:
(a) about 40-70% by weight of at least one (C 1 -C 8 ) alkyl acrylate,
(b) about 20-50% by weight of at least one (C 1 -C 8 ) alkyl methacrylate,
(c) about 4-10% by weight of a latent crosslinking monomer selected from acrylamide and methacrylamide, and
(d) about 0.5-4% by weight of at least one alpha, beta-ethylenically unsaturated carboxylic acid selected from acrylic acid, methacrylic acid, and itaconic acid; and
(3) said third stage is formed by emulsion polymerization, in the presence of said second stage polymerization product, of a third monomer composition consisting essentially of:
(a) about 50-100% by weight of methyl methacrylate, and
(b) about 0-50% by weight of a comonomer selected from those comonomers copolymerizable with methyl methacrylate and having a calculated T g of less than 0° C.
In another aspect, this invention comprises a process for producing a film or sheet comprising calendering the composition of the invention.
In still another aspect, this invention comprises a process which comprises treating a textile material with the calendered film or sheet of the invention and curing the polymeric film on the textile material, with or without a crushed foam layer between the textile material and the coating.
In still further aspects, this invention comprises articles of manufacture produced by the processes of the invention.
DETAILED DESCRIPTION OF THE INVENTION
In this specification, the term "acrylic" is used in a general sense to describe polymers wherein a predominant proportion of the monomers is of the acrylic or methacrylic type, including acids, esters, amides and substituted derivatives thereof.
The first stage polymer is formed by emulsion polymerization of a first monomer composition having a T g of about (-) 10° C. or lower consisting essentially of (a) about 70-95% by weight of at least one (C 1 -C 8 ) alkyl acrylate, preferably about 76-86% by weight of butyl acrylate, (b) about 0-15% alkyl methacrylate, preferably about 6-15% by weight of methyl methacrylate, (c) about 4-10% by weight of at least one of acrylamide or methacrylamide, preferably about 7% by weight of methacrylamide, and (d) about 0.5-4% by weight of at least one of acrylic acid, methacrylic acid, or itaconic acid, preferably about 1% by weight of itaconic acid.
The second stage polymer is formed by emulsion polymerization, in the presence of the first stage polymer, of a second monomer composition having a T g of about (-) 10° to (+) 60° C. consisting essentially of (a) about 40-70% by weight of at least one (C 1 -C 8 ) alkyl acrylate, preferably about 47-57% by weight of butyl acrylate, (b) about 20-50% by weight of at least one (C 1 -C 8 ) alkyl methacrylate, preferably 35-45% by weight of methyl methacrylate, (c) about 4-10% by weight of acrylamide or methacrylamide, preferably about 7% by weight of methacrylamide, and (d) 0.5-4% by weight of at least one of acrylic acid, methacrylic acid, or itaconic acid, preferably about 1% of itaconic acid.
The third stage polymer is formed by the emulsion polymerization, in the presence of the product of the second stage polymerization, of a third monomer composition consisting essentially of (a) about 50-100% by weight of methyl methacrylate, and (b) 0-50% by weight of a comonomer copolymerizable with methyl methacrylate, preferably 100% by weight of methyl methacrylate.
Part of the alkyl acrylate, up to a maximum of about 20% by weight, in the first and second monomer compositions may be replaced with non-crosslinking (with respect to the alkyl acrylate) monoethylenically unsaturated monomer having alpha, beta-ethylenic unsaturation. Examples of such comonomers include vinyl and vinylidene halides such as the chlorides; vinyl esters such as vinyl formate and acetate; mixtures of ethylene and the vinyl esters; (meth)acrylic esters of alcohol ethers such as diethylene glycol monoethyl ether; styrene and aromatic ring-alkyl styrenes; alpha olefins such as ethylene, butylene and propylene; vinyl ethers, and compatible mixtures thereof.
The same group of comonomers mentioned in the foregoing paragraph may also constitute the comonomers which may be used with methyl methacrylate in the third monomer composition.
The most preferred calenderable acrylic composition of the invention is that composition within the scope of the above, the particles of which comprise about 45% by weight of a polymeric first stage, about 45% by weight of a polymeric second stage, and about 10% by weight of a polymeric third stage, wherein
(1) the first monomer composition consists essentially of
(a) about 86% by weight of butyl acrylate,
(b) about 6% by weight of methyl methacrylate,
(c) about 7% by weight of methacrylamide, and
(d) about 1% by weight of itaconic acid;
(2) the second monomer composition consists essentially of
(a) about 57% by weight of butyl acrylate,
(b) about 35% by weight of methyl methacrylate,
(c) about 7% by weight of methacrylamine, and
(d) about 1% by weight of itaconic acid; and
(3) the third monomer composition consists essentially of methyl methacrylate.
Preferably, only a "latent crosslinking monomer", meaning a polyfunctional monomer wherein a portion of the functionality enters into copolymerization with other monomers in the monomer composition and the residual functionality causes "crosslinking" (that is, interaction or association) between the polymer stages upon subsequent complete drying, is used and no polyethylenically unsaturated monomer which crosslinks during initial polymerization is included in the monomer compositions. The type of functionality selected to provide "latent cross-linking", appears to provide sufficient interaction which prevents the polymer from becoming completely molten but still permits development of the required "nerve" mentioned above. Although the mechanism of this interaction is not fully understood, this interaction appears to be well-established and is a critical element of the invention. A completely crosslinked system, which can be achieved only by the addition of conventional crosslinking monomer, does not achieve the objects of the invention. The latent crosslinking monomer is selected from acrylamide and methacrylamide and is used in the amounts of 4-10% by weight in the first and second monomer compositions. Preferably, about 7% by weight of methacrylamide is used.
The T g of the first and second stage polymer compositions are determinable in a known manner either experimentally or by calculation. The method of calculating the T g based upon the T g of homopolymers of individual monomers is described by Fox, Bull Am. Physics Soc., 1, 3, 123 (1956). Examples of T g of the homopolymers which permit such calculations are the following:
______________________________________HOMOPOLYMER OF Tg______________________________________n-octyl acrylate -80° C.n-decyl methacrylate -60° C.2-ethylhexyl acrylate -70 ° C.octyl methacrylate -20° C.n-tetradecyl methacrylate 9° C.methyl acrylate 9° C.n-tetradecyl acrylate 20° C.methyl methacrylate 105° C.acrylic acid 106° C.______________________________________
Monomers may be selected to obtain the appropriate T g through use of the "Rohm and Haas Acrylic Glass Temperature Analyzer", publication CM-24L/cb of Rohm and Haas Company, Philadelphia, Penn.
The heteropolymer compositions are prepared by emulsion polymerization techniques based on a two-stage polymerization and gradual addition of the monomer emulsions in each of the two stages. While it is advantageous to initiate and catalyze the reaction in each stage in a conventional manner, wherein the initiator is activated either thermally or by a redox reaction, thermal initiation is preferred from the standpoint of better storage stability of the resulting polymer emulsion and balance of properties as a textile treating resin. The latex particles size should be relatively small, of the order of about 300 nm or less, preferably about 150-200 nm. As is well-known, given the same polymer backbone, particle size is controlled primarily by the type and level of emulsifier used in each stage of the emulsion polymerization. Molecular weight of the heteropolymers generally is of the order of about 70,000 to 2,000,000, preferably about 250,000 to 1,000,000.
The foregoing and other aspects of two-stage heteropolymer emulsion polymerization are well-known as described, for example, in U.S. Pat. Nos. 3,812,205, 3,895,028, 3,461,188 and 3,457,209 except for the critical monomer selection described herein.
The polymers may be conveniently isolated (and then dried) by either of two methods. The first method, freeze drying, has the advantage that it permits isolation of the polymer at low temperature and thereby minimizes any premature interaction within the polymer. For example, a Vir-Tis Freeze Drying Apparatus may be used. More particularly, a given polymer may be freeze-dried using this apparatus by diluting 400 g of the emulsion to 25% T.S., placing the diluted mixture in a 2-l. round bottom flask, swirling the mixture in an acetone-dry ice bath until the emulsion mixture is frozen, and then connecting the flask to the freeze drying apparatus and maintaining the system under reduced pressure. Ordinarily, after about 16 hours of being exposed to the freeze-drying apparatus under reduced pressure, the polymer is obtained in dry particulate form. While desirable for use with small quantities of polymer emulsion, the freeze-dry method would not be practical for large-scale operation.
For larger-scale operation, the "coagulation" method of isolating the polymers is used. Effective coagulation can be achieved by a salt coagulation technique using a 0.59% aqueous solution of aluminum sulfate adjusted to 35° C. While maintaining effective agitation, the polymer emulsion, maintained at 35° C., is slowly added up to a concentration of 35 parts emulsion per 100 parts of salt solution. The temperature is critical in that temperatures lower than 35° C. give a very fine coagulum which is difficult to filter and temperatures higher than 35° C. appear to result in pre-mature crosslinking and non-calenderable polymer is obtained. Alternatively, coagulation can be achieved by adding a cationic surfactant, for example Hyamine 3500® (available from the Rohm and Haas Company), to a diluted polymer emulsion. In either case, the resulting coagulum can be isolated on a Buchner funnel, washed, and then dried (for example, airdried for several days, vacuum dried, or forced air at relatively low temperatures such as 100° C).
Films or sheets of the multiple-stage polymer, or heteropolymer, of the invention may be prepared by calendering the dried heteropolymer and the films may then be stored in rolls or applied in the calendering operation of any form of textile fabric to obtain a variety of useful textile articles. In one end use application, the calendered heteropolymer may be used as a transfer film which is laminated with an adhesive to a suitable fabric in the manufacture of upholstery materials. The adhesive in such application may be any known adhesive useful for adhering acrylic films to fabrics. For example, the adhesive may be in the form of a dry, crushed foam acrylic latex coating, as set forth in Hoey, U.S. Pat. Re. No. 28,682 reissued Jan. 13, 1976, applied to a fabric substrate. The calendered heteropolymer film of this invention may then be applied as a top film to the adhesive-bearing adhesive-fabric composite to provide a laminated upholstery material.
The following examples illustrate but a few embodiments of the invention. All parts and percentages are by weight unless otherwise indicated. The abbreviations used have the following meaning:
______________________________________SLS = sodium lauryl sulfate SSF = sodium sulfoxylate formaldehydeBA = butyl acrylate t-BHP = t-butyl hydro- peroxideMMA = methyl methacrylate VAc = vinyl acetateMAM = methacrylamide MPA = mercapto propionic acidAM = acyrlamide AA = acrylic acidIA = itaconic acid MAA = methacrylic acidME = monomer emulsion MlMAM = N-methylol- methacrylamide: methacrylamide (1:1)NaPS = sodium persulfate MlAM = N-methylol acrylamide:acrylamide (9:1)Sty = styrene ALMA = allyl methacrylate______________________________________
EXAMPLE 1 --PREPARATION OF HETEROPOLYMER
a. (38.7 BA/2.7 MMA/3.15MAM/0.45IA)/(25.7BA/15.7MMA /3.15MAM/0.45IA)/10 MMA
The following ingredients are provided:
______________________________________Monomer Emulsions I II III______________________________________SLS (28%) 295.2g 295.2g 34.4gH.sub.2 O 3983.Oml 3983.0ml 1920.40mlBA 7485.44g 4961.28g 0MMA 522.24g 3046.40g 1936.0gMAM 609.28g 609.28g 0IA 87.04g 87.04g 0H.sub.2 O (rinse) 140ml 140ml 80mlInitial ChargeSLS (28%) 31.08gH.sub.2 O 5000mlME #I 400gNaPS/H.sub.2 O 29.2g/208Cofeed CatalystNaPS/H.sub.2 O 29.2g/1952mlCharge III CatalystFeSO.sub.4 . H.sub.2 O 80ml(0.15% in H.sub.2 O)t-BHP/H.sub.2 O 8g/56mlSSF/H.sub.2 O 6.96g/160mlChaser Catalystt-BHP/H.sub.2 O 8g/56mlSSF/H.sub.2 O 6.4g/106ml______________________________________
To a suitable reaction vessel there is added the Initial Charge and the temperature of the charged reaction vessel is maintained at 80-86° C. After about 10-15 minutes, the remainder of ME #I and 976 ml of the Cofeed Catalyst are gradually added with stirring over a period of about 90 minutes. After 30 minutes, ME #II and 976 ml of the Cofeed Cataylst are gradually added with stirring over a period of about 90 minutes. After about 30 minutes, the charged reaction vessel is cooled to about 60° C. and ME #III is added in one portion. After about 20 minutes Charge III Catalyst is added while maintaining the temperature at about 55-60° C. Upon completion of this addition, the reaction mixture is stirred for about fifteen minutes and then the Chaser Catalyst is added. After allowing the reaction mixture to stir for about 15 minutes, the mixture is allowed to cool to room temperature and then it is filtered. The product is characterized as follows:
______________________________________ Particle Size (u) Viscosity,Solids Gum B/G/R pH #2/60______________________________________50.7% 2.8g .139/.144/.145 4.5 161 cps______________________________________
EXAMPLE 1.b.
Following substantially the above-described procedure except for the selection of the particular monomers and their proportions, the following polymers can be prepared:
(1) (38.7BA/2.7MMA/3.15 MAM/1IA)//(23.4BA/18MMA/3.15MAM/ 0.45IA)//10MMA
(2) (38.7BA/2.7MMA/3.15MAM/1IA)//(21.15BA/20.25MMA/ 3.15MAM/0.45IA)//10MMA
(3) 32.85BA/4.95MMA/3.15MAM/1IA//25.65BA/15.75MMA/3.15MAM/0.45IA//10MMA
(4) 34.2BA/7.2MMA/3.15MAM/1IA//25.65BA/15.75MMA/3.15MAM/0.45IA//10MMA
EXAMPLE 2--COMPARATIVE CALENDERABILITY OF ACRYLIC POLYMERS
The following acrylic polymers are produced by emulsion polymerization, dried, isolated, and calendered on a two roll mill calendering apparatus consisting of two 10"×15"steam heated rolls. The results are summarized in Table I.
______________________________________Poly-mer Composition______________________________________A Example 1.a. (above)B 95 (66EA/32.7MMA/1.3MMA)/5(66EA/ 31MMA/1MMA/ 2 N-([beta-(alpha-methacryloxyacetamido) ethyl])-ethylene urea)C 66EA/31MMA/1MMA/2 N-([beta-(alpha-methacryloxy- acetamido)ethyl])-ethylene ureaD 58BA/39.5VAc/1.8IA/0.7AAE 68BA/30MMA/7M1MAM/1IAF 47.75EA/47.75BA/3AM/1.5IA/0.05MPAG 43BA/2.5MMA/3.5MAM/0.5ALMA/1IA//27.5BA 17.5MMA/3.5MMA/3.5M1MAM/0.5IAH 43BA/3MMA/3.5MAM/0.5IA//28.5BA/17.7MMA/ 3.5M1MAM/0.5IAJ 75 Polymer F/25 Polymer BK 43BA/3MMA/3.5MAM/0.5IA//28.5BA/ 17.5MMA/3.5MAM/0.5IAL 38.7BA/2.7MMA/3.15MAM/0.45IA//25.7BA/ 15.7MMA/3.15MAM/0.45IA/10MMA + 0.2MPAM 38.7BA/3.7MMA/3.15MAM/0.45IA//25.65BA/ 15.75MMA/3.15M1MAM/0.45IA//10MMA______________________________________
TABLE I__________________________________________________________________________Calenderability of Acrylic Polymers Nominal Roll FluxingPolymerT300.sup.a Temp.,(°F.) Aids Comments__________________________________________________________________________A 0 215 b Very good film at thickness of 1.5 mil and greaterB (+)16 300 b No film formation, gummyB (+)16 210 b No film formation, gummy, stalling millC (+)7 300 b No film formation, gummyC (+)7 210 b No film formation, gummyD (-)9 210 b Tacky, sticking to both rollsE (-)8 300 b "Cheezy" opaque film, little fluxingE (-)8 360 b "Cheezy" opaque film, little fluxingE (-)8 210 b "Cheezy" opaque film, little fluxingF (-)18 290 b Fluxed well, film tacky and gummyF (-)18 220 b No film formationG (-)8 300 b Sluggish fluxing, poor film, opaqueG (-)8 220 b Sluggish fluxing, poor film, opaqueH (-)8 300 b "Cheezy" opaque filmH (-)8 220 b "Cheezy" opaque filmJ (-)8 220 b Gummy, no film formationK (-)8 300 b Tacky film; holes in film; fluxed wellK (-)8 215 b Less tacky film, good film thickness of 4 units and greaterL 0 215 b Fluxed well, film somewhat tackyM 0 215 b Fluxed poorly; poor film quality; slight roll sticking__________________________________________________________________________ .sup.a T.sub.300 = glass transition temperature °C. .sup.b 4% Harshaw W701.sup.R carbon black + 4% stearic acid + 4% polymeri processing aid (36MMA/4EA/24BA/36Sty); post added
The results in Table I indicate that highly thermoplastic acrylic polymers, for example Polymer B, merely soften and become gummy without developing any useful film properties or characteristics when introduced into a calendering apparatus.
Also, polymers having a relatively high degree of crosslinking resulting from the use of methylolacrylamide provide weak film properties, apparently due to poor film coalescence resulting from excessive crosslinking. In this regard, reference is made to Polymers E, G, H, and M.
Polymer F demonstrates that high molecular weight is important. While this polymer has functionality similar to that of the polymers of the invention, no interpolymer interactions occur and the polymer remains gummy on the calender as a result of its low molecular weight.
Polymer K shows improvement over Polymer F in that the film fluxed well and is less tacky.
Polymer A, according to the invention, provides very good film formation in the range of thickness 1.5-10 mils. Especially advantageous is the observation that this polymer can be calendered successfully at a roll temperature of 215° F., which temperature is substantially below the 300-400° F. temperature range required in calendering PVC and related vinyl polymer systems. Processing of Polymer A at higher temperatures resulted in increased tack in the film. The use of mercapto propionic acid in the polymerization of the monomers of Polymer A to provide lower molecular weight resulted in increased tack in the film (Polymer L). Polymer M is a repeat of Polymer A.
EXAMPLE 3 --PERFORMANCE PROPERTIES OF CALENDERED ACRYLIC FILM
Composites are prepared by casting a foam produced from Polymer F above on woven and non-woven fabric substrate at a level of 6-8 dry ounces per square yard and then drying the foam coated fabric. For a comparative study, films are produced from Polymer A both by emulsion casting and by calendering the dried and isolated polymer. The respective films are applied to the foam surface of the intermediate foam-fabric composite and thereafter the foam layer is crushed by passing the film-covered intermediate foam-fabric composite through embossing plates. Samples of the film-covered, crushed foam-coated fabric are cured by exposure thereof to a temperature of 300° F. for four minutes. The test results, which are summarized in Table II, show that the polymer according to the invention adequately fluxes and flows on a calender and provides a film which duplicates an emulsion cast film of the same polymer, which represents maximum film formation.
TABLE II______________________________________Composites of acrylic Film-Covered Fabrics Emulsion CalenderedProperty Casted Film.sup.a Film.sup.a______________________________________Tensile Strength, psi (film only) 540 490Elongation, % (film only) 415 325Taber Abrasion, H-18/500g/1000 45 59cycles(ASTM D-1175-71)Blocking 3 2Bally Flex (cycles) 400,000 350,000(Society Leather Technologists and Chemists Method SLP-14)Stoll Flex (cycles) 200 200(Federal Test Method Std. No. 191, Method 5300, using 616 tensionand 0.5lb pressure)Newark Seam Tear (cycles) 325,000 300,000(ASTM D-2097-69)Hoffman Scratch (g)One Eye Twill 700 1,800Napped and Sheared 1,600 2,000Wyzenbeek Abrasion (cycles) 25,000 45,000(ASTM D-1175-64)Cold Crack (°F.) (-)15 (-)15______________________________________ .sup.a film thickness = 2.5-3 mils | There is disclosed a calenderable, soft, three-stage acrylic heteropolymer having a calculated T g of about (-) 40° to (=) 20° C. which is suitable for producing films and sheets useful to coat textile materials and other substrates to form composites. The heteropolymer can be coagulated and then introduced into a calendering apparatus to produce films and sheets at substantially lower temperatures than are required for calendering vinyl halide polymers. | 8 |
BACKGROUND OF THE INVENTION
The present invention relates generally to a coupling quartz crystal resonator, and particularly to a GT-cut quartz crystal resonator in which plural longitudinal coupling modes are coupled and to a method for manufacturing the same.
Conventionally, an AT-cut quartz crystal resonator has been used for consumer products which require a resonator with excellent temperature characteristics and small CI (crystal impedance). Lately, in accordance with the miniaturization of various consumer products, miniaturization of the AT-cut quartz resonator has also been required. Miniaturization of this type resonator, however, is difficult because of the frequent occurrence of spurious vibrations and the resultant high CI. Unlike a tuning fork flexural quartz crystal resonator, it is difficult to minimize the size of the AT-cut quartz crystal resonator for use in a watch. Accordingly, a method of forming a resonator by photography which applies an IC technique has recently been applied to the manufacture, for example, of a tuning fork quartz crystal resonator and a GT-cut quartz crystal resonator (U.S. Pat. No. 4,350,918), and resultantly an extremely miniature resonator can be provided. However, U.S. Pat. No. 4,350,918 does not teach the electrode arrangement, a method for adjusting the frequency, a method for adjusting the temperature coefficient or the specific shape of the pedestal. On the contrary, the present invention discloses the above features.
Since, however, the GT-cut quartz resonator is supported at both ends, unlike the conventional type, it is necessary to improve the method for manufacturing the resonator unit. Accordingly, the present invention also provides a method for manufacturing a quartz crystal resonator unit having excellent shock resistance and frequency-temperature characteristics.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the invention to provide a coupling quartz crystal resonator, particularly a GT-cut quartz crystal resonator having excellent frequency-temperature characteristics (referred to as temperature characteristic hereafter).
It is another object of the invention to provide a GT-cut quartz crystal resonator having a small CI (Crystal Impedance).
It is another object of the invention to provide a GT-cut quartz crystal resonator which possesses excellent shock resistance.
It is another object of the invention to provide a resonator supporting structure to enable mounting of the resonator in a simple mounting operation.
BRIEF EXPLANATION OF THE DRAWINGS
FIGS. 1(A) and 1(B) show an embodiment of the shape of the coupling resonator according to the present invention,
FIG. 1(A) shows a plan view and FIG. 1(B) shows a side view,
FIGS. 2(A) and 2(B) show another embodiment of the shape of the coupling resonator according to the present invention, FIG. 2(A) shows a plan view and FIG. 2(B) show a side view,
FIGS. 3(A) and 3(B) show another embodiment of the shape of the coupling resonator according to the present invention, FIG. 3(A) shows a plan view and FIG. 3(B) shows a side view,
FIG. 4 shows the cut directions of the GI-cut quartz resonator according to the present invention,
FIG. 5 shows the relationship between the cut angle φ and the temperature coefficients α, β of the coupling quartz crystal resonator according to the present invention,
FIG. 6 shows the relationship between the side ratio R and the temperature coefficients α, β of the GT-cut quartz crystal resonator according to the present invention,
FIG. 7 shows the relationship between the side ratio R and the temperature coefficient α when the dimensions of the supporting portions of the GT-cut quartz crystal resonator are used as parameter,
FIGS. 8(A) and 8(B) show an embodiment of electrode arrangement of the shape of the coupling resonator according to the present invention, FIG. 8(A) shows a plan view and FIG. 8(B) shows a side view,
FIGS. 9(A) and 9(B) show another embodiment of electrode arrangement of the shape of the coupling resonator according to the present invention, FIG. 9(A) shows a plan view and FIG. 9(B) shows a side view,
FIG. 10 shows another embodiment of electrode arrangement of the shape of the coupling resonator according to the present invention,
FIG. 11 shows a plan view of another embodiment of electrode arrangement of the shape of the coupling resonator according to the present invention,
FIGS. 12-19 show plan views showing other embodiments of electrode arrangement of the shape of the coupling resonator according to the present invention,
FIGS. 20(A) and 20(B) show another embodiment of electrode arrangement of the shape of the coupling resonator according to the present invention,
FIG. 21 shows a plan view of another embodiment of electrode arrangement and masses of the shape of the coupling resonator according to the present invention,
FIG. 22 shows a plan view of another embodiment the electrode arrangement and masses of the shape of the coupling resonator according to the present invention,
FIG. 23 shows a half view of the GT-cut quartz crystal resonator whose resonant portion and supporting portions are made in one piece,
FIG. 24 shows the relationship between each of the positions of the resonator in FIG. 23 and the distorsion,
FIG. 25(A) shows the histogram showing the distribution of the CI value, FIG. 25(B) shows another histogram showing the distribution of the CI value,
FIG. 26 shows the relationship between the amount of the eliminated masses and the deviation Δα of the primary temperature coefficient α,
FIG. 27 shows another relationship between the amount of the eliminated masses and the deviation Δα of the primary temperature coefficient α,
FIG. 28 shows another relationship between the amount of the eliminated masses and the deviation Δα of the primary temperature coefficient α,
FIG. 29 shows the relationship between the amount of the eliminated masses and the variation of the resonance frequency of the main vibration,
FIGS. 30(A), 30(B) and 30(C) show an embodiment of the GI-cut quartz resonator mounted on a pedestal according to the present invention, FIG. 30(A) shows a top plan view, FIG. 30(B) shows a lower side view of FIG. 30(A) and FIG. 30(C) shows a bottom view of FIG. 30(B),
FIGS. 31(A), 31(B) and 31(C) show another embodiment of the GT-cut quartz resonator mounted on a pedestal according to the present invention, FIG. 31(A) shows a top plan view, FIG. 31(B) shows a lower side view of FIG. 31(A) and FIG. 31(C) shows a bottom view of FIG. 31(B),
FIG. 32 is a graph showing the temperature characteristic according to the present invention,
FIGS. 33(A) and 33(B) show an embodiment of the shape and electrode arrangement of the GT-cut coupling resonator according to the present invention, in which the resonance portion and the supporting portions are formed in one piece, FIG. 33(A) shows a plan view and FIG. 33(B) shows a side view,
FIG. 34 is a graph showing the temperature characteristics of a GT-cut quartz crystal resonator formed by photolithography,
FIG. 35 is a graph showing the relationship between the side ratio R and the primary temperature coefficient α of the GT-cut quartz crystal resonator whose resonant portion and the supporting portions are formed in one piece,
FIG. 36 is a graph showing the relationship between the etching time and the side ratio R of the GT-cut quartz crystal resonator according to the present invention,
FIG. 37 is a graph showing the relationship between the etching time and the deviation Δα of the primary temperature coefficient α of the GT-cut quartz crystal resonator according to the present invention,
FIG. 38 is a graph showing the relationship between the primary temperature coefficient α and the etching time to make α zero in case α=1 ppm/°C. and 2.5 ppm/°C. after etching the GT-cut quartz crystal resonator according to the present invention,
FIG. 39 is a graph showing an embodiment of the temperature characteristics after adjusting the temperature coefficient by the method of the present invention,
FIGS. 40(A), 40(B) and 40(C) show an embodiment of the GT-cut quartz crystel resonator mounted on a pedestal according to the present invention, FIG. 40(A) is a top plan view, FIG. 40(B) is a lower side view of FIG. 40(A) and FIG. 40(C) is a bottom view of FIG. 40(B),
FIGS. 41(A), 41(B) and 41(C) show another embodiment of the GT-cut quartz crystal resonator mounted on the pedestal according to the present invention, FIG. 41(A) is a top plan view, FIG. 41(B) is a lower side view of FIG. 41(A) and FIG. 41(C) is a bottom view of FIG. 41(B),
FIG. 42 is a plan view of an embodiment of the present invention, wherein the pedestal shown in FIGS. 40(A), 40(B) and 40(C) is mounted on the support lead wires provided on the stem,
FIG. 43 is a plan view of another embodiment of the present invention, wherein the pedestal shown in FIGS. 41(A), 41(B) and 41(C) is mounted on the support lead wires provided on the stem,
FIG. 44 is a plan view showing an embodiment wherein the masses are deposited on the GT-cut quartz crystal resonator by evaporation,
FIG. 45 is a plan view showing another embodiment wherein the masses are deposited on the GT-cut quartz crystal resonator by evaporation,
FIG. 46 is a graph showing the relationship between the amount of the masses and the deviation of the resonance frequency of the main vibration,
FIG. 47 is a graph showing the relationship between the amount of the masses and the primary temperature coefficient α, and
FIG. 48 is a perspective view showing external appearance of an embodiment of the coupling resonator unit obtained by the manufacturing method of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
FIGS. 1(A) and 1(B) show one embodiment of the shape of a GT-cut coupling resonator according to the present invention, in which a resonant portion 1 is made in one piece with two supporting portions 2 at both sides of the resonant portion by etching. FIG. 1(A) is a plan view and FIG. 2(B) is a side view.
Recesses or openings 3 are provided at both the supporting portions 2 between the resonant portion 1 and mount portions 4. The recesses 3 are provided to enclose and confine the exciting energy of the resonant portion 1 so that the exciting energy of the resonant portion is not transmitted to the mount portions 4. Therefore, energy is not lost by mounting the resonator, and a resonator having a small CI value is obtained.
FIGS. 2(A) and 2(B) show another embodiment of the shape of a coupling GT-cut quartz crystal resonator according to the present invention, in which a resonator portion 5 and two supporting portions 6 at both sides of the resonant portion are made in one piece by etching. FIG. 2(A) shows a plan view and FIG. 2(B) shows a side view. Recesses or openings 7 are provided at both the supporting portions 6 between the resonant portion 5 and mount portions 8. The recesses 7 are provided for the same reason as that explained above with reference to FIGS. 1(A) and 1(B).
FIGS. 3(A) and 3(B) show another embodiment of the shape of a coupling GT-cut quartz crystal resonator according to the present invention, in which a resonant portion 9 and two supporting portions 10 at both sides of the resonant portion are formed in one piece by etching.
FIG. 3(A) shows a plan view and FIG. 3(B) shows a side view. Recesses 11 are provided at both the supporting portion 10 between the resonant portion 9 and mount portions 12. The recesses 11 are provided for the same reason as explained with reference to FIGS. 1(A) and 1(B).
In the resonators shown in FIGS. 1(A), 1(B), 2(A), 2(B), 3(A) and 3(B), the resonance freqencies of two modes are determined by the width W and the length L dimensions.
When the resonance frequency of the main vibration determined by the width W is fW and the resonance frequency of the spurious vibration determined by the length L is fL, the temperature characteristic is substantially determined by the balance of both resonance frequencies; Δf=fW-fL. Namely, the temperature characteristics is determined by the side ratio R=W/L.
FIG. 4 shows the cut directions, i.e. formation directions by etching of the GT-cut quartz crystal resonator according to the present invention. X axis, Y axis and Z axis are respectively the electrical axis, mechanical axis and optical axis of a quartz crystal. A quartz crystal resonator 13 is formed to become YXlt (φ/θ) by the IRE standard. X' axis, Y' axis and Z' axis are respectively the new axes after turning the X, Y and Z axes.
FIG. 5 shows the relationship between the cut angle φ of the GT-cut quartz crystal resonator, whose resonant portion is formed in one piece with the supporting portions by etching, and the primary and the secondary temperature coefficients α and β. The shape of the resonator, i.e. the side ratio R, and the cut angle θ are fixed. As understood from FIG. 5, the primary and the secondary temperature coefficients α and β shift from the negative value to the positive value as the cut angle θ increases. α varies less than β per 1 degree change of the cut angle. α and β are almost zero when the cut angle θ≈51, so that an excellent temperature characteristic is obtained.
FIG. 6 shows the relationship between the side ratio R=W/L of the GT-cut quartz crystal resonator according to the present invention and the primary and the secondary temperature coefficients α and β. The cut angles φ and θ are fixed. As understood from FIG. 6, the primary and the secondary temperature coefficients α and β vary from the negative value to the positive value as the side ratio R increases. β varies less than α per unit change of the side ratio R. α and β are almost zero when the side ratio R≈0.98, so that an excellent temperature characteristic is obtained.
FIG. 7 shows the relationship between the side ratio R=W/L and the primary temperature coefficient α when the dimension of the supporting portions of the GT-cut quartz crystal resonator are used as a parameter. A supporting portion B is designed to suppress the spurious vibration more than the supporting portion A. The side ratio which is needed to set α at zero is different in the supporting portion A and the supporting portion B. The side ratio R to set α at zero is larger in the supporting portion B than in the supporting portion A. Therefore an excellent temperature characteristic of the GT-cut quartz crystal resonator according to the present invention is obtained by a combination of the cut angles φ=48°-53°, θ=(45°-55°) and the side ratio R=0.9-1.2.
FIGS. 8(A) and 9(B) show an embodiment of electrode arrangement of the coupling resonator according to the present invention. FIG. 8(A) shows a plan view and FIG. 8(B) shows a side view. Exciting electrodes 16 and 17 are uniformly arranged on the lower and upper opposed major surfaces of a resonant portion 15 of a quartz crystal resonator 14. The exciting electrode 16 elongates to one supporting portion and the exciting electrode 17 elongates to the other supporting portion. In this case the electrodes are respectively deposited on one side of each of the supporting portions but not both sides, so that no electric field is applied to the supporting portions.
FIGS. 9(A) and 9(B) show another embodiment of electrode arrangement of the coupling resonator according to the present invention. FIG. 9(A) shows a plan view and FIG. 9(B) shows a side view. Exciting electrodes 20 and 21 are deposited on lower and upper opposed major surfaces of a resonant portion 19 of a quartz crystal resonator 18 except for the peripheral portion.
FIG. 10 show another embodiment of electrode arrangement of the coupling resonator according to the present invention. An exciting electrode 24 and masses 25 and 26 for frequency adjustment are deposited on a resonant portion 23 of a quartz crystal resonator 22. The exciting electrode is not electrically connected to the masses. The exciting electrode is arranged on almost the overall major surface of the resonant portion of the resonator except for the positions of the masses. Although not shown, a rear exciting electrode may be arranged on the overall rear major surface of the resonant portion or the rear electrode and masses may be deposited symmetrically to the exciting electrode 24 and the masses 25 and 26.
FIG. 11 shows a plan view of another embodiment of the electrode arrangement of the coupling resonator according to the present invention. An exciting electrode 29 is arranged on a resonant portion 28 of a quartz crystal resonator 27 except for the positions of masses 30, 31, 32 and 33 for frequency adjustment provided at the four corners of the resonant portion.
FIG. 12 shows a plan view of another embodiment of electrode arrangement of the coupling resonator according to the present invention. An exciting electrode 35 and masses 36, 37, 38 and 39 for frequency adjustment are deposited on a resonant portion 34. The exciting electrode is arranged on the overall surface of the resonant portion except for the position of the masses.
FIG. 13 is a plan view showing another embodiment of electrode arrangement of the coupling resonator according to the present invention. An exciting electrode 40 indicated by oblique lines and masses 41-50 for frequency adjustment are deposited on the resonant portion.
FIG. 14 shows a plan view of another embodiment of electrode arrangement of the coupling resonator according to the present invention. An exciting electrode 51 and masses 52 and 53 are deposited on the resonant portion.
FIG. 15 shows a plan view of another embodiment of electrode arrangement of the coupling resonator according to the present invention. An exciting electrode 54 and masses 55 and 56 for frequency adjustment are deposited on the resonant portion. FIG. 16 shows a plan view of another embodiment of electrode arrangement of the coupling resonator according to the present invention. An exciting electrode 57 and masses 58, 59, 60 and 61 are deposited on the resonant portion. FIG. 17 shows a plan view of another embodiment of electrode arrangement of the coupling resonator according to the present invention. An exciting electrode 62 and masses 63-70 for frequency adjustment are deposited on the resonant portion. FIG. 18 shows a plan view of another embodiment of the resonator according to the present invention. An exciting electrode 71 and a mass 72 for frequency adjustment are deposited on the resonant portion. FIG. 19 shows a plan view of another embodiment of electrode arrangement of the coupling resonator according to the present invention. An exciting electrode 73 and a mass 74 for frequency adjustment are deposited on the resonant portion. Although not shown, rear exciting electrodes may be deposited on the overall rear surface of the resonant portion, or may be deposited symmetrically to the exciting electrodes and the masses for frequency adjustment, as illustrated in FIG. 10. Further, although plural masses are deposited on the resonant portion in FIGS. 10-17, it is to be noted that the same effect is obtained by depositing one mass though the amount of frequency adjustment is different.
FIGS. 20(A) and 20(B) show a plan view and a side view of another embodiment of electrode arrangement of the coupling resonator according to the present invention. Exiting electrodes 78 and 79 are respectively deposited on the overall upper and lower opposed major surfaces of a resonant portion 76 and a supporting portion 77 of a quartz crystal resonator 75. By depositing the exciting electrodes on the resonant portion and the supporting portions, the efficiency of the electric field can be more improved and thus the IC value can be made smaller.
FIG. 21 show a plan view of another embodiment of electrode arrangement and masses on the coupling resonator according to the present invention. Exciting electrodes 78, 78' (not shown) are uniformly arranged on the overall upper surface and lower surface (not shown) of the resonant portion and respective ones of the supporting portions of the quartz crystal resonator, further masses 80 and 81 with electrode load effect are deposited on the electrode 78 at both sides of the resonant portion.
FIG. 22 shows a plan view of another embodiment of electrode arrangement and masses of the present invention. Exciting electrodes 82 and 82' (not shown) are uniformly deposited on the overall upper surface and lower surface (not shown) of the resonant portion and respective ones of the supporting portions 83 and 84 of the quartz crystal resonator in a similar manner to FIG. 21. Further, masses 85, 86, 87 and 88 with electrode load effect are deposited on four corners on the electrode 82 of the resonant portion.
The electrode load effects comprise the following three effects:
(1) The exciting electrode at the side of the resonant portion serves as a mass by increasing the thickness. Therefore the resonance frequency f and the temperature characteristics can be changed.
(2) Reflection of the elastic wave at the side of the resonant portion is reduced and the spurious vibration can be restricted by the electrode load effect.
(3) The exciting energy can be trapped inside the resonant portion. Therefore the CI value is further reduced.
Although FIGS. 21 and 22 show embodiments in which the masses with electrode load effect are deposited on the exciting electrode on the overall surface of the resonant portion, it is to be noted that the masses may be arranged on the exciting electrodes in FIGS. 12-18 without deteriorating the electrode load effect.
Subsequently, the manner in which the CI value varies in accordance the area of the resonant portion covered by the exciting electrodes will be illustrated.
FIG. 23 shows one half of the GT-cut quartz crystal resonator according to the present invention whose resonant portion and supporting portions are made in one piece. The calculated value of the relationship between displacement and each position of the section taken on line A--A is shown. The displacement is zero at point c, and the absolute value of the displacement becomes larger at both ends, i.e., the displacement is largest at point a and point e (displacement u 1 =-u 2 ).
FIG. 24 shows the relationship between each of the positions and the distortion. The distortion is the largest at point c and becomes smaller at the end portions. As understood by FIG. 24, the distortion is not zero at points a and e. This means that the CI value of the quartz crystal resonator is different in case the exciting electrode is arranged at the ends of the resonant portion as compared to the case in which the exciting electrode is not arranged at the ends of the resonant portion. Namely the low CI value is obtained when the exciting electrode is also arranged at the end of the resonant portion.
FIG. 25 is a histogram showing the distribution of the experimentally obtained CI value in the case where the exciting electrodes are arranged on the overall upper and lower surfaces of the resonant portion as in FIGS. 8(A) and 8(B) and in the case where the exciting electrodes are arranged on some part of the resonant portion (about 75% of the resonant portion) as in FIGS. 9(A) and 9(B). FIG. 25(A) is the histogram showing the distribution of the CI value against the number n=200 when the exciting electrodes are arranged on some part of the resonant portion. The average CI value X=140 (Ω). FIG. 25(B) is the histogram showing the distribution of the CI value against the number n=200 when the exciting electrodes are arranged on the overall upper and lower surfaces of the resonant portion. The average CI value X=84 (Ω). It shows that the CI value is reduced by about 40% when the exciting electrodes are arranged on the overall upper and lower surfaces of the resonant portion. The resonance frequency and the frequency-temperature characteristics are adjusted by laser when the exciting electrodes and the masses are separately provided as in FIGS. 10-19. On the other hand, the resonance frequency and the frequency-temperature characteristics are adjusted by evaporation when the exciting electrodes are provided on the overall surfaces of the resonant portion and the masses are deposited thereon as in FIGS. 21 and 22.
Now an embodiment of adjusting the frequency-temperature coefficient and the resonance frequency by the addition or reduction of the masses will be illustrated in detail.
FIG. 26 shows the relationship between the amount of the eliminated masses 25 and 26 in FIG. 10 scattered by laser and the deviation Δα of the primary temperature coefficient α. The primary temperature coefficient α shifts to the positive side and increases in a positive sense with an increase in the amount of the eliminated masses.
FIG. 27 shows the relationship between the amount of the eliminated masses 30, 31, 32 and 33 in FIG. 11 scattered by laser and the deviation Δα of the primary temperature coefficient α. The primary temperature coefficient α shifts to the negative side and increases in a negative sense with an increase in the amount of the eliminated masses. It is found from FIGS. 26 and 27 that the primary temperature coefficient α shifts to the positive side by eliminating the masses in case of the arrangement of the masses in FIG. 10, while the primary temperature coefficient α shifts to the negative side by eliminating the masses in case of the arrangement of the masses in FIG. 11. It has been found that the primary temperature coefficient α does not deviate when a mass is arranged at positions between the masses 25 and 26 in FIG. 10 and the masses 30, 31, 32, and 33 in FIG. 11. FIG. 12 shows such an arrangement of the masses.
FIG. 28 shows the relationship between the amount of the masses 36, 37, 38 and 39 in FIG. 12 eliminated by laser and the deviation Δα of the primary temperature coefficient α. It has been found that the primary temperature characteristic α does not vary by eliminating the masses.
FIG. 29 shows the relationship between the amount of the masses 25 and 26 in FIG. 10, the masses 30, 31, 32 and 33 in FIG. 11, and the masses 36, 37, 38 and 39 in FIG. 12 eliminated by laser and the variation of the resonance frequency of the main vibration. Straight lines D, E and F correspond respectively to the relationship between the amount of the eliminated masses and the variation of the main resonance frequency in case of FIG. 10, FIG. 12 and FIG. 11. It is understood that the resonance frequency of the main vibration becomes higher as the amount of the eliminated masses increases. Although the frequency adjustments by reduction of the masses have been illustrated in the present embodiments, it is to be noted that the above-noted phenomenon is completely reversed when the masses are added. Further, although the explanation has been made with respect to FIGS. 10, 11 and 12, the resonance frequency and the frequency-temperature characteristics, or only the resonance frequency, can be changed by adjustment of the masses shown in FIGS. 13-19.
FIGS. 30(A), 30(B) and 30(C) show an embodiment of a GT-cut quartz resonator 90 mounted on a pedestal 94 according to the present invention. FIG. 30(A) shows a top plan view, FIG. 30(B) shows a lower said view of FIG. 30(A) and FIG. 30(C) shows a bottom view of FIG. 30(B). The pedestal 94 has a recessed center portion bounded at opposite ends by pedestal end portions 95 and 96 and electrodes 97, 98 and 99 are arranged on both of the end portions 95 and 96 in the manner shown. The electrodes 98 and 99 are connected through side electrodes 100, 101 and an electrode 102 arranged on the lower surface of the pedestal 94.
A quartz resonator 90 is supported on both end portions 95 and 96 of the pedestal 94 with the above electrode arrangement and secured with adhesives or solders 103 and 104 at the end of the resonator. By this arrangement, an exciting electrode 92 is connected to the electrode 97, and an exciting electrode 93 is connected to the electrode 99 so that the exciting electrode 93 has the same polarity as the electrode 98 through the electrodes 100, 102 and 101. Namely, by the above electrode arrangement at two-terminal structure of the electrodes 97 and 98 is made. The electrodes 100, 101 and 102 are not drawn to scale but have been drawn thicker for easy understanding of the drawing. Thus the resonator with excellent shock resistance is attained by mounting the resonator on the pedestal.
Although the electrode 102 is arranged on the lower surface of the pedestal, it may be arranged inside the pedestal.
FIGS. 31(A), 31(B) and 31(C) show another embodiment of a GT-cut quartz resonator 105 mounted on a pedestal 106 according to the present invention. FIG. 31(A) shows a top plan view, FIG. 31(B) shows a lower side view of FIG. 3(A) and FIG. 31(C) shows a bottom view of FIG. 31(B). The pedestal 101 has a generally concave shape with a recessed center portion and opposite end portions 107 and 108. Recesses 109, 110, 111 and 112 are provided at both end portions 107 and 108, and electrodes 113, 114 and 115 are arranged on both of the end portions in the manner shown. The electrodes 114 and 115 are connected through side electrodes 116, 117 and bottom electrode 118 arranged on the lower surface of the pedestal 116. A quartz resonator 105 is mounted in the recesses 111 and 112 of the pedestal 106 and secured with adhesives or solders 119 and 120 at the end of the resonator. By the above arrangement, an exciting electrode 121 is connected to the electrode 113 and an exciting electrode 122 is connected to the electrode 115. The exciting electrodes 121 and 122 are of the same polarity as the electrode terminals 113 and 114. Thus the resonator mounted in the recesses not only has excellent shock resistance but also is easily set and improved in workability. The pedestal on which the resonator is mounted is then mounted on lead wires, and thereafter sealed in now vacuum or a housing which is under filled with N 2 .
The effect of the thickness of the resonator will now be described.
In manufacturing resonators, the spurious vibration is generally a main factor which deteriorates the yield of the resonators. In this invention, the spurious vibration may be generated at frequencies near the main vibration frequency due to the plate thickness. Accordingly, the plate thickness is selected between 50μ and 100μ to eliminate the spurious vibration. The lower limit value of 50μ is selected because it is the minimum thickness in mass production and the plate of 50μ thickness can be easily handled. The upper limit value of 100μ is selected to enable processing of the resonator by photolithographic etching because the resonator cannot be processed mechanically because of its complicated shape. The thickness of the resonator is selected from the range of 50μ-100μ according to the frequency. The higher the resonance frequency is, i.e., the smaller the width W of the resonator is, the smaller the thickness of the plate is.
FIG. 32 shows a curve of the temperature characteristic according to the present invention. It is understood from FIG. 32 that an excellent temperature characteristic is obtained.
A method for manufacturing a resonator unit will now be described in detail.
FIGS. 33(A) and 33(B) shown an embodiment of the shape and electrode arrangement of a GT-cut coupling resonator according to the present invention, in which a resonant portion 124 is made in one piece with two supporting portions 125 at both sides of the resonant portion. FIG. 33(A) is a plan view and FIG. 33(B) is a side view. Exiting electrodes 128 and 129 are respectively provided uniformly on the overall lower and upper surfaces 126 and 127 of the resonant portion 124 of a quartz crystal 123. The exciting electrode 128 elongates to one supporting portion 125 and the exciting electrode 129 elongates to the other. Each exciting electrode is formed on only one surface of the supporting portion and this no electric field is applied between opposed faces of the two supporting portions. Accordingly the energy of the resonant portion is sealed in the interior of the resonant portion as much as possible lest it should be transferred to the supporting portion as discussed hereinbefore.
FIG. 34 shows an example of the temperature characteristic of the GT-cut quartz crystal resonator formed by photolithography, in which the temperature characteristics differ according to the coupling strength. Line a indicates a strong coupling between the main vibration and the spurious vibration, and line b indicates a weak coupling between the two. The primary temperature coefficient α disperses between 2.5×10 -6 /°C. and 1.0×10 -6 /°C., and consequently an excellent temperature characteristic cannot be obtained. Ordinary resonators have such temperature characteristics.
FIG. 35 shows the relationship between the side ratio R=W/L and the primary temperature coefficient α of the GI-cut quartz crystal resonator according to the present invention, in which the resonance portion and the supporting portions are made in one piece. The primary temperature coefficient α becomes larger with an increase in the side ratio R. The primary temperature coefficient α changes by about 1.3 ppm/°C. when the side ratio R changes by 0.01.
FIG. 36 shows the relationship between the etching time and the side ratio R of the GT-cut quartz crystal resonator according to the present invention. The side ratio R becomes gradually smaller with increase in the etching time. Experimentation has shown that the side ratio R decreases by about 0.01 after 60 min. etching.
FIG. 37 shows the relationship between the etching time and the deviation Δα in the primary temperature coefficient α of the GT-cut quartz crystal resonator according to the present invention. The deviation of the primary temperature coefficient Δα after 20 min. etching is about -0.5 ppm/°C. Δα becomes smaller with an increase in the etching time, and Δα is -1.3 ppm/°C. after 60 min. etching.
Now, a method of adjusting the frequency-temperature coefficient will be described.
The GT-cut quartz crystal resonator shown in FIGS. 33(A) and 33(B) formed by photolithography is designed to have the following features:
(1) The primary temperature coefficient α has a positive value. More specifically, the primary temperature coefficient α should be in the range of between +2.5 ppm/°C. and +1.0 ppm/°C.
(2) The resonance frequency of the main vibration has a higher value than the reference frequency f 0 to be tuned in, normally by 500-1000 ppm.
This type of resonator can be easily obtained by selecting the shape and etching time. The resonator formed by etching is brought to an arbitrary temperature t 1 . The temperature t 1 is read by a thermometer such as a thermistor, and the resonance frequency f 1 of the main vibration is also measured. Then, the resonator is brought to another arbitrary temperature t 2 , and the resonance frequency f 2 of the main vibration is also measured in the similar manner. The primary temperature coefficient α is obtained by the following formula using t 1 , t 2 and f 1 , f 2 . ##EQU1## The formula can be rewritten as follows by use of the reference frequency f 0 to be tuned in. ##EQU2## α is found by formulae (1) and (2). Namely the temperature coefficient after etching of the external shape of the resonator is experimentally found.
FIG. 38 shows the relationship between the primary temperature coefficient α and the external shape etching time needed to make α zero of the GT-cut quartz crystal resonator according to the present invention, in case of line A whose α is 1 ppm/°C. and line B whose α is 2.5 ppm/°C.
When α is 1 ppm/°C., α is made zero after 45 min. etching. When α is 2.5 ppm/°C. α is made zero after 115 min. etching. Thus the primary temperature coefficient α is found by temperatures t 1 and t 2 and the resonance frequencies f 1 and f 2 . Since the etching time has a linear relationship with respect to α, the primary temperature coefficient α can be made near zero by controlling the etching times for each α. The secondary and tertiary temperature coefficients of the GT-cut quartz resonator according to the present invention are negligible since they are considerably small in comparison with the primary temperature coefficient α.
FIG. 39 shows a graph of the temperature characteristic whose temperature coefficient α is adjusted by the method of the present invention. A straight line C is the temperature characteristic after etching the external shape, in which the primary temperature coefficient α is as large as about 1.5 ppm/°C. and the temperature characteristic is unsatisfactory. On the contrary, a straight line D is the temperature characteristic after 70 min. etching, in which the primary temperature coefficient α is considerably small, such as about 0.1 ppm/°C., and an excellent temperature characteristic is obtained. Although the temperature characteristic of the straight line D obtained in FIG. 39 is excellent, the resonance frequency of the main vibration should be regulated since it deviates from the reference frequency f 0 by 3000-5000 ppm. The resonator is mounted on a pedestal after etching the external shape thereof.
FIGS. 40(A), 40(B) and 40(C) show an embodiment of a GT-cut quartz crystal resonator 132 mounted on a pedestal 136 according to the present invention. FIG. 40(A) is a top plan view, FIG. 40(B) is a lower side view of FIG. 40(A), and FIG. 40(C) is a bottom view of FIG. 40(B). The pedestal 136 has a generally concave shape and has a recessed center portion and two spaced-apart end portions 137,138 and electrodes 139, 140 and 141 are arranged on the end portions 137 and 138. The electrode 140 is connected to the electrode 141 via side electrodes 142, 143 and a bottom electrode 144 arranged on the lower surface of the pedestal 136. A quartz crystal resonator 132 is mounted and supported on both end portions 137, 138 of the pedestal 136 with the above electrode arrangement, and secured at the ends thereof by adhesives or solders 145, 146. By such a construction, an exciting electrode 134 is connected to the electrode 139, and an exciting electrode 135 is connected to the electrode 141 so that the exciting electrode 135 is of the same polarity as the electrode 140 via the electrodes 142, 144 and 143. The above electrode arrangement on the pedestal 136 constitutes a two-terminal structure of the electrodes 139 and 140. The electrodes 142, 143 and 144 are drawn thicker than a scale to be easily understood. Such a resonator mounted on a pedestal has an excellent shock resistance.
FIGS. 41(A), 41(B) and 41(C) show another embodiment of the invention, in which a GT-cut quartz crystal resonator 147 is mounted on a pedestal 148 according to the present invention. FIG. 41(A) is a top plan view, FIG. 41(B) is a lower side view of FIG. 41(A), and FIG. 41(C) is a bottom view of FIG. 41(B). The pedestal 148 has a generally concave shape and has a recessed center portion with two spaced-apart end portions 149,150, and recesses 151, 152, 153 and 154 are provided at both end portions 149, 150 on which electrodes 155, 156 and 157 are arranged. The electrode 156 is connected to the electrode 157 via side electrodes 158, 159 and a bottom electrode 160 arranged on a lower surface of the pedestal 148. A quartz crystal resonator 147 is mounted and supported in the recesses 153, 154 of the pedestal 148 with the above electrode arrangement, and secured by adhesives or solder 161, 162 at the end thereof. By such a construction, an exciting electrode 163 is connected to the electrode 155 and an exciting electrode 164 is connected to the electrode 156. The exciting electrode 164 is at the same polarity as the electrode 156 through electrodes 158, 160 and 159. By mounting the resonator in the recesses, a resonator with excellent shock resistance is obtained. Further the resonator is easily set and its workability is improved.
The pedestal, on which the resonator is mounted, is then mounted on the lead wires.
FIG. 42 is a plan view of an embodiment of the invention, in which a pedestal 165 similar to that shown in FIGS. 40(A), 40(B) and 40(C) is mounted on support lead wires 167 and 168 provided on a stem 166. An exciting electrode 170 disposed on a quartz crystal resonator 169 is connected to an electrode 171 on the pedestal 165, while a rear exciting electrode (not shown) is connected to an electrode 172 and further connected to an electrode 173 through a lower electrode (not shown). The terminal electrodes 171 and 173 are secured to the support lead wires 167 and 168 with adhesives or solders 174 and 175 to form two terminals 176 and 177.
FIG. 43 is a plan view of another embodiment of the invention, in which a pedestal 178 similar to that shown in FIGS. 41(A), 41(B) and 41(C) is mounted on support lead wires 180 and 181 provided on a stem 179. A quartz crystal resonator 182 is arranged in recesses 184 and 185 provided on the pedestal 178 and secured by adhesives or solders 186 and 187. An exciting electrode 183 of the quartz crystal resonator 182 is connected to an electrode 188 and a rear exciting electrode (not shown) is connected to an electrode 189, and further connected to an electrode 190 through side and lower electrodes (not shown). The support lead wires 180, 181 provided on the stem 179 are arranged in recesses 191 and 192 formed in the pedestal 178 and secured with adhesives or solders 193 and 194, and connected to the electrodes 188 and 190 to define two terminals 195 and 196. As shown, the pedestal recesses 184,185 and 191,192 are covered at least in part by the respective exciting electrodes 188,190. The pedestal is made of insulating materials such as ceramics or quartz crystal, and the electrodes are made of gold or silver. The two-terminal structure is constructed when the quartz crystal resonator is mounted on the pedestal by arranging the electrode structure on the pedestal whereby the support lead wires can be easily mounted and the workability is improved.
Next, a method used to tune the resonance frequency of the main vibration to the reference frequency f 0 will be described.
FIG. 44 shows as embodiment in which masses 206, 207, 208 and 209 are deposited on the GT-cut quartz crystal resonator in FIG. 42 by evaporation. FIG. 45 shows another embodiment in which masses 210, 211, 212 and 213 are deposited on the GT-cut quartz crystal resonator in FIG. 43 by evaporation. FIG. 46 shows the relationship between the amount of the masses and the variation of the resonance frequency of the main vibration. It is understood that the resonance frequency of the main vibration becomes lower in accordance with an increase in the amount of the masses, and the resonance frequency of the main vibration can be tuned to the reference frequency f 0 even if the former deviates from the latter by 5000 ppm. FIG. 47 shows the relationship between the masses 206, 207, 208 and 209 in FIG. 44 and the masses 210, 211, 212 and 213 in FIG. 45 deposited on the resonator and the primary temperature coefficient α. No deviation α is found due to the presence of the masses. Namely, it is found that the resonance frequency of the main vibration can be tuned to the reference frequency f 0 without varying the temperature characteristics. Then the quartz crystal resonators in FIGS. 44 and 45 are sealed in a housing in vacuum or in N 2 . The sealing in vacuum is suitable in case the electrical property of the resonator has priority; while the sealing in N 2 is suitable in case the workability has priority. FIG. 48 shows a perspective view of a coupling resonator unit obtained by the manufacturing method according to the present invention.
As illustrated, a coupling quartz crystal resonator with excellent frequency-temperature characteristics, small CI value, excellent shock resistance and easy mounting process is provided by molding the resonant portion and the supporting portions of the resonator in one piece by photolithography; improving the structure of the supporting portions; selecting the optimum side ratio; arranging the exciting electrodes on the overall or partial surfaces of the resonant portion of the resonator; depositing masses for adjusting the resonance frequency and the frequency-temperature characteristics on the resonant portion; and mounting the resonator on the pedestal. Accordingly the coupling quartz crystal resonator according to the present invention is suitable for use in various consumer products.
Further, the manufacturing method of the coupling resonator unit according to the present invention comprises the steps of: molding the external shape of the resonator by etching; mounting the resonator on the pedestal; mounting the pedestal on the lead wires; tuning the resonance frequency of the resonator to the reference frequency; and sealing the resonator. The present invention provides a coupling resonator unit with excellent temperature characteristics in which the resonance frequency of the main vibration is tuned to the reference frequency. Since the quartz crystal resonator is mounted on the pedestal, the resonator unit with improved workability and excellent shock resistance is provided. Further, the terminal electrodes are arranged on one side of the pedestal according to the present invention (two-terminal structure), the lead wires are easily mounted and the workability is improved. | A mounting is provided for a GT-cut, coupled mode piezoelectric resonator. The mount includes pedestals with recesses. Portions of the resonator are mounted in the recesses. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of copending application Ser. No. 695,500 filed Jan. 28, 1985 now U.S. Pat. No. 4,564,385 which is a continuation-in-part of copending application Ser. No. 373,815, filed Apr. 30, 1982 now abandoned, which is a division of application Ser. No. 136,171 filed Apr. 15, 1980, now U.S. Pat. No. 4,344,789, which is a continuation-in-part of application Ser. No. 38,043 filed May 11, 1979, since abandoned.
FIELD OF THE INVENTION
This invention relates to certain substituted diphenyl ether oxime derivatives and to the use of same to control the growth of noxious plants, i.e., weeds.
DESCRIPTION OF THE INVENTION
This invention provides herbicidally active substituted diphenyl ether oxime compounds represented by the Formula I: ##STR1## wherein: X and Y are the same or different halogen;
Z is nitro, halogen or cyano;
R is hydrogen, halogen, C 1 to C 4 alkyl or haloalkyl, C 1 to C 4 alkoxy or alkylthio, or mono or dialkylamino;
R 1 is hydrogen, or C 1 to C 4 alkyl;
R 2 is hydrogen or C 1 to C 10 alkyl, haloalkyl or alkoxyalkyl; and
n is 0, 1, 2 or 3.
It is, of course, understood that agronomically acceptable salts of the Formula I compounds are within the scope of this invention, e.g., compounds wherein R 2 is an alkali metal ion, ammonium or substituted ammonium ion. Stereo and optical isomers of the Formula I compounds are also included.
Suitable alkyl radicals of which the various `R` groups are representative include methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl or iso-butyl. Chloromethyl, chloroethyl, dichloroethyl, bromomethyl, bromoethyl, trifluoromethyl, trifluoroethyl, trichloromethyl and the like are exemplary haloalkyls. As examples of alkoxy and alkylthio radicals there may be mentioned methoxy, ethoxy, propoxy, methylthio, ethylthio or the like. Mono or dialkyl amino groups include methylamino, dimethylamino, methylethylamino, diethylamino or the like. Halogens represented by X, Y, and Z include bromine, chlorine or fluorine. Sodium, potassium or lithium, preferably sodium or potassium, are exemplary of alkali metal ion represented by R 2 .
Preferred compounds of the Formula I are those wherein X and Y are fluorine or chlorine; Z is nitro or halogen; R is alkyl or haloalkyl; R 1 is hydrogen; R 2 is alkyl or haloalkyl; and n is 0.
Compounds of the Formula I may be prepared using techniques known to and starting materials available to the art. For example, a Formula I compound may be prepared by a transoximation reaction between an appropriately substituted diphenyl ether ketone or aldehyde of the Formula II: ##STR2## wherein X, Y, Z and R are as previously defined, with an appropriately substituted aldoxime or ketoxime-O-alkanoic acid. ##STR3## wherein R 1 and R 2 and n are as previously defined and R 3 and R 4 are hydrogen or lower alkyl. The resulting diphenyl ether oxime-O-alkanoic acid may then be esterified by reaction with a suitably substituted alcohol.
The following Example is illustrative of the preparation of a certain compound of this invention.
EXAMPLE
Preparation of: 5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime-O-(acetic acid, methyl ester).
(a) A reactor was charged with 10.71 grams (1.05 equiv.) of m-hydroxyacetophenone and 75 milliliters of dimethyl sulfoxide. To this stirred mixture were added 12.42 grams (1.2 equiv.) of anhydrous potassium carbonate and then 16.2 grams (1.0 equiv.) of 3,4-difluoro-5-chlorobenzotrifluoride. This stirred mixture was heated for four hours at 59° C. and then poured into a mixture of 200 milliliters of toluene and 300 milliliters of water. After phase separation, the organic phase was washed consecutively with 100 milliliters of 2 percent aqueous sodium hydroxide and 10 percent aqueous sodium chloride. The washed organic phase was dried over anhydrous magnesium sulfate, filtered and stripped of solvent affording 23.62 grams of clear, yellow oil identified by spectral analyses as 3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)acetophenone.
(b) A reactor was charged with 20 grams (1.0 equiv.) of the acetophenone, prepared as described in paragraph (a), and 55 milliliters of concentrated sulfuric acid. This stirred mixture was cooled to -10° C. and 6.48 grams (1.2 equiv.) of a V/V mixture of 70 percent nitric acid, 29 percent sulfuric acid and 1.0 percent water was added over a period of 50 minutes, the temperature rising to 0° C. over the addition period. After stirring for one hour at 0° C. to -12° C., the mixture was poured into 500 grams of ice and extracted with 500 milliliters of methylene chloride. After phase separation, the organic phase was washed consecutively with 500 milliliters of water, 250 milliliters of 2 percent aqueous sodium hydroxide and 500 milliliters of water. The washed organic phase was dried over anhydrous magnesium sulfate, filtered and stripped of solvent affording 21.53 grams of tan solid which HPLC analysis showed to be a mixture (77.8 area %, 15.9 area %) of two major products. The solid was recrystalized in 100 milliliters of 95 percent ethanol affording 15.32 grams of a crystalline solid (melting at 118°-123° C., 99.1% purity) identified by spectral analyses as 5-(2-chloro-6-fluoro-4-trifluoro-methylphenoxy)-2-nitroacetophenone.
(c) A reactor was charged with 14.0 grams (1.0 equiv.) of the 2-nitroacetophenone, prepared as described in paragraph (b), 4.86 grams (1.2 equiv.) of aminooxyacetic acid.hemihydrochloride and 140 milliliters of methanol. The mixture was refluxed for about 6 hours and an additional 0.77 gram (0.2 equiv.) of aminooxyacetic acid.hemihydrochloride was added. After refluxing an additional 18 hours, the mixture was stripped of solvent and the residue was dissolved in 200 milliliters of methylene chloride. This solution was washed consecutively with 2 percent aqueous sodium hydroxide and 5 percent aqueous sodium chloride then dried over anhydrous magnesium sulfate. Filtration and removal of solvent afforded 16.92 grams of an orange-yellow oil which crystallized on standing (m.p. 85°-89° C.) identified by spectral analysis as the desired product, 5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime-O-(acetic acid, methyl ester).
Although preparation of a certain compound of the invention has been illustrated by the foregoing example, it is to be understood that other compounds of the invention may be readily prepared by those skilled in the art using the same or similar techniques and by varying the choice of starting materials.
Some examples of such other compounds of the invention are 5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime-O-(acetic acid, methyl ester); 5-(2,6-difluoro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime-O-(acetic acid, methyl ester); 5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime-O-(propionic acid, methyl ester); 5-(2,6-difluoro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime-O-(propionic acid, methyl ester); 5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitroacetophonenon oxime-O-(propionic acid, methyl ester) and the like.
Weed control in accordance with this invention is effected by application, either before or after emergence of weeds, of a herbicidally effective amount of a compound of this invention. It is, of course, to be understood that the term "a compound of this invention" also includes mixtures of such compounds.
The term "herbicidally effective amount" is that amount of a compound of this invention required to so injure or damage weeds such that the weeds are incapable of recovering following application. The quantity of a compound of this invention applied in order to exhibit a satisfactory herbicidal effect may vary over a wide range and depends on a variety of factors, such as, for example, hardiness of a particular weed species, extent of weed infestation, climatic conditions, soil conditions, method of application, and the like. Typically, less than one pound per acre of a compound of this invention would be expected to provide satisfactory weed control, although in some instances application rates in excess of one pound per acre; e.g., up to 5 or more pounds per acre might be required. Of course, the efficacy of a paticular compound against a particular weed species may readily be determined by routine laboratory or field testing in a manner well known to the art. It is expected that satisfactory weed control can be had at a rate of application in the range of 0.01 to 1.0 pound per acre.
Of course, a compound of this invention can be formulated according to routine methods with any of several known and commonly used herbicidal diluents, adjuvants and carriers. The formulations can contain liquid carriers and adjuvants such as organic solvents, as well as emulsifiers, stabilizers, dispersants, suspending agents, spreaders, penetrants, wetting agents and the like. Typical carriers utilized in dry formulations include clay, talc, diatomaceous earth, silica and the like. Preferred formulations are those in the form of wettable powders, flowables, dispersible granulates or aqueous emulsifiable concentrates which can be diluted with water at the site of application. Also, dry formulations such as granules, dusts, and the like, may be used.
When desired, a compound of this invention can be applied in combination with other herbicidal agents in an effort to achieve even broader vegetative control. Typical herbicides which can be conveniently combined with Formula I compound include atrazine, hexazinone, metribuzin, ametryn, cyanazine, cyprazine, prometon, prometryn, propazine, simazine, terbutryn, propham, alachlor, acifluorfen, bentazon, metolachlor and N,N-dialkyl thiocarbamates such as EPTC, butylate or vernolate. These, as well as other herbicides described, for example, in the Herbicide Handbook of the Weed Society of America, may be used in combination with a compound or compounds of the invention. Typically such formulations will contain from about 5 to about 95 percent by weight of a compound of this invention.
The herbicidal formulations contemplated herein can be applied by any of several methods known to the art. Generally, the formulation will be surface applied as an aqueous spray. Such application can be carried out by conventional ground equipment, or if desired, the sprays can be aerially applied. Soil incorporation of such surface applied herbicides is accomplished by natural leaching, and is, of course, facilitated by natural rainfall and melting snow. If desired, however, the herbicides can be incorporated into the soil by conventional tillage means.
The compound prepared as described in the Example was tested for herbicidal efficacy, against a variety of broadleaf and grassy weed species, under controlled laboratory conditions of light, humidity and temperature. A solvent solution of said compound was applied, both preemergence and postemergence, to test flats containing the various weed species, and herbicidal efficacy was determined by periodic visual inspection, after application of the compounds. Herbicidal efficacy was determined on a Numerical Injury Rating scale of from 0 (no injury) to 10 (all plants dead).
A NIR of 7 to 9 indicates sever injury; a NIR of 4 to 6 indicates moderate injury, i.e. plant growth is reduced to the extent that normal growth would be expected only under ideal conditions; and a NIR of 1 to 3 indicates slight injury.
The following table gives the preemergence and postemergence NIR for the compound prepared as described in the Example against each of the broadleaf and grassy weed species to which it was applied. The compound was applied at a rate of 0.5 pound per acre and the NIR was determined three weeks after application. The broadleaf (BL) weeds used in the test were coffeeweed (COFE), jimsonweed (JMWD), tall morningglory (MNGY), teaweed (TEAW), velvetleaf (VTLF), sicklepod (SKPD) and lambsquarter (LMBQ). The grassy weeds used in the test were barnyardgrass (BNGS), Johnsongrass (JNGS), wild oats (WOAT) and yellow foxtail (YLFX).
______________________________________ NIR Preemergence Postemergence______________________________________BL-Weeds:COFE 10 10JMWD 9 10MNGY 10 10TEAW 10 10VTLF 8 10SKPD 7 10LMBQ 10 --Average BL NIR 9.1 10GR-Weeds:BNGS 8 10JNGS 2 8WOAT 2 10YLFX 9 10Average GR NIR 5.2 9.5______________________________________
Basis these screening tests, compounds of this invention can be effectively used for preemergence or postemergence control of a wide variety of broadleaf and grassy weeds. Typical of the various species of vegetative growth that may be controlled, combated, or eliminated are, for example, annuals such as pigweed, lambsquarters, foxtail, crabgrass, wild mustard, field pennycress, ryegrass, goose grass, chickweed, wild oats, velvetleaf, purslane, barnyardgrass, smartweed, knotweed, cocklebur, kochia, medic, ragweed, hemp nettle, spurrey, pondweed, carpetweed, morningglory, ducksalad, cheatgrass, fall panicum, jimsonweed, witchgrass, watergrass, wild turnip, and similar annual grasses and weeds. Biennials that may be controlled include wild barley, campion, burdock, bull thistle, roundleaved mallow, purple star thistle and the like. Also controlled by the compounds of this invention are perennials such as quackgrass, Johnsongrass, Canada thistle, curly dock, filed chickweed, dandelion, Russian knapweed aster, horsetail ironweed, sesbania, cattail, wintercress, horsenettle, nutsedge, milkweed, sicklepod, and the like.
Also from the preliminary screening results it is believed that certain of the compounds of the invention, particularly the haloalkyl esters, have improved selectivity and soil persistence. In addition, the invention compounds could be used to effectively control weeds growing amongst crops such as wheat, oats, rice, barley, corn, soybeans, rice, peanuts and the like without causing significant damage to the growing crop.
Although the invention has been described in considerable detail by the foregoing, it is to be understood that many variations may be made therein by those skilled in the art without departing from the spirit and scope thereof as defined by the appended claims. | This invention relates to certain herbicidally active substituted diphenyl ether oxime derivatives, herbicidal compositions of the same and the use thereof for preemergence and postemergence control of noxious plants, i.e., weeds. | 2 |
RELATED APPLICATIONS
[0001] This application is a continuation of and claims priority to U.S. application Ser. No. 10/770966 filed on Feb. 3, 2004, which claims priority from U.S. application Ser. No. 10/134097 filed on Apr. 25, 2002, which in turn claims priority from U.S. Provisional Application No. 60/286803, filed Apr. 26, 2001. The entire disclosure of each of those applications is hereby incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The field of the invention relates generally to transmissions, and more particularly the invention relates to continuously variable transmissions.
[0004] 2. Description of the Related Art
[0005] The present invention relates to the field of continuously variable transmissions and includes several novel features and inventive aspects that have been developed and are improvements upon the prior art. In order to provide an infinitely variable transmission, various traction roller transmissions in which power is transmitted through traction rollers supported in a housing between torque input and output disks have been developed. In such transmissions, the traction rollers are mounted on support structures which, when pivoted, cause the engagement of traction rollers with the torque disks in circles of varying diameters depending on the desired transmission ratio.
[0006] However, the success of these traditional solutions has been limited. For example, in one solution, a driving hub for a vehicle with a variable adjustable transmission ratio is disclosed. This method teaches the use of two iris plates, one on each side of the traction rollers, to tilt the axis of rotation of each of the rollers. However, the use of iris plates can be very complicated due to the large number of parts that are required to adjust the iris plates during transmission shifting. Another difficulty with this transmission is that it has a guide ring that is configured to be predominantly stationary in relation to each of the rollers. Since the guide ring is stationary, shifting the axis of rotation of each of the traction rollers is difficult.
[0007] One improvement over this earlier design includes a shaft about which a driving member and a driven member rotate. The driving member and driven member are both mounted on the shaft and contact a plurality of power adjusters disposed equidistantly and radially about the shaft. The power adjusters are in frictional contact with both members and transmit power from the driving member to the driven member. A support member located concentrically over the shaft and between the power adjusters applies a force to keep the power adjusters separate so as to make frictional contact against the driving member and the driven member. A limitation of this design is the absence of means for generating an adequate axial force to keep the driving and driven members in sufficient frictional contact against the power adjusters as the torque load on the transmission changes. A further limitation of this design is the difficulty in shifting that results at high torque and very low speed situations as well as insufficient means for disengaging the transmission and coasting.
[0008] Therefore, there is a need for a continuously variable transmission with an improved power adjuster support and shifting mechanism, means of applying proper axial thrust to the driving and driven members for various torque and power loads, and means of disengaging and reengaging the clutch for coasting.
SUMMARY OF THE INVENTION
[0009] The systems and methods have several features, no single one of which is solely responsible for its desirable attributes. Without limiting the scope as expressed by the claims that follow, its more prominent features will now be discussed briefly. After considering this discussion, and particularly after reading the section entitled “Detailed Description of the Preferred Embodiments” one will understand how the features of the system and methods provide several advantages over traditional systems and methods.
[0010] In one aspect, a continuously variable transmission is disclosed having a longitudinal axis, and a plurality of speed adjusters. Each speed adjuster has a tiltable axis of rotation is located radially outward from the longitudinal axis. Also provided are a drive disk that is annularly rotatable about the longitudinal axis and also contacts a first point on each of the speed adjusters and a support member that is also annularly rotatable about the longitudinal axis. A bearing disk is provided that is annularly rotatable about the longitudinal axis as well, and at least two axial force generators. The axial force generators are located between the drive disk and the bearing disk and each axial force generator is configured to apply an axial force to the drive disk.
[0011] In another aspect, a bearing disk annularly rotatable about the longitudinal axis is disclosed along with a disengagement mechanism. The disengagement mechanism can be positioned between the bearing disk and the drive disk and is adapted to cause the drive disk to disengage the drive disk from the speed adjusters.
[0012] In yet another aspect, an output disk or rotatable hub shell is disclosed along with a bearing disk that is annularly rotatable about the longitudinal axis of the transmission. A support member is included that is annularly rotatable about the longitudinal axis as well, and is adapted to move toward whichever of the drive disk or the output disk is rotating more slowly.
[0013] In still another aspect, a linkage subassembly having a hook is disclosed, wherein the hook is attached to either the drive disk or the bearing disk. Included is a latch attached to either the drive disk or and the bearing disk.
[0014] In another aspect, a plurality of spindles having two ends is disclosed, wherein one spindle is positioned in the bore of each speed adjuster and a plurality of spindle supports having a platform end and spindle end is provided. Each spindle support is operably engaged with one of the two ends of one of the spindles. Also provided is a plurality of spindle support wheels, wherein at least one spindle support wheel is provided for each spindle support. Included are annular first and second stationary supports each having a first side facing the speed adjusters and a second side facing away from the speed adjusters. Each of the first and second stationary supports have a concave surface on the first side and the first stationary support is located adjacent to the drive disk and the second stationary support is located adjacent to the driven disk.
[0015] Also disclosed is a continuously variable transmission having a coiled spring that is positioned between the bearing disk and the drive disk.
[0016] In another aspect, a transmission shifting mechanism is disclosed comprising a rod, a worm screw having a set of external threads, a shifting tube having a set of internal threads, wherein a rotation of the shifting tube causes a change in the transmission ratio, a sleeve having a set of internal threads, and a split shaft having a threaded end.
[0017] In yet another aspect, a remote transmission shifter is disclosed comprising a rotatable handlegrip, a tether having a first end and a second end, wherein the first end is engaged with the handlegrip and the second end is engaged with the shifting tube. The handlegrip is adapted to apply tension to the tether, and the tether is adapted to actuate the shifting tube upon application of tension.
[0018] These and other improvements will become apparent to those skilled in the art as they read the following detailed description and view the enclosed figures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIG. 1 is a cutaway side view of an embodiment of the transmission.
[0020] FIG. 2 is a partial end cross-sectional view taken on line II-II of FIG. 1 .
[0021] FIG. 3 is a perspective view of a split shaft and two stationary supports of the transmission of FIG. 1 .
[0022] FIG. 4 is a schematic cutaway side view of the transmission of FIG. 1 shifted into low.
[0023] FIG. 5 is a schematic cutaway side view of the transmission of FIG. 1 shifted into high.
[0024] FIG. 6 is a schematic side view of a ramp bearing positioned between two curved ramps of the transmission of FIG. 1 .
[0025] FIG. 7 is a schematic side view of a ramp bearing positioned between two curved ramps of the transmission of FIG. 1 .
[0026] FIG. 8 is a schematic side view of a ramp bearing positioned between two curved ramps of the transmission of FIG. 1 .
[0027] FIG. 9 is a perspective view of the power adjuster sub-assembly of the transmission of FIG. 1 .
[0028] FIG. 10 is a cutaway perspective view of the shifting sub-assembly of the transmission of FIG. 1 .
[0029] FIG. 11 is a perspective view of a stationary support of the transmission of FIG. 1 .
[0030] FIG. 12 is a perspective view of the screw and nut of the transmission of FIG. 1 .
[0031] FIG. 13 is a schematic perspective view of the frame support of the transmission of FIG. 1 .
[0032] FIG. 14 is a partial cutaway perspective view of the central ramps of the transmission of FIG. 1 .
[0033] FIG. 15 is a perspective view of the perimeter ramps of the transmission of FIG. 1 .
[0034] FIG. 16 is a perspective view of the linkage sub-assembly of the transmission of FIG. 1 .
[0035] FIG. 17 is a perspective view of the disengagement mechanism sub-assembly of the transmission of FIG. 1 .
[0036] FIG. 18 is a perspective view of the handlegrip shifter of the transmission of FIG. 1 .
[0037] FIG. 19 is a cutaway side view of an alternative embodiment of the transmission of FIG. 1 .
[0038] FIG. 20 is a cutaway side view of yet another alternative embodiment of the transmission of FIG. 1 .
[0039] FIG. 21 is a perspective view of the transmission of FIG. 20 depicting a torsional brace.
[0040] FIG. 22 is a perspective view of an alternative disengagement mechanism of the transmission of FIG. 1 .
[0041] FIG. 23 is another perspective view of the alternative disengagement mechanism of FIG. 22 .
[0042] FIG. 24 is a view of a sub-assembly of an alternative embodiment of the axial force generators of the transmission of FIG. 20 .
[0043] FIG. 25 is a schematic cross sectional view of the splines and grooves of the axial force generators of FIG. 24 .
[0044] FIG. 26 is a perspective view of an alternative disengagement mechanism of the transmission of FIG. 1 .
[0045] FIG. 27 is a perspective view of the alternative disengagement mechanism of FIG. 26 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0046] Embodiments of the invention will now be described with reference to the accompanying figures, wherein like numerals refer to like elements throughout. The terminology used in the description presented herein is not intended to be interpreted in any limited or restrictive manner simply because it is being utilized in conjunction with a detailed description of certain specific embodiments of the invention. Furthermore, embodiments of the invention may include several novel features, no single one of which is solely responsible for its desirable attributes or which is essential to practicing the inventions herein described.
[0047] The transmissions described herein are of the type that utilize speed adjuster balls with axes that tilt as described in U.S. patent application Ser. No. 09/695,757, filed on Oct. 24, 2000 and the information disclosed in that application is hereby incorporated by reference for all that it discloses. A drive (input) disk and a driven (output) disk are in contact with the speed adjuster balls. As the balls tilt on their axes, the point of rolling contact on one disk moves toward the pole or axis of the ball, where it contacts the ball at a circle of decreasing diameter, and the point of rolling contact on the other disk moves toward the equator of the ball, thus contacting the disk at a circle of increasing diameter. If the axis of the ball is tilted in the opposite direction, the disks respectively experience the converse situation. In this manner, the ratio of rotational speed of the drive disk to that of the driven disk, or the transmission ratio, can be changed over a wide range by simply tilting the axes of the speed adjuster balls.
[0048] With reference to the longitudinal axis of embodiments of the transmission, the drive disk and the driven disk can be located radially outward from the speed adjuster balls, with an idler-type generally cylindrical support member located radially inward from the speed adjuster balls, so that each ball makes three-point contact with the inner support member and the outer disks. The drive disk, the driven disk, and the support member can all rotate about the same longitudinal axis. The drive disk and the driven disk can be shaped as simple disks or can be concave, convex, cylindrical or any other shape, depending on the configuration of the input and output desired. The rolling contact surfaces of the disks where they engage the speed adjuster balls can have a flat, concave, convex or other profile, depending on the torque and efficiency requirements of the application.
[0049] Referring to FIGS. 1 and 2 , an embodiment of a continuously variable transmission 100 is disclosed. The transmission 100 is shrouded in a hub shell 40 , which functions as an output disk and is desirable in various applications, including those in which a vehicle (such as a bicycle or motorcycle) has the transmission contained within a driven wheel. The hub shell 40 can, in certain embodiments, be covered by a hub cap 67 . At the heart of the transmission 100 are a plurality of speed adjusters 1 that can be spherical in shape and are circumferentially spaced more or less equally or symmetrically around the centerline, or axis of rotation, of the transmission 100 . In the illustrated embodiment, eight speed adjusters 1 are used. However, it should be noted that more or fewer speed adjusters 1 can be used depending on the use of the transmission 100 . For example, the transmission may include 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or more speed adjusters. The provision for more than 3, 4, or 5 speed adjusters can provide certain advantages including, for example, widely distributing the forces exerted on the individual speed adjusters 1 and their points of contact with other components of the transmission 100 . Certain embodiments in applications with low torque but a high transmission ratio can use few speed adjusters 1 but large speed adjusters 1 , while certain embodiments in applications where high torque and a transmission high transmission ratio can use many speed adjusters 1 and large speed adjusters 1 . Other embodiments in applications with high torque and a low transmission ratio can use many speed adjusters 1 and small speed adjusters 1 . Finally, certain embodiments in applications with low torque and a low transmission ratio may use few speed adjusters 1 and small speed adjusters 1 .
[0050] Spindles 3 are inserted through holes that run through the center of each of the speed adjusters 1 to define an axis of rotation for each of the speed adjusters 1 . The spindles 3 are generally elongated shafts about which the speed adjusters 1 rotate, and have two ends that extend out of either end of the hole through the speed adjusters 1 . Certain embodiments will have cylindrical shaped spindles 3 , though any shape can be used. The speed adjusters 1 are mounted to freely rotate about the spindles 3 . In FIG. 1 , the axes of rotation of the speed adjusters 1 are shown in an approximately horizontal direction (i.e., parallel to the main axis of the transmission 100 ).
[0051] FIGS. 1, 4 and 5 , can be utilized to describe how the axes of the speed adjusters 1 can be tilted in operation to shift the transmission 100 . FIG. 4 depicts the transmission 100 shifted into a low transmission ratio, or low, while FIG. 5 depicts the transmission 100 shifted into a high transmission ratio, or high. Now also referring to FIGS. 9 and 10 , a plurality of spindle supports 2 are attached to the spindles 3 near each of the ends of the spindles 3 that extend out of the holes bored through the speed adjusters 1 , and extend radially inward from those points of attachment toward the axis of the transmission 100 . In one embodiment, each of the spindle supports 2 has a through bore that receives one end of one of the spindles 3 . The spindles 3 preferably extend through and beyond the spindle supports 2 such that they have an exposed end. In the embodiments illustrated, the spindles 3 advantageously have spindle rollers 4 coaxially and slidingly positioned over the exposed ends of the spindles 3 . The spindle rollers 4 are generally cylindrical wheels fixed axially on the spindles 3 outside of and beyond the spindle supports 2 and rotate freely about the spindles 3 . Referring also to FIG. 11 , the spindle rollers 4 and the ends of the spindles 3 fit inside grooves 6 that are cut into a pair of stationary supports 5 a, 5 b.
[0052] Referring to FIGS. 4, 5 and 11 , the stationary supports 5 a, 5 b are generally in the form of parallel disks annularly located about the axis of the transmission on either side of the power adjusters 1 . As the rotational axes of the speed adjusters 1 are changed by moving the spindle supports 2 radially out from the axis of the transmission 100 to tilt the spindles 3 , each spindle roller 4 fits into and follows a groove 6 cut into one of the stationary supports 5 a, 5 b. Any radial force, not rotational but a transaxial force, the speed adjusters 1 may apply to the spindles 3 is absorbed by the spindles 3 , the spindle rollers 4 and the sides 81 of the grooves 6 in the stationary supports 5 a, 5 b. The stationary supports 5 a, 5 b are mounted on a pair of split shafts 98 , 99 positioned along the axis of the transmission 100 . The split shafts 98 , 99 are generally elongated cylinders that define a substantial portion of the axial length of the transmission 100 and can be used to connect the transmission 100 to the object that uses it. Each of the split shafts 98 , 99 has an inside end near the middle of the transmission 100 and an outside end that extends out of the internal housing of the transmission 100 . The split shafts 98 , 99 are preferably hollow so as to house other optional components that may be implemented. The stationary supports 5 a, 5 b, each have a bore 82 , through which the split shafts 98 , 99 are inserted and rigidly attached to prevent any relative motion between the split shafts 98 , 99 and the stationary supports 5 a, 5 b. The stationary supports 5 a, 5 b are preferably rigidly attached to the ends of the split shafts 98 , 99 closest to the center of the transmission 100 . A stationary support nut 90 may be threaded over the split shaft 99 and tightened against the stationary support 5 b on corresponding threads of the stationary support 5 a, 5 b. The grooves 6 in the stationary supports 5 a, 5 b referred to above, extend from the outer circumference of the stationary supports 5 a, 5 b radially inwardly towards the split shafts 98 , 99 . In most embodiments, the groove sides 81 of the grooves 6 are substantially parallel to allow the spindle rollers 4 to roll up and down the groove sides 81 as the transmission 100 is shifted. Also, in certain embodiments, the depth of the grooves 6 is substantially constant at the circumference 9 of the stationary supports 5 a, 5 b, but the depth of the grooves 6 becomes shallower at points 7 closer to the split shaft 98 , 99 , to correspond to the arc described by the ends of the spindles 3 as they are tilted, and to increase the strength of the stationary supports 5 a, 5 b. As the transmission 100 is shifted to a lower or higher transmission ratio by changing the rotational axes of the speed adjusters 1 , each one of the pairs of spindle rollers 4 , located on the opposite ends of a single spindle 3 , move in opposite directions along their corresponding grooves 6 .
[0053] Referring to FIGS. 9 and 11 , stationary support wheels 30 can be attached to the spindle supports 2 with stationary support wheel pins 31 or by any other attachment method. The stationary support wheels 30 are coaxially and slidingly mounted over the stationary support wheel pins 31 and secured with standard fasteners, such as ring clips for example. In certain embodiments, one stationary support wheel 30 is positioned on each side of a spindle 2 with enough clearance to allow the stationary support wheels 30 to roll radially on concave surfaces 84 of the stationary supports 5 a, 5 b when the transmission 100 is shifted. In certain embodiments, the concave surfaces 84 are concentric with the center of the speed adjusters 1 .
[0054] Referring to FIGS. 2, 3 , and 11 , a plurality of elongated spacers 8 are distributed radially about, and extend generally coaxially with, the axis of the transmission. The elongated spacers 8 connect the stationary supports 5 a to one another to increase the strength and rigidity of the internal structure of the transmission 100 . The spacers 8 are oriented generally parallel to one another, and in some embodiments, each one extends from a point at one stationary support 5 a near the outer circumference to a corresponding point on the other stationary support 5 b. The spacers 8 can also precisely fix the distance between the stationary supports 5 a, 5 b, align the grooves 6 of the stationary supports 5 a, 5 b, ensure that the stationary supports 5 a, 5 b are parallel, and form a connection between the split shafts 98 , 99 . In one embodiment, the spacers 8 are pressed through spacer holes 46 in the stationary supports 5 a, 5 b. Although eight spacers 8 are illustrated, more or less spacers 8 can be used. In certain embodiments, the spacers 8 are located between two speed adjusters 1 .
[0055] Referring to FIGS. 1, 3 , and 13 , the stationary support 5 a, in certain embodiments, is rigidly attached to a stationary support sleeve 42 located coaxially around the split shaft 98 , or alternately, is otherwise rigidly attached to or made an integral part of the split shaft 98 . The stationary sleeve 42 extends through the wall of the hub shell 40 and attaches to a frame support 15 . In some embodiments, the frame support 15 fits coaxially over the stationary sleeve 42 and is rigidly attached to the stationary sleeve 42 . The frame support 15 uses a torque lever 43 , in some embodiments, to maintain the stationary position of the stationary sleeve 42 . The torque lever 43 provides rotational stability to the transmission 100 by physically connecting the stationary sleeve 42 , via the frame support 15 , and therefore the rest of the stationary parts to a fixed support member of the item to which the transmission 100 is to be mounted. A torque nut 44 threads onto the outside of the stationary sleeve 42 to hold the torque lever 43 in a position that engages the frame support 15 . In certain embodiments, the frame support 15 is not cylindrical so as to engage the torque lever 43 in a positive manner thereby preventing rotation of the stationary sleeve 42 .
[0056] For example, the frame support 15 could be a square of thickness equal to the torque lever 43 with sides larger than the stationary sleeve and with a hole cut out of its center so that the square may fit over the stationary sleeve 42 , to which it may then be rigidly attached. Additionally, the torque lever 43 could be a lever arm of thickness equal to that of the frame support 15 with a first end near the frame support 15 and a second end opposite the first. The torque lever 43 , in some embodiments, also has a bore through one of its ends, but this bore is a square and is a slightly larger square than the frame support 15 so the torque lever 43 could slide over the frame support 15 resulting in a rotational engagement of the frame support 15 and the torque lever 43 . Furthermore, the lever arm of the torque lever 43 is oriented so that the second end extends to attach to the frame of the bike, automobile, tractor or other application that the transmission 100 is used upon, thereby countering any torque applied by the transmission 100 through the frame support 15 and the stationary sleeve 42 . A stationary support bearing 48 fits coaxially around the stationary sleeve 42 and axially between the outside edge of the hub shell 40 and the torque lever 43 . The stationary support bearing 48 supports the hub shell 40 , permitting the hub shell 40 to rotate relative to the stationary support sleeve 42 .
[0057] Referring to FIGS. 1 and 10 , in some embodiments, shifting is manually activated by rotating a rod 10 , positioned in the hollow split shaft 98 . A worm screw 11 , a set of male threads in some embodiments, is attached to the end of the rod 10 that is in the center of the transmission 100 , while the other end of the rod 10 extends axially to the outside of the transmission 100 and has male threads affixed to its outer surface. In one embodiment, the worm screw 11 is threaded into a coaxial sleeve 19 with mating threads, so that upon rotation of the rod 10 and worm screw 11 , the sleeve 19 moves axially. The sleeve 19 is generally in the shape of a hollow cylinder that fits coaxially around the worm screw 11 and rod 10 and has two ends, one near stationary support 5 a and one near stationary support 5 b. The sleeve 19 is affixed at each end to a platform 13 , 14 . The two platforms 13 , 14 are each generally of the form of an annular ring with an inside diameter, which is large enough to fit over and attach to the sleeve 19 , and is shaped so as to have two sides. The first side is a generally straight surface that dynamically contacts and axially supports the support member 18 via two sets of contact bearings 17 a, 17 b. The second side of each platform 13 , 14 is in the form of a convex surface. The platforms 13 , 14 are each attached to one end of the outside of the sleeve 19 so as to form an annular trough around the circumference of the sleeve 19 . One platform 13 is attached to the side nearest stationary support 5 a and the other platform 14 is attached to the end nearest stationary support 5 b. The convex surface of the platforms 13 , 14 act as cams, each contacting and pushing multiple shifting wheels 21 . To perform this camming function, the platforms 13 , 14 preferably transition into convex curved surfaces 97 near their perimeters (farthest from the split shafts 98 , 99 ), that may or may not be radii. This curve 97 contacts with the shifting wheels 21 so that as the platforms 13 , 14 move axially, a shifting wheel 21 rides along the platform 13 , 14 surface in a generally radial direction forcing the spindle support 2 radially out from, or in toward, the split shaft 98 , 99 , thereby changing the angle of the spindle 3 and the rotation axis of the associated speed adjuster 1 . In certain embodiments, the shifting wheels 21 fit into slots in the spindle supports 2 at the end nearest the centerline of the transmission 100 and are held in place by wheel axles 22 .
[0058] Still referring to FIGS. 1 and 10 , a support member 18 is located in the trough formed between the platforms 13 , 14 and sleeve 19 , and thus moves in unison with the platforms 13 , 14 and sleeve 19 . In certain embodiments, the support member 18 is generally of one outside diameter and is generally cylindrical along the center of its inside diameter with a bearing race on each edge of its inside diameter. In other embodiments, the outer diameter of the support member 18 can be non-uniform and can be any shape, such as ramped or curved. The support member 18 has two sides, one near one of the stationary supports Sa and one near the other stationary support 5 b. The support member 18 rides on two contact bearings 17 a, 17 b to provide rolling contact between the support member 18 and the sleeve 19 . The contact bearings 17 a, 17 b are located coaxially around the sleeve 19 where the sleeve 19 intersects the platforms 13 , 14 allowing the support member 18 to freely rotate about the axis of the transmission 100 . The sleeve 19 is supported axially by the worm screw 11 and the rod 10 and therefore, through this configuration, the sleeve 19 is able to slide axially as the worm screw 11 positions it. When the transmission 100 is shifted, the sleeve 19 moves axially, and the bearings 17 a, 17 b, support member 18 , and platforms 13 , 14 , which are all attached either dynamically or statically to the sleeve, move axially in a corresponding manner.
[0059] In certain embodiments, the rod 10 is attached at its end opposite the worm screw 11 to a shifting tube 50 by a rod nut 51 , and a rod flange 52 . The shifting tube 50 is generally in the shape of a tube with one end open and one end substantially closed. The open end of shifting tube 50 is of a diameter appropriate to fit over the end of the split shaft 98 that extends axially out of the center of the transmission 100 . The substantially closed end of the shifting tube 50 has a small bore through it so that the end of the rod 10 that is opposite of the worm screw 11 can pass through it as the shifting tube 50 is placed over the outside of the split shaft 98 . The substantially closed end of the shifting tube 50 can then be fixed in axial place by the rod nut 51 , which is fastened outside of the shifting tube 50 , and the rod flange 52 , which in turn is fastened inside of the shifting tube's 50 substantially closed end, respectively. The shifting tube 50 can, in some embodiments, be rotated by a cable 53 attached to the outside of the shifting tube 50 . The cable 53 , in these embodiments, is attached to the shifting tube 50 with a cable clamp 54 and cable screw 56 , and then wrapped around the shifting tube 50 so that when tension is applied to the cable 53 a moment is developed about the center of the axis of the shifting tube 50 causing it to rotate. The rotation of shifting tube 50 may alternately be caused by any other mechanism such as a rod, by hand rotation, a servo-motor or other method contemplated to rotate the rod 10 . In certain embodiments, when the cable 53 is pulled so that the shifting tube 50 rotates clockwise on the split shaft 98 , the worm screw 11 rotates clockwise, pulling the sleeve 19 , support member 18 and platforms 13 , 14 , axially toward the shifting tube 50 and shifting the transmission 100 towards a low transmission ratio. A worm spring 55 , as illustrated in FIG. 3 , that can be a conical coiled spring capable of producing compressive and torsional force, attached at the end of the worm screw 11 , is positioned between the stationary support 5 b and the platform 14 and resists the shifting of the transmission 100 . The worm spring 55 is designed to bias the shifting tube 50 to rotate so as to shift the transmission 100 towards a low transmission ratio in some embodiments and towards a high transmission ratio in other embodiments.
[0060] Referring to FIGS. 1, 10 , and 11 , axial movement of the platforms 13 , 14 , define the shifting range of the transmission 100 . Axial movement is limited by inside faces 85 on the stationary supports 5 a, 5 b, which the platforms 13 , 14 contact. At an extreme high transmission ratio, platform 14 contacts the inside face 85 on one of the stationary supports 5 a, 5 b, and at an extreme low transmission ratio, the platform 13 contacts the inside face 85 on the other one of the stationary supports 5 a, 5 b. In many embodiments, the curvature of the convex radii of the platforms 13 , 14 , are functionally dependant on the distance from the center of a speed adjuster 1 to the center of the wheel 21 , the radius of the wheel 21 , the distance between the two wheels 21 that are operably attached to each speed adjuster 1 , and the angle of tilt of the speed adjuster 1 axis.
[0061] Although a left hand threaded worm screw 11 is disclosed, a right hand threaded worm screw 11 , the corresponding right hand wrapped shifting tube 50 , and any other combination of components just described that is can be used to support lateral movement of the support member 18 and platforms 13 , 14 , can be used. Additionally, the shifting tube 50 can have internal threads that engage with external threads on the outside of the split shaft 98 . By adding this threaded engagement, the shifting tube 50 will move axially as it rotates about the split shaft 98 causing the rod 10 to move axially as well. This can be employed to enhance the axial movement of the sleeve 19 by the worm screw 11 so as to magnify the effects of rotating the worm screw 11 to more rapidly shift the gear ratio or alternatively, to diminish the effects of rotating the worm screw 11 so as to slow the shifting process and produce more accurate adjustments of the transmission 100 .
[0062] Referring to FIGS. 10 and 18 , manual shifting may be accomplished by use of a rotating handlegrip 132 , which can be coaxially positioned over a stationary tube, a handlebar 130 , or some other structural member. In certain embodiments, an end of the cable 53 is attached to a cable stop 133 , which is affixed to the rotating handlegrip 132 . In some embodiments, internal forces of the transmission 100 and the conical spring 55 tend to bias the shifting of the transmission towards a lower transmission ratio. As the rotating handlegrip 132 is rotated by the user, the cable 53 , which can be wrapped along a groove around the rotating handlegrip 132 , winds or unwinds depending upon the direction of rotation of the cable 53 , simultaneously rotating the shifting tube 50 and shifting the transmission 100 towards a higher transmission ratio. A set of ratchet teeth 134 can be circumferentially positioned on one of the two sides of the rotating handlegrip 132 to engage a mating set of ratchet teeth on a first side of a ratcheted tube 135 , thereby preventing the rotating handlegrip 132 from rotating in the opposite direction. A tube clamp 136 , which can bean adjustable screw allowing for variable clamping force, secures the ratcheted tube 135 to the handlebar 130 . When shifting in the opposite direction, the rotating handlegrip 132 , is forcibly rotated in the opposite direction toward a lower transmission ratio, causing the tube clamp 136 to rotate in unison with the rotating handlegrip 132 . A handlebar tube 137 , positioned proximate to the ratcheted tube 135 , on a side opposite the ratchet teeth 134 , is rigidly clamped to the handlebar 130 with a tube clamp 138 , thereby preventing disengagement of the ratcheted tube 135 from the ratchet teeth 134 . A non-rotating handlegrip 131 is secured to the handlebar 130 and positioned proximate to the rotating handlegrip 132 , preventing axial movement of the rotating handlegrip 132 and preventing the ratchet teeth 134 from becoming disengaged from the ratcheted tube 135 .
[0063] Now referring to embodiments illustrated by FIGS. 1, 9 , and 11 , a one or more stationary support rollers 30 can be attached to each spindle support 2 with a roller pin 31 that is inserted through a hole in each spindle support 2 . The roller pins 31 are of the proper size and design to allow the stationary support rollers 30 to rotate freely over each roller pin 31 . The stationary support rollers 30 roll along concave curved surfaces 84 on the sides of the stationary supports 5 a, 5 b that face the speed adjusters 1 . The stationary support rollers 30 provide axial support to prevent the spindle supports 2 from moving axially and also to ensure that the spindles 2 tilt easily when the transmission 100 is shifted.
[0064] Referring to FIGS. 1, 12 , 14 , and 17 , a three spoked drive disk 34 , located adjacent to the stationary support 5 b, partially encapsulates but generally does not contact the stationary support 5 b. The drive disk 34 may have two or more spokes or may be a solid disk. The spokes reduce weight and aid in assembly of the transmission 100 ine embodiments using them, however a solid disk can be used. The drive disk 34 has two sides, a first side that contacts with the speed adjusters 1 , and a second side that faces opposite of the first side. The drive disk 34 is generally an annular disk that fits coaxially over, and extends radially from, a set of female threads or nut 37 at its inner diameter. The outside diameter of the drive disk 34 is designed to fit within the hub shell 40 , if the hub shell 40 employed is the type that encapsulates the speed adjusters 1 and the drive disk 34 , and engages with the hub cap 67 . The drive disk 34 is rotatably coupled to the speed adjusters 1 along a circumferential bearing surface on the lip of the first side of the drive disk 34 . As mentioned above, some embodiments of the drive disk 34 have a set of female threads 37 , or a nut 37 , at its center, and the nut 37 is threaded over a screw 35 , thereby engaging the drive disk 34 with the screw 35 . The screw 35 is rigidly attached to a set of central screw ramps 90 that are generally a set of raised surfaces on an annular disk that is positioned coaxially over the split shaft 99 . The central screw ramps 90 are driven by a set of central drive shaft ramps 91 , which are similarly formed on a generally annular disk. The ramp surfaces of the central drive ramps 91 and the central screw ramps 90 can be linear, but can be any other shape, and are in operable contact with each other. The central drive shaft ramps 91 , coaxially and rigidly attached to the drive shaft 69 , impart torque and an axial force to the central screw ramps 90 that can then be transferred to the drive disk 34 . A central drive tension member 92 , positioned between the central drive shaft ramps 91 and the central screw ramps 90 , produces torsional and/or compressive force, ensuring that the central ramps 90 , 91 are in contact with one another.
[0065] Still referring to FIGS. 1, 12 , 14 , and 17 , the screw 35 , which is capable of axial movement, can be biased to move axially away from the speed adjusters 1 with an annular thrust bearing 73 that contacts a race on the side of the screw 35 that faces the speed adjusters 1 . An annular thrust washer 72 , coaxially positioned over the split shaft 99 , contacts the thrust bearing 73 and can be pushed by a pin 12 that extends through a slot in the split shaft 99 . A compression member 95 capable of producing a compressive force is positioned in the bore of the hollow split shaft 99 at a first end. The compression member 95 , which may be a spring, contacts the pin 12 on one end, and at a second end contacts the rod 10 . As the rod 10 is shifted towards a higher transmission ratio and moves axially, it contacts the compression member 95 , pushing it against the pin 12 . Internal forces in the transmission 100 will bias the support member 18 to move towards a high transmission ratio position once the transmission ratio goes beyond a 1:1 transmission ratio towards high and the drive disk 34 rotates more slowly than the hub shell 40 . This bias pushes the screw 35 axially so that it either disconnects from the nut 37 and no longer applies an axial force or a torque to the drive disk 34 , or reduces the force that the screw 35 applies to the nut 37 . In this situation, the percentage of axial force applied to the drive disk 34 by the perimeter ramps 61 increases. It should be noted that the internal forces of the transmission 100 will also bias the support member 18 towards low once the support member 18 passes beyond a position for a 1:1 transmission ratio towards low and the hub shell 40 rotates more slowly than the drive disk 34 . This beneficial bias assists shifting as rpm's drop and torque increases when shifting into low.
[0066] Still referring to FIGS. 1, 12 , 14 , and 17 , the drive shaft 69 , which is a generally tubular sleeve having two ends and positioned coaxial to the outside of the split shaft 99 , has at one end the aforementioned central drive shaft ramps 91 attached to it, while the opposite end faces away from the drive disk 34 . In certain embodiments, a bearing disk 60 is attached to and driven by the drive shaft 69 . The bearing disk 60 can be splined to the drive shaft 69 , providing for limited axial movement of the bearing disk 60 , or the bearing disk 60 can be rigidly attached to the drive shaft 69 . The bearing disk 60 is generally a radial disk coaxially mounted over the drive shaft 69 extending radially outward to a radius generally equal to that of the drive disk 34 . The bearing disk 60 is mounted on the drive shaft 69 in a position near the drive disk 34 , but far enough away to allow space for a set of perimeter ramps 61 , associated ramp bearings 62 , and a bearing race 64 , all of which are located between the drive disk 34 and the bearing disk 67 . In certain embodiments, the plurality of perimeter ramps 61 can be concave and are rigidly attached to the bearing disk 60 on the side facing the drive disk 34 . Alternatively, the perimeter ramps 61 can be convex or linear, depending on the use of the transmission 100 . Alternatively, the bearing race 64 , can be replaced by a second set of perimeter ramps 97 , which may also be linear, convex, or concave, and which are rigidly attached to the drive disk 34 on the side facing the bearing disk 60 . The ramp bearings 62 are generally a plurality of bearings matching in number the perimeter ramps 61 . Each one of the plurality of ramp bearings 62 is located between one perimeter ramp 61 and the bearing race 64 , and is held in its place by a compressive force exerted by the ramps 61 and also by a bearing cage 63 . The bearing cage 63 is an annular ring coaxial to the split shaft 99 and located axially between the concave ramps 61 and convex ramps 64 . The bearing cage 63 has a relatively large inner diameter so that the radial thickness of the bearing cage 63 is only slightly larger than the diameter of the ramp bearings 62 to house the ramp bearings 62 . Each of the ramp bearings 62 fits into a hole that is formed in the radial thickness of the bearing cage 63 and these holes, together with the previously mentioned compressive force, hold the ramp bearings 62 in place. The bearing cage 63 , can be guided into position by a flange on the drive disk 34 or the bearing disk 60 , which is slightly smaller than the inside diameter of the bearing cage 63 .
[0067] Referring to FIGS. 1, 6 , 7 , 8 , and 15 , the bearing disk 60 , the perimeter ramps 61 , and a ramp bearing 62 of one embodiment are depicted. Referring specifically to FIG. 6 , a schematic view shows a ramp bearing 62 contacting a concave perimeter ramp 61 , and a second convex perimeter ramp 97 . Referring specifically to FIG. 7 , a schematic view shows the ramp bearing 62 , the concave perimeter ramp 61 , and the second convex perimeter ramp 97 of FIG. 6 at a different torque or transmission ratio. The position of the ramp bearings 62 on the perimeter ramps 61 depicted in FIG. 7 produces less axial force than the position of the ramp bearings 62 on the perimeter ramps 61 depicted in FIG. 6 . Referring specifically to FIG. 8 , a ramp bearing 62 is shown contacting a convex perimeter ramp 61 , and a concave second perimeter ramp 97 in substantially central positions on those respective ramps. It should be noted that changes in the curves of the perimeter ramps 61 , 97 change the magnitude of the axial force applied to the power adjusters 1 at various transmission ratios, thereby maximizing efficiency in different gear ratios and changes in torque. Depending on the use for the transmission 100 , many combinations of curved or linear perimeter ramps 61 , 97 can be used. To simplify operation and reduce cost, in some applications one set of perimeter ramps may be eliminated, such as the second set of perimeter tramps 97 , which are then replaced by a bearing race 64 . To further reduce cost, the set of perimeter ramps 61 may have a linear inclination.
[0068] Referring to FIG. 1 , a coiled spring 65 having two ends wraps coaxially around the drive shaft 69 and is attached at one end to the bearing disk 60 and at its other end to the drive disk 34 . The coiled spring 65 provides force to keep the drive disk 34 in contact with the speed adjusters 1 and biases the ramp bearings 62 up the perimeter ramps 61 . The coiled spring 65 is designed to minimize the axial space within which it needs to operate and, in certain embodiments, the cross section of the coiled spring 65 is a rectangle with the radial length greater than the axial length.
[0069] Referring to FIG. 1 , the bearing disk 60 preferably contacts an outer hub cap bearing 66 on the bearing disk 60 side that faces opposite the concave ramps 61 . The outer hub cap bearing 66 can be an annular set of roller bearings located radially outside of, but coaxial with, the centerline of the transmission 100 . The outer hub cap bearing 66 is located radially at a position where it may contact both the hub cap 67 and the bearing disk 60 to allow their relative motion with respect to one another. The hub cap 67 is generally in the shape of a disk with a hole in the center to fit over the drive shaft 69 and with an outer diameter such that it will fit within the hub shell 40 . The inner diameter of the hub cap engages with an inner hub cap bearing 96 that is positioned between the hub cap 67 and the drive shaft 69 and maintains the radial and axial alignment of the hub cap 67 and the drive shaft 69 with respect to one another. The edge of the hub cap 67 at its outer diameter can be threaded so that the hub cap 67 can be threaded into the hub shell 40 to encapsulate much of the transmission 100 . A sprocket or pulley 38 or other drive train adapter, such as gearing for example, can be rigidly attached to the rotating drive shaft 69 to provide the input rotation. The drive shaft 69 is maintained in its coaxial position about the split shaft 99 by a cone bearing 70 . The cone bearing 70 is an annular bearing mounted coaxially around the split shaft 99 and allows rolling contact between the drive shaft 69 and the split shaft 99 . The cone bearing 70 may be secured in its axial place by a cone nut 71 which threads onto the split shaft 99 or by any other fastening method.
[0070] In operation of certain embodiments, an input rotation from the sprocket or pulley 38 is transmitted to the drive shaft 69 , which in turn rotates the bearing disk 60 and the plurality of perimeter ramps 61 causing the ramp bearings 62 to roll up the perimeter ramps 61 and press the drive disk 34 against the speed adjusters 1 . The ramp bearings 62 also transmit rotational energy to the drive disk 34 as they are wedged in between, and therefore transmit rotational energy between, the perimeter ramps 61 and the convex ramps 64 . The rotational energy is transferred from the drive disk 34 to the speed adjusters 1 , which in turn rotate the hub shell 40 providing the transmission 100 output rotation and torque.
[0071] Referring to FIG. 16 , a latch 115 rigidly attaches to the side of the drive disk 34 that faces the bearing disk 60 and engages a hook 114 that is rigidly attached to a first of two ends of a hook lever 113 . The engaging area under the latch 1 15 opening is larger than the width of the hook 114 and provides extra room for the hook 114 to move radially, with respect to the axis, within the confines of the latch 114 when the drive disk 34 and the bearing disk 60 move relative to each other. The hook lever 113 is generally a longitudinal support member for the hook 114 and at its second end, the hook lever 113 has an integral hook hinge 116 that engages with a middle hinge 119 via a first hinge pin 111 . The middle hinge 119 is integral with a first end of a drive disk lever 112 , a generally elongated support member having two ends. On its second end, the drive disk lever 112 has an integral drive disk hinge 117 , which engages a hinge brace 110 via the use of a second hinge pin 118 . The hinge brace 110 is generally a base to support the hook 114 , the hook lever 113 , the hook hinge 116 , the first hinge pin 111 , the middle hinge 119 , the drive disk lever 112 the second hinge pin 118 , and the drive disk hinge 117 , and it is rigidly attached to the bearing disk 60 on the side facing the drive disk 34 . When the latch 73 and hook 72 are engaged the ramp bearings 62 are prevented from rolling to an area on the perimeter ramps 61 that does not provide the correct amount of axial force to the drive disk 34 . This ensures that all rotational force applied to the ramp bearings 62 by perimeter ramps 61 is transmitted to the drive disk 34 .
[0072] Referring to FIGS. 1 and 17 , a disengagement mechanism for one embodiment of the transmission 100 is described to disengage the drive disk 34 from the speed adjusters 1 in order to coast. On occasions that input rotation to the transmission 100 ceases, the sprocket or pulley 38 stops rotating but the hub shell 40 and the speed adjusters 1 can continue to rotate. This causes the drive disk 34 to rotate so that the set of female threads 37 in the bore of the drive disk 34 wind onto the male threaded screw 35 , thereby moving the drive disk 34 axially away from the speed adjusters 1 until the drive disk 34 no longer contacts the speed adjusters 1 . A toothed rack 126 , rigidly attached to the drive disk 34 on the side facing the bearing disk 60 , has teeth that engage and rotate a toothed wheel 124 as the drive disk 34 winds onto the screw 35 and disengages from the power adjusters 1 . The toothed wheel 124 , has a bore in its center, through which a toothed wheel bushing 121 is located, providing for rotation of the toothed wheel 124 . Clips 125 that are coaxially attached over the toothed wheel bushing 121 secure the toothed wheel 124 in position, although any means of fastening may be used. A preloader 120 , coaxially positioned over and clamped to the central drive shaft ramps 91 , extends in a direction that is radially outward from the center of the transmission 100 . The preloader 120 , of a resilient material capable of returning to its original shape when flexed, has a first end 128 and a second end 127 . The first end of the preloader 128 extends through the toothed wheel bushing 121 and terminates in the bearing cage 63 . The first end of the preloader 128 biases the bearing cage 63 and ramp bearings 62 up the ramps 61 , ensuring contact between the ramp bearings 62 and the ramps 61 , and also biases the toothed wheel 124 against the toothed rack 126 . A pawl 123 , engages the toothed wheel 124 , and in one embodiment engages the toothed wheel 124 on a side substantially opposite the toothed rack 126 . The pawl 123 has a bore through which a pawl bushing 122 passes, allowing for rotation of the pawl 123 . Clips 125 , or other fastening means secure the pawl 123 to the pawl bushing 121 . A pawl spring 122 biases rotation of the pawl 123 to engage the toothed wheel 124 , thereby preventing the toothed wheel 124 from reversing its direction of rotation when the drive disk 34 winds onto the screw 35 . The pawl bushing 121 is positioned over a second end of the preloader 127 , which rotates in unison with the drive shaft 69 .
[0073] Referring again to FIG. 1 , a coiled spring 65 , coaxial with and located around the drive shaft 69 , is located axially between and attached by pins or other fasteners (not shown) to both the bearing disk 60 at one end and drive disk 34 at the other end. In certain embodiments, the coiled spring 65 replaces the coiled spring of the prior art so as to provide more force and take less axial space in order to decrease the overall size of the transmission 100 . In some embodiments, the coiled spring 65 is produced from spring steel wire with a rectangular profile that has a radial length or height greater than its axial length or width. During operation of the transmission 100 , the coiled spring 65 ensures contact between the speed adjusters 1 and the drive disk 34 . However, once the drive disk 34 has disengaged from the speed adjusters 1 , the coiled spring 65 is prevented from winding the drive disk 34 so that it again contacts the speed adjusters 1 by the engagement of the toothed wheel 124 and the pawl 123 . When the input sprocket, gear, or pulley 38 , resumes its rotation, the pawl 123 also rotates, allowing the toothed wheel 124 to rotate, thus allowing the drive disk 34 to rotate and unwind from the screw 35 due to the torsional force created by the coiled spring 65 . Relative movement between the pawl 123 and the toothed wheel 124 is provided by the fact that the first end of the preloader 128 rotates at approximately half the speed as the second end of the preloader 127 because the first end of the preloader 128 is attached to the bearing cage 63 . Also, because the ramp bearings 62 are rolling on the perimeter ramps 61 of the bearing disk 60 , the bearing cage 63 will rotate at half the speed as the bearing disk 60 .
[0074] Referring now to FIG. 19 , an alternative embodiment of the transmission 100 of FIG. 1 is disclosed. In this embodiment, an output disk 201 replaces the hub shell 40 of the transmission 100 illustrated in FIG. 1 . Similar to the drive disk 34 , the output disk 201 contacts, and is rotated by, the speed adjusters 1 . The output disk 201 is supported by an output disk bearing 202 that contacts both the output disk 201 and a stationary case cap 204 . The case cap 204 is rigidly attached to a stationary case 203 with case bolts 205 or any other fasteners. The stationary case 203 can be attached to a non-moving object such as a frame or to the machine for which its use is employed. A gear, sprocket, or pulley 206 is attached coaxially over and rigidly to the output disk 201 outside of the case cap 204 and stationary case 203 . Any other type of output means can be used however, such as gears for example. A torsional brace 207 can be added that rigidly connects the split shaft 98 to the case cap 204 for additional support.
[0075] Referring now to FIGS. 20 and 21 , an alternative embodiment of the transmission 100 of FIG. 1 is disclosed. A stationary support race 302 is added on a side of stationary support 5 a facing away from the speed adjusters 1 and engages with a stationary support bearing 301 and a rotating hub shell race 303 to maintain correct alignment of the stationary support 5 a with respect to the rotating hub shell 40 . A torsional brace 304 is rigidly attached to the stationary support 5 a and can then be rigidly attached to a stationary external component to prevent the stationary supports 5 a, 5 b from rotating during operation of the transmission 300 . A drive shaft bearing 306 is positioned at an end of the drive shaft 69 facing the speed adjusters 1 and engages a drive shaft race 307 formed in the same end of the drive shaft 69 and a split shaft race 305 formed on a radially raised portion of the split shaft 99 to provide additional support to the drive shaft 69 and to properly position the drive shaft 69 relative to the stationary supports 5 a, 5 b.
[0076] Referring now to FIGS. 22 and 23 , an alternative disengagement mechanism 400 of the transmission 100 of FIG. 1 is disclosed. A toothed wheel 402 is coaxially positioned over a wheel bushing 408 and secured in position with a clip 413 or other fastener such that it is capable of rotation. The wheel bushing 408 is coaxially positioned over the first end of a preloader 405 having first and second ends (both not separately identified in FIGS. 22 , and 23 ). The preloader 405 clamps resiliently around the central drive shaft ramps 91 . The first end of the preloader 405 extends into the bearing cage 63 , biasing the bearing cage 63 up the perimeter ramps 61 . Also positioned over the wheel bushing 408 is a lever 401 that rotates around the wheel bushing 408 and that supports a toothed wheel pawl 411 and a pinion pawl 409 . The toothed wheel pawl 411 engages the toothed wheel 402 to control its rotation, and is positioned over a toothed wheel bushing 414 that is pressed into a bore in the lever 401 . A toothed wheel pawl spring 412 biases the toothed wheel pawl 411 against the toothed wheel 402 . The pinion pawl 409 , positioned substantially opposite the toothed wheel pawl 411 on the lever 401 , is coaxially positioned over a pinion pawl bushing 415 that fits into another bore in the lever 401 and provides for rotational movement of the pinion pawl 409 . A pinion pawl spring 410 biases the pinion pawl 409 against a pinion 403 .
[0077] Referring now to FIGS. 1, 22 and 23 , the pinion 403 has a bore at its center and is coaxially positioned over a first of two ends of a rod lever 404 . The rod lever is an elongated lever that engages the pinion pawl 409 during coasting until input rotation of the sprocket, pulley, or gear 38 resumes. A bearing disk pin 406 that is affixed to the bearing disk 60 contacts a second end of the rod lever 404 , upon rotation of the bearing disk 60 , thereby pushing the rod lever 404 against a drive disk pin 407 , which is rigidly attached to the drive disk 34 . This action forces the first end of the rod lever 404 to swing away from the toothed wheel 402 , temporarily disconnecting the pinion 403 from the toothed wheel 402 , allowing the toothed wheel 402 to rotate. A lever hook 401 is attached to the the lever 401 and contacts a latch (not shown) on the drive disk 34 and is thereby pushed back as the coiled spring 65 biases the drive disk 34 to unwind and contact the speed adjusters 1 . During occasions that the input rotation of the sprocket, pulley, or gear 38 ceases, and the speed adjusters 1 continue to rotate, the drive disk 34 winds onto the screw 35 and disengages from the speed adjusters 1 . As the drive disk 34 rotates, the drive disk pin 407 disengages from the rod lever 404 , which then swings the pinion 403 into contact with the toothed wheel 402 , preventing the drive disk 34 from re-engaging the speed adjusters 1 .
[0078] Referring to FIGS. 24 and 25 , a sub-assembly of an alternative set of axial force generators 500 of the transmission 300 of FIG. 20 is disclosed. When rotated by the input sprocket, gear, or pulley 38 , a splined drive shaft 501 rotates the bearing disk 60 , which may have grooves 505 in its bore to accept and engage the splines 506 of the splined drive shaft 501 . The central drive shaft ramps 508 are rigidly attached to the bearing disk 60 or the splined drive shaft 501 and rotate the central screw ramps 507 , both of which have bores that clear the splines 506 of the splined drive shaft 501 . The central tension member 92 (illustrated in FIG. 1 ) is positioned between the central drive shaft ramps 508 and the central screw ramps 507 . A grooved screw 502 having a grooved end and a bearing end is rotated by the central screw ramps 90 and has grooves 505 on its bearing end that are wider than the splines 506 on the splined drive shaft 501 to provide a gap between the splines 506 and the grooves 505 . This gap between the splines 506 and the grooves 505 allows for relative movement between the grooved screw 502 and/or bearing disk 60 and the splined drive shaft 501 . On occasions when the grooved screw 502 is not rotated by the central drive shaft ramps 508 and the central screw ramps 507 , the splines 506 of the splined drive shaft 501 contact and rotate the grooves 505 on the grooved screw 502 , thus rotating the grooved screw 502 . An annular screw bearing 503 contacts a race on the bearing end of the grooved screw 502 and is positioned to support the grooved screw 502 and the splined drive shaft 501 relative to the axis of the split shaft 99 . The bore of the grooved screw 502 is slightly larger than the outside diameter of the splined drive shaft 501 to allow axial and rotational relative movement of the grooved screw 502 . A screw cone race 504 contacts and engages the annular screw bearing 503 and has a hole perpendicular to its axis to allow insertion of a pin 12 . The pin 12 engages the rod 10 , which can push on the pin 12 and move the grooved screw 502 axially, causing it to disengage from, or reduce the axial force that it applies to, the nut 37 .
[0079] Referring to FIG. 26 , an alternative disengagement means 600 of the disengagement means 400 of FIGS. 22 and 23 is disclosed. The lever 401 is modified to eliminate the T-shape used to mount both the pinion pawl 409 and the toothed wheel pawl 411 so that the new lever 601 has only the toothed wheel pawl 411 attached to it. A second lever 602 , having a first end and a second end. The pinion pawl 409 is operably attached to the first end of the second lever 602 . The second lever 602 has a first bore through which the first end of the preloader 405 is inserted. The second lever 602 is rotatably mounted over the first end of the preloader 405 . The second lever 602 has a second bore in its second end through which the second end of the preloader 603 is inserted. When rotation of the sprocket, gear, or pulley 38 ceases, the drive disk 34 continues to rotate forward and wind onto the screw 36 until it disengages from the speed adjusters 1 . The first end of the preloader 405 rotates forward causing the pinion pawl 409 to contact and rotate the pinion 403 clockwise. This causes the toothed wheel 402 to rotate counter-clockwise so that the toothed wheel pawl 411 passes over one or more teeth of the toothed wheel 402 , securing the drive disk 34 and preventing it from unwinding off of the screw 36 and contacting the speed adjusters 1 . When rotation of the sprocket, gear, or pulley 38 resumes, the second end of the preloader 603 rotates, contacting the second end of the second lever 602 causing the pinion pawl 409 to swing out and disengage from the pinion 403 , thereby allowing the drive disk 34 to unwind and reengage with the speed adjusters 1 .
[0080] With this description in place, some of the particular improvements and advantages of the present invention will now be described. Note that not all of these improvements are necessarily found in all embodiments of the invention.
[0081] Referring to FIG. 1 , a current improvement in some embodiments includes providing variable axial force to the drive disk 34 to respond to differing loads or uses. This can be accomplished by the use of multiple axial force generators. Axial force production can switch between a screw 35 and a nut 37 , with associated central drive shaft ramps 91 and screw ramps 90 , to perimeter ramps 61 , 64 . Or the screw 35 , central ramps 90 , 91 , and perimeter ramps 61 , 64 can share axial force production. Furthermore, axial force at the perimeter ramps 61 , 64 can be variable. This can be accomplished by the use of ramps of variable inclination and declination, including concave and convex ramps. Referring to FIG. 1 and FIGS. 6-8 and the previous detailed description, an embodiment is disclosed where affixed to the bearing disk 60 is a first set of perimeter ramps 61 , which may be concave, with which the ramp bearings 62 contact. Opposite the first set of perimeter ramps 61 are a second set of perimeter ramps 97 that are attached to the drive disk 34 , which may be convex, and which are in contact with the ramp bearings 62 . The use of concave and convex ramps to contact the ramp bearings 62 allows for non-linear increase or decrease in the axial load upon the drive disk 34 in response to adjustments in the position of the speed adjusters 1 and the support member 18 .
[0082] Another improvement of certain embodiments includes positively engaging the bearing disk 60 and the drive disk 34 to provide greater rotational transmission and constant axial thrust at certain levels of torque transmission. Referring to an embodiment illustrated in FIG. 1 as described above, this may be accomplished, for example, by the use of the hook 114 and latch 115 combination where the hook 114 is attached to the bearing cage 63 that houses the ramp bearings 62 between the drive disk 34 and the bearing disk 60 , and the latch 115 is attached to the drive disk 34 that engages with the hook 114 when the ramp bearings 62 reach their respective limit positions on the ramp faces. Although such configuration is provided for example, it should be understood that the hook 114 and the latch 115 may be attached to the opposite component described above or that many other mechanisms may be employed to achieve such positive engagement of the bearing disk 60 and the drive disk 34 at limiting positions of the ramp bearings 62 .
[0083] A further improvement of certain embodiments over previous designs is a drive disk 34 having radial spokes (not separately identified), reducing weight and aiding in assembly of the transmission 100 . In a certain embodiment, the drive disk 34 has three spokes equidistant from each other that allow access to, among other components, the hook 114 and the latch 115 .
[0084] Another improvement of certain embodiments includes the use of threads 35 , such as acme threads, to move the drive disk 34 axially when there is relative rotational movement between the drive disk 34 and the bearing disk 60 . Referring to the embodiment illustrated in FIG. 1 , a threaded male screw 35 may be threaded into a set of female threads 37 , or a nut 37 , in the bore of the drive disk 34 . This allows the drive disk 34 to disengage from the speed adjusters 1 when the drive disk 34 ceases to provide input torque, such as when coasting or rolling in neutral, and also facilitates providing more or less axial force against the speed adjusters 1 . Furthermore, the threaded male screw 35 is also designed to transmit an axial force to the drive disk 34 via the set of female threads 37 .
[0085] Yet another improvement of certain embodiments over past inventions consists of an improved method of shifting the transmission to higher or lower transmission ratios. Again, referring to the embodiment illustrated in FIG. 1 , this method can be accomplished by using a threaded rod 10 , including, for example, a left hand threaded worm screw 11 and a corresponding right hand threaded shifting tube 50 , or sleeve, that operates remotely by a cable 53 or remote motor or other remote means. Alternatively, left-handed threads can be used for both the worm screw 11 and the shifting tube, or a non-threaded shifting tube 50 could be used, and any combinations thereof can also be used as appropriate to affect the rate of shifting the transmission 100 with respect to the rate of rotation of the shifting tube 50 . Additionally, a conical spring 55 can be employed to assist the operator in maintaining the appropriate shifting tube 50 position. The worm screw 11 is preferably mated with a threaded sleeve 19 so as to axially align the support member 18 so that when the worm screw 11 is rotated the support member 18 will move axially.
[0086] Another improvement of some embodiments over past inventions is the disengagement mechanism for the transmission 100 . The disengagement mechanism allows the input sprocket, pulley, or gear 38 to rotate in reverse, and also allows the transmission 100 to coast in neutral by disengaging the drive disk 34 from the speed adjusters 1 .
[0087] The foregoing description details certain embodiments of the invention. It will be appreciated, however, that no matter how detailed the foregoing appears in text, the invention can be practiced in many ways. As is also stated above, it should be noted that the use of particular terminology when describing certain features or aspects of the invention should not be taken to imply that the terminology is being re-defined herein to be restricted to including any specific characteristics of the features or aspects of the invention with which that terminology is associated. The scope of the invention should therefore be construed in accordance with the appended claims and any equivalents thereof. | A continuously variable transmission is disclosed for use in rotationally or linearly powered machines and vehicles. The transmission provides a simple manual shifting method for the user. Further, the practical commercialization of traction roller transmissions requires improvements in the reliability, ease of shifting, function and simplicity of the transmission. The present invention includes a continuously variable transmission that may be employed in connection with any type of machine that is in need of a transmission. For example, the transmission may be used in (i) a motorized vehicle such as an automobile, motorcycle, or watercraft, (ii) a non-motorized vehicle such as a bicycle, tricycle, scooter, exercise equipment or (iii) industrial equipment, such as a drill press, power generating equipment, or textile mill. | 5 |
RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Application Serial No. 60/939,730, filed May 23, 2007, the entirety of which is incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] This invention relates to a method and an apparatus for hydrolysis treatment of cellulosic fiber material.
[0003] In conventional systems, wood chips (or other cellulosic or fiber material) can undergo hydrolysis in a single vessel prior to treatment or cooking in a digester, such as described in U.S. Pat. Nos. 3,380,883 and 3,413,189. In such systems, hydrolysis occurs under acidic conditions in the slurry of wood chips, e.g., cellulosic material, passing through a top section of the vessel with the continued treatment of cooking in lower sections of the vessel followed by washing in the bottom of the vessel. In the upper region of the vessel, hydrolysate, e.g., sugars such pentose and hexose, is extracted from wood chips and the hydrolysate is recovered.
[0004] Hydrolysis occurs throughout the upper region of the vessel by the introduction of steam, acid and/or water in a con-current flow in the upper region. In the lower region of the vessel, the cellulosic material is cooked and wash and is subsequently discharged as pulp from the vessel.
BRIEF DESCRIPTION OF THE INVENTION
[0005] A novel hydrolysis system has been developed for a pulping system. The hydrolysis and digesting of cellulosic material, e.g., wood chips, is performed in a single pressurized reactor vessel. The cellulosic material undergoes hydrolysis in an upper zone of the vessel. The hydrolysis takes place in the vessel at the vessel in the conditions of pH of 1 to 6, preferably 3 to 4, and at temperatures in a range of 150° C. to about 170° C., and preferably in a range of 160° C. to 170° C. Hydrolysate and liquids are removed from the reactor through an upper extraction screen in the vessel. A wash zone of the vessel is below the upper extraction screen and above the cooking zones of the vessel. Wash liquid flows upward through the wash zone and to an extraction screen. Wash liquid is also extracted from the vessel through a wash liquid extraction screen at the bottom of the wash zone.
[0006] The cool wash liquid reduces the temperature of the cellulosic material flowing through the wash zone to suppress the hydrolysis reactions of the cellulosic material. Substantially all of the hydrolysis reactions are suppressed in the wash zone and much of the hydrosate is removed with the wash liquid and liquor flowing through the upper extraction screen at the top of the wash zone and from an extraction screen(s) at the bottom of the wash zone (s). Multiple wash zones below the upper extraction screen and above the cooking zones may be used to flush hydrolysate from the cellulosic material and ensure that hydrolysis has stopped prior to the cooking zones.
[0007] A chemical, such as in an amount of 0.01 percent (%) to 5%, preferably 0.1 percent to 1 percent, of the wood in the slurry in the vessel may be included in the wash liquid added to the wash zone. The wash water or wash liquid (if chemical has been added) suppresses hydrolysis reactions in the cellulosic material below the extraction screen. This wash liquid has a temperature in a range of 10° C. to 70° C. cooler than the hydrolysis temperature, and preferably 20° C. to 50° C. cooler, and most preferably 25° C. to 35° C. cooler. Further, the wash liquid preferably has a pH in a range of 3 to 7, and most preferably in a pH range of 4 to 5. Chemicals, such as sodium hydroxide (NaOH), essentially sulfur free white liquor or a mixture of these chemicals, may be added to the wash liquid. The chemical(s) are added to the wash water to suppress hydrolysis and remove hydrosate, and optionally to adjust the pH of the wash liquid. The addition of the chemicals to the wash water results in substantially more hydrolysate being extracted from the cellulosic material flowing through the wash zone, that would occur if the wash liquid was purely water.
[0008] Chemical digesting of cellulosic material is performed below the hydrolysis and wash zones. Cooking chemicals are introduced into the vessel to cooking zones in the vessel and below the wash zones. Pulp generated from cooking the cellulosic material is discharged from the bottom of the vessel.
[0009] The process disclosed herein reduces the risk of precipitation of lignin and other dissolved wood components by delaying the introduction of alkali until after hydrolysis has been accomplished. The process may also reduce alkali consumption during chemical digesting of cellulosic material.
[0010] A reaction vessel has been developed including: a material input receiving cellulosic material and a material discharge for the cellulosic material, wherein the cellulosic material flows through the reaction vessel from the material input to the material discharge; a hydrolysate and liquid extraction screen; a hydrolysis zone between the material input and the hydrolysate and liquid extraction screen, wherein the hydrolysis zone is maintained at or above at a hydrolysis temperature at which a hydrolysis reaction occurs in the cellulosic material; a wash zone between the hydrolysate and liquid extraction screen and a wash liquid extraction screen and a wash liquid extraction screen in which the hydrolysis is substantially suppressed; a wash liquid inlet port for introducing a wash liquid into the wash zone, wherein at least a portion of the wash liquid entering the wash liquid inlet port flows through the wash zone to the hydrolysate and liquid extraction screen, and wherein the wash liquid is introduced to the wash zone at a temperature below the hydrolysis temperature and the wash liquid suppresses the hydrolysis in the second vessel zone; a cooking zone below the wash zone, wherein said cooking zone includes a cooking liquor injection port; a cooking liquor extraction screen below the cooking zone, and a pulp discharge below the cooking liquor extraction screen for discharging digested cellulosic material.
[0011] A reaction vessel has been developed comprising: a material input receiving cellulosic material and a material discharge for the cellulosic material, wherein the cellulosic material flows through the reaction vessel from the material input to the material discharge; a steam inlet receiving steam to heat and pressurize the cellulosic material in the vessel; a hydrolysate and liquid extraction screen; a hydrolysis zone below the material input and above the hydrolysate and liquid extraction screen, wherein the hydrolysis zone is maintained at or above a hydrolysis temperature at which a hydrolysis reaction occurs in the cellulosic material; a cooling zone below the hydrolysate and liquid extraction screen and above a cooling liquid extraction screen, wherein the cooling zone is maintained at a temperature below the hydrolysis temperature; a water inlet port for introducing water into the cooling zone, wherein at least a portion of the water entering the cooling inlet port flows through the cooling zone upward to and is extracted by the hydrolysate and liquid extraction screen, and wherein the water is introduced to the cooling zone at a temperature below the hydrolysis temperature; a first liquid extraction screen below the cooling zone and above a cooking zone; the cooking zone includes a cooking liquor injection port, and a cooking liquor extraction screen at or below the cooking zone and above the material discharge.
[0012] A method has been developed to produce pulp from cellulosic material comprising: introducing cellulosic material to an upper inlet of a pressurized reaction vessel; adding pressure and heat energy to the vessel; hydrolyzing the cellulosic material in an hydrolysis zone of the reaction vessel; extracting hydrolysate and liquid from the cellulosic material through a hydrolysate and liquid extraction screen below the hydrolysis zone and above a cooling zone of the vessel; introducing a cooling liquid to the cooling zone, wherein the cooling liquid suppresses hydrolysis of the cellulosic material in the cooling zone and wherein at least a portion of the cooling liquid flows upward through the cellulosic material to and is extracted by the extraction screen; digesting the cellulosic material in a cooking zone below the cooling zone by injecting a cooling liquor in the cooking zone, and discharging the digested cellulosic mater from a discharge port of the vessel wherein the port is below the cooking zone.
BRIEF DESCRIPTION OF THE DRAWING
[0013] FIG. 1 is a schematic diagram of a continuous pulping vessel which performs hydrolysis and digesting of cellulosic material.
DETAILED DESCRIPTION OF THE INVENTION
[0014] FIG. 1 shows a single vessel 10 for a steam phase hydrolysis and digesting system. The vessel may be a cylindrical reactor vessel arranged vertically and may be over 100 feet tall. The vessel may be pressurized to a pressure above atmospheric pressure. The vessel may be a component of a pulp processing plant.
[0015] The vessel 10 includes an internal top separator 12 . A slurry of cellulosic material is conveyed to the top separator via pipe 14 from a conventional chip feed system 16 . A screw conveyor in the separator 12 discharges the slurry of cellulosic material into an upper zone of the vessel. The top separator also extracts liquid from the slurry. The extracted liquid is discharged from the vessel via pipe 13 and may be recirculated to the chip feed system.
[0016] Cellulosic material and the liquid remaining in the slurry are discharged from the top separator 12 and fall through a gas phase 20 in an upper elevation of the vessel. The discharged cellulosic material falls through the gas phase and to the top of the chip level 22 in the vessel, if the vessel is a vapor phase vessel. If the vessel is a hydraulic vessel, the discharged material from the top separator directly enters a slurry that fills the vessel.
[0017] As new cellulosic material falls from the separator, material already at or below the chip level 22 is forced further down into the vessel. The liquor level 24 in the vessel may be at or near the chip level. Preferably, the liquid level is such that the top of the chip solids in the cellulosic material, generally represented by the top of the chip level 22 , is entirely submerged below the liquid level 24 .
[0018] Steam or other pressurized fluid 17 at above atmospheric pressure is introduced via pipe 18 to the gas phase zone 20 at the top of the vessel to provide heat and pressure to the vessel. Steam is preferably the principal external source of heat energy to the vessel. The vessel may be controlled based on pressure provided by the steam (or an inert gas) introduced to the top of the vessel. The use of a vapor or steam phase vessel 10 should reduce operating problems associated with gas formation by hydrolysis that may occur in the top of the vessel. However, a hydraulic vessel may still benefit from the introduction of wash liquid in an upper wash zone as is disclosed herein.
[0019] Hydrolysis occurs below the liquid surface level 24 and in an upper zone (A) of the vessel. The upper zone (A) extends generally from the liquid surface level 24 to the first (upper) extraction screen(s) 26 . The upper zone (A) is maintained at conditions that promote hydrolysis, such as being maintained at a temperature of at least 150 degrees Celsius or preferably at least 170 degrees Celsius. However, the temperature promoting hydrolysis may be below 150 to 170 degrees Celsius if chemicals, e.g., by adding an acidic solution to the liquor in the upper zone (A). Hydrolysate is generated in the upper zone A and is removed by the first extraction screen (or screen set) 26 .
[0020] Dissolved lignin in the upper zone (A) is not desired as the dissolve lignin may flow with the wash water through the through screen 26 . Lignin which has been dissolved under alkaline conditions, e.g., pH greater than 11 , tends to precipitate at pH levels lower than a pH of 11 . Preferably the pH of the upper zone (A) is below 11 and the upper zone is maintained at conditions that do not cause substantial amounts of lignin to dissolve in that zone.
[0021] The extracted liquid from screen 26 passes through a pipe 28 and to a flash tank 30 . Steam 31 generated in the flash tank may be used as heat energy in the pulp plant, such as to heat the upper zone of the vessel. The liquid from the flash tank may be recirculated via pipe 130 to the chip feed system to transport the slurry of cellulosic material to the vessel 10 and/or recovered, such as to extract sugars from the hydrolysate.
[0022] A wash zone (B) in the vessel is between the first extraction screen 26 and a wash liquid extraction screen 33 . Wash liquid 36 is supplied to the wash zone B to, in part, suppress hydrolysis in zone B. In wash zone B, counter-current washing occurs of the chip material moving downward through the vessel. The flow of material through the vessel is generally down and a counter-current flow of liquid is generally up. The general counter-flow direction of the wash liquid, e.g., wash water alone or with chemicals, in zone B is upward (see up arrow in zone B) and the general flow direction of the cellulosic materials is downward (see down arrow in zone B) through the vessel.
[0023] The wash liquid, e.g., either simply water or a mixture of water and chemicals, preferably has a temperature of 10° C. to 70° C. cooler than the hydrolysis temperature, more preferably 20° C. to 50° C. cooler, and most preferably 25° C. to 35° C. cooler. The pH of the wash liquid is preferably 3 to 7, and more preferably 4 to 5. The wash liquid is supplied to upper elevations of the vessel, such as zone B, from a wash liquid source 36 and by recirculating liquor extracted from the wash extraction screen 33 . The wash liquid and the recirculating liquor are sufficient to create an upward flow of fluids through zone B to the upper extraction screen 26 . Preferably, most of the washing of the cellulosic material occurs in zone B.
[0024] The wash liquid in source 36 may be simply wash water or a combination of wash water and chemicals such as one or more of sodium hydroxide (NaOH) and essentially sulfur free white liquor. Preferably, essentially sulfur free white liquor has no more than 0.10 parts per million (ppm) of sulfur compounds. For example, the amount of chemicals added to the wash water may be 0.01% to 5%, preferably 0.1% to 1%, of the amount of cellulosic material, e.g., wood, in the slurry flowing through the vessel. The chemicals are provided from a chemical source 53 and flow through pipe 57 to mix with wash water 34 in the source of wash liquid 36 . The mixture 36 of wash liquid and chemicals (if any) flow through wash liquid pipe 59 and mix with a recirculation flow of extracted liquor flowing through wash liquid extraction pipe 37 and back into the wash zone B through wash liquid inlet port 61 .
[0025] As the wash liquid flows upward through zone B to the upper extraction screen 26 , the wash liquid mixes with the cellulosic material flowing down through zone B to the upper extraction screen 26 . The wash liquid tends to cool the material and flush acids and other compounds from the materials. The acids and other compounds flow out through the extraction screen 26 . The cooling and flushing of the cellulosic material tends to suppress and preferably stop hydrolysis reactions occurring in the cellulosic material.
[0026] Con-current washing may occur below the second screen 33 as the cellulosic material flows downward (see arrow in zone C) to a third extraction screen 38 . In zone C, fluid flows generally downward con-currently, e.g., in the same flow direction, with the cellulosic material. Zone C is a wash and buffer zone that removes any remaining hydrolysate from the cellulosic material. The remaining hydrolysate is extracted in fluid passing through the extraction screen 38 and flows through pipe 40 to a flash tank 42 . As with flash tank 30 , steam from the flash tank 42 may be recovered as heat energy, e.g., introduced to the top of the vessel 10 , and liquid from the tank 42 may be recirculated to the chip feed system and recovered for other purposes, such as the recovery of sugars from the hydrolysate. Hydrolysate from screens 38 and 26 can be circulated via lines 19 A and 19 B to the to the top of the treatment vessel, if desired.
[0027] The hydrolysis cooling and wash zones (B and C) remove hydrolysate from the cellulosic material moving down through the vessel. Zones B and C buffer the cellulosic material undergoing hydrolysis in zone A from the cellulosic material undergoing digestion, e.g., cooking, in zones D and E. The wash zones are immediately below the hydrolysis zone (A) in the vessel. The wash liquid may be purposefully maintained at temperatures below hydrolysis temperature of the cellulosic material by adjusting the amount of wash liquid, which is cooler than the material in zone B, supplied to zone B and by adjusting the amount of cool water 34 supplied to the wash liquid 36 . The wash liquid cools the slurry of cellulosic material and liquor in zone B to suppress hydrolysis and assists with the removal of hydrolysate from the cellulosic material by washing the hydrolysate form the cellulosic material and removing the hydrolysate as the wash liquid is extracted through screen 26 .
[0028] Preferably, the temperature of the cellulosic material as it moves down from the buffer section (zone C) is below normal hydrolysis temperatures. The temperature of the cellulosic material is cooled by the cool wash liquid flowing into zones B, and optionally zone C, where the wash liquid is below the normal hydrolysis temperatures.
[0029] The wash liquid may also adjust the pH level of the material to be near or above neutral prior to the cooking zones (D and E). Removing hydrolysate and adjusting the pH level of the cellulosic material above the cooking zones generally should assist in minimizing or preventing precipitation of dissolved lignin present in the cooking chemicals in the cooking zones.
[0030] The wash liquid and liquor extraction and recirculation pipe 37 may include a pH monitor 44 . The pH of the recirculating wash liquid and liquor extracted through screen 33 and to be returned to the vessel through pipe 37 is monitored 44 . The amount of wash liquid 36 added to the recirculating wash liquid and liquor in pipe 37 may be determined, in part, to maintain the pH of the wash liquid and liquor flowing from line 37 to the vessel within a predetermined range such as between 4 pH and 10 pH, or in a narrower range of 6 pH to 10 pH or 6 pH to 8 pH. If the pH of the extracted wash liquid and liquor in pipe 37 is at a higher pH than the predetermined pH range, the amount of wash liquid 36 being added to pipe 37 may be increased. The pH of the wash liquid is typically at a pH of 7 and increasing the amount of wash liquid added to pipe 37 should reduce the pH of the liquid in pipe 37 towards a pH of 7. Further, an acid chemical, see chemical source 53 , may be added to the recirculation pipe 37 to assist in pH control of the wash liquid and liquor flowing through the pipe to the vessel. If the pH of the extracted wash liquid and liquor in pipe 37 is at the low end or below the predetermined pH range, chemicals from source 53 having a high pH may be added to the wash liquid 36 to be introduced to the flow in pipe 37 .
[0031] The diameter of the vessel 10 in the hydrolysis and washing sections (zones A to C) may be relatively uniform. Similarly, the diameter of the vessel in the cooking zones (zones D to F) may be relatively uniform and may be uniform with respect to zones A to C. Alternatively, one or more of the zones, e.g., D to F, may have a larger diameter than zones at higher elevations.
[0032] Cooking of the cellulosic material occurs in zones D and E that are below the wash and buffer zones (A to C) of the vessel. Cooking is chemically treating the cellulosic materials to dissolve lignins from the cellulosic material. Cooking chemicals are preferably not introduced to the top of the vessel 10 and preferably not above the third extraction screen 38 .
[0033] The cooking zones (D to E, and optionally F) are below the washing and buffer zones (B and C). In the cooking zones, cooking chemicals are injected to provide quick and thorough penetration of cooking chemicals into the cellulosic material. The cooking zones may be arranged such that the upper cooking zone (D) operates at a reduced temperature as compared to lower cooking zone(s) (E and F). The cooking zones may include con-current and counter-current liquor flow. Cooking zones D and F are shown with a counter-current liquor flow, and zone E is shown with con-current liquor flow.
[0034] Cooking chemicals (liquor) 50 are introduced to the vessel preferably in zone D. A cooking liquor recirculation pipe 52 recovers black liquor from an extraction screen 54 immediately below zone D. Additional cooking liquor 50 , e.g., white liquor, is mixed with the cooking liquor being recirculated and introduced into zone D from pipe 52 . The cooking liquor may be heated to cause the cellulosic material to begin cooking. The cooking process may begin as the cooking liquor is introduced the cooking zones, e.g., zone D. Additional cooking liquor may be removed at one or more extraction screens 58 at various elevations of zones E and F. The temperature of the cellulosic material may remain relatively constant as the material moves through zones E and F to the pulp discharge 56 at the bottom 32 of the vessel.
[0035] Cooking in the vessel may be with multiple stages where the cellulosic material passing through the first stage (upper elevation-zone D) is at a lower temperature than the cellulosic material at other stages (lower elevations-zones E and F). An optional cooking operation includes cooking of the cellulosic material as the material is introduced to the cooking liquor. Yet another cooking operation may include cooking the cellulosic material, once introduced to the cooking liquor, at different temperatures as the cooking process proceeds, e.g., zone D is a temperature higher than zones E and F.
[0036] Zone F may be a final cooking zone or a wash zone. Wash water, from a wash water source 34 , is introduced to the bottom 32 of the vessel and flows upward through the lowermost zone F from a source 34 of wash water. In the final wash zone, e.g., zone F, the wash water removes cooking chemicals from the cellulosic material just prior to discharge of the cellulosic material from the treatment or digester vessel.
[0037] Heat recovery methods may be continuously used to recover heat energy discharged by the flash tanks and the extraction screens 26 , 33 . For example if heat can be recovered from the circulation streams such as from wash liquid and liquor extraction and recirculation pipe 37 , such recovery could involve the use of heat exchangers or the like. It may also be necessary to pre-heat liquid 18 injected to the top of the vessel. This pre-heating could be accomplished via use of hot streams extracted from the vessel in heat exchange contact with the circulation pipes.
[0038] While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. | A reaction vessel including: a material input receiving cellulosic material and a material discharge for the cellulosic material, wherein the cellulosic material flows through the reaction vessel from the material input to the material discharge; a hydrolysate and liquid extraction screen; a hydrolysis zone between the material input and the hydrolysate and liquid extraction screen; a wash zone between the hydrolysate and liquid extraction screen and a wash liquid extraction screen; a wash liquid inlet port for introducing a wash liquid into the wash zone, wherein at least a portion of the wash liquid entering the wash liquid inlet port flows through the wash zone and is extracted by the hydrolysate and liquid extraction screen; a cooking zone between the wash zone and the material discharge and a cooking liquor extraction screen at or below the cooking zone and above the material discharge. | 3 |
RELATED APPLICATIONS
[0001] This application claims the priority of Japanese Patent Application No. 2007-258356 filed on Oct. 2, 2007, which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to disruption apparatuses, and more specifically, to a vacuum disruption apparatus with triple variable intersecting ultrasonic beams, for disrupting cells.
BACKGROUND OF THE INVENTION
[0003] Extraction of intracellular components requires cell disruption. In mass disruption of living cells, prolonged overloading of cells must be avoided.
[0004] Cells, especially cells of animals, without cell walls have a low physical strength and a high resilience, and mass and quantitative disruption of those cells require advanced skills.
[0005] Conventionally, an ultrasonic beam has been applied to disrupt relatively small objects, such as cells, under moderate conditions. For example, an apparatus disclosed in Japanese Unexamined Patent Application Publication No. 2005-211837 has been used, but the disruption has been often uneven and has not necessarily been satisfactory in terms of disruption rate.
[0006] Injection of a substance into cells has also been conducted to disrupt cells. If the substance to be transferred into a cell is a low-molecular substance, the cell may absorb the substance, but high-molecular substances such as protein and genes require forced transfer, which requires advanced manual operation skills such as injection into each cell by a capillary tube.
DISCLOSURE OF THE INVENTION
Problem to be Solved by the Invention
[0007] In view of the related art described above, it is an object of the present invention to provide an apparatus for disrupting a relatively small object efficiently without chemical loading.
Means to Solve the Problem
[0008] A vacuum disruption apparatus with triple variable intersecting ultrasonic beams, according to the present invention includes
[0009] a vacuum disruption vessel for containing and sealing a sample to be disrupted;
[0010] at least three ultrasonic generation units for emitting ultrasonic beams toward the vacuum disruption vessel; and
[0011] an ultrasonic modulation unit for varying intensities and frequencies of the ultrasonic from the ultrasonic generation units.
[0012] It is preferred that the vacuum disruption vessel of the apparatus has a vacuum pressure of 1 to 10 −3 Pa.
[0013] It is preferred that the ultrasonic modulation unit of the apparatus can vary the oscillating frequency of ultrasonic from each of the ultrasonic generation units within a range of 17 to 20 kHz.
[0014] It is preferred that the disruption apparatus disrupts cells.
[0015] It is preferred that the apparatus transfers a high-molecular substance included in a dispersion medium for cell into cells.
[0016] The disruption apparatus according the present invention emits three intersecting ultrasonic beams toward the object to be disrupted in a vacuum, so that highly-efficient and uniform disruption can be performed.
[0017] If the object to be disrupted is a living cell, a high-molecular substance, such as a gene or protein, can be introduced into the cell efficiently by disrupting just a part of the cell membrane and allowing the high-molecular substance to coexist in the dispersion medium for cell.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a sectional side view of a vacuum disruption apparatus with triple variable intersecting ultrasonic beams, of an embodiment of the present invention.
[0019] FIG. 2 is a top view of the apparatus shown in FIG. 1 .
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0020] A preferred embodiment of the present invention will be described below with reference to the drawings.
[0021] FIG. 1 is a side view showing a general structure of a vacuum disruption apparatus 10 with triple variable intersecting ultrasonic beams, of an embodiment of the present invention.
[0022] The disruption apparatus 10 shown in FIG. 1 includes a processing tank 14 disposed in an upper part of a main unit 12 of the apparatus, a vacuum disruption vessel 16 disposed in the processing tank 14 , a first ultrasonic generator 18 , a second ultrasonic generator 20 , and a third ultrasonic generator 22 which are disposed at the bottom part of the processing tank 14 , and an ultrasonic modulator 24 with an operating panel for varying the intensities and frequencies of ultrasonic from each of the ultrasonic generators 18 , 20 , and 22 .
[0023] The processing tank 14 has an inverted trapezoidal bottom consisting of a first oblique face 14 a on which an oscillating face 18 a of the ultrasonic generator 18 is disposed, a horizontal bottom face 14 b on which an oscillating face 20 a of the ultrasonic generator 20 is disposed, and a second oblique face 14 c on which an oscillating face 22 a of the ultrasonic generator 22 is disposed.
[0024] In the processing tank 14 , the vacuum disruption vessel 16 made of metal or glass, which propagates vibration (ultrasonic) well, is disposed. The ultrasonic generators 18 , 20 , and 22 are disposed in such a manner that the normal lines of the oscillating faces 18 a , 20 a , and 22 a intersect in the vacuum disruption vessel 16 . The processing tank 14 and the vacuum disruption vessel 16 contain water. In the vacuum disruption vessel 16 , a plurality of glass containers 26 , which transmit ultrasonic easily, can be placed.
[0025] In the ultrasonic modulator 24 , the oscillating frequencies, oscillating intensities, and emission modes (continuous emission or intermittent emission) for each of the ultrasonic generators 18 , 20 , and 22 , and the unit emission time, unit interval time, processing time, and the like for the intermittent emission mode can be changed with the operating panel. The temperature of the water in the processing tank 14 , the vacuum pressure of the vacuum disruption vessel 16 , and the like can also be changed on the same panel. It is also preferred that a computer which is separately connected to the apparatus can be used for changing the above-mentioned conditions instead of the operating panel.
[0026] The vacuum disruption vessel 16 is held by a holder 28 and placed in the processing tank 14 , and the vacuum disruption vessel 16 can be mounted and removed together with the holder 28 . The structure of the holder 28 is as shown in the top view of the apparatus in FIG. 2 . As clearly shown in the figure, the holder 28 has a handle 28 a formed by a rectangular frame and a panel 28 b for holding the top of the vacuum disruption vessel 16 , both edges of the panel 28 b being secured to the top of the main unit 12 of the apparatus.
[0027] In this embodiment, the vacuum disruption vessel 16 has a sample solution inlet valve 32 at the top and a sample solution outlet valve 34 at the bottom. The sample solution outlet valve 34 is connected to a peristaltic pump, which is not shown in the figure, through an outlet tube 36 . The valves 32 and 34 allow continuous incoming and outgoing flow of a sample solution.
[0028] The vacuum disruption apparatus 10 with triple variable intersecting ultrasonic beams, of the embodiment is configured, in outline, as described above and the operation thereof will be described next.
[0029] Cell Disruption
[0030] A glass container 26 containing a cell suspension is placed in the vacuum disruption vessel 16 , and then the vacuum disruption vessel 16 (having a capacity of about 3 liters) is sealed and placed in the processing tank 14 (having a capacity of about 12 liters). The vacuum disruption vessel 16 is decompressed by a vacuum pump, which is not shown in the figure, through a decompression valve 30 . It is preferred to bring the vacuum pressure to 1 to 10 −3 Pa, for disruption of usual cells of living creatures.
[0031] The ultrasonic generators 18 , 20 , and 22 start to generate ultrasonic oscillations with an operation in the ultrasonic modulator 24 . The oscillating intensities and oscillating frequencies at the first, second, and third ultrasonic generators 18 , 20 , and 22 are as listed below.
[0000]
TABLE 1
Oscillating frequency
Oscillating intensity
First ultrasonic
20 kHz
200 W
generator
Second ultrasonic
20 kHz
200 W
generator
Third ultrasonic
20 kHz
200 W
generator
[0032] A unit time of ultrasonic emission was set to 10 seconds, and a unit time of emission interval was also set to 10 seconds. The ultrasonic emission and interval were repeated alternately for one hour.
[0033] The resultant cell disruption rate was about 100% (when observed with a microscope).
[0034] When the apparatus was used as a double-intersecting-ultrasonic-beam disruption unit by activating the first and second ultrasonic generators only, the disruption rate was about 40%. When the first, second, and third ultrasonic generators were activated in an atmosphere, the disruption rate was 50%.
[0035] Gene Injection
[0036] As in cell disruption, a glass container 26 containing a cell suspension is placed in the vacuum disruption vessel 16 , and then the vacuum disruption vessel 16 is sealed and decompressed by the vacuum pump, which is not shown in the figure, through the decompression valve 30 . It is preferred to bring the vacuum pressure to about 10 −2 Pa, for injection into usual cells of living creatures.
[0037] The ultrasonic generators 18 , 20 , and 22 start to generate ultrasonic oscillations with an operation in the ultrasonic modulator 24 . The oscillating intensities and oscillating frequencies at the first, second, and third ultrasonic generators 18 , 20 , and 22 are as listed below.
[0000]
TABLE 2
Oscillating frequency
Oscillating intensity
First ultrasonic generator
19 kHz
150 W
Second ultrasonic generator
19 kHz
150 W
Third ultrasonic generator
19 kHz
150 W
[0038] A unit time of ultrasonic emission was set to 3 seconds, and a unit time of emission interval was set to 10 seconds. The ultrasonic emission and interval were repeated alternately for half an hour.
[0039] The resultant rate of gene transfer into cells was about 50%.
[0040] When the apparatus was used as a double-intersecting-ultrasonic-beam disruption unit by activating the first and second ultrasonic generators only, the transfer rate was 10% to 20%. When the first, second, and third ultrasonic generators were activated in an atmosphere, the transfer rate was also 10% to 20%.
[0041] Frequency and Transfer Rate
[0042] The inventors studied the relationship between the ultrasonic oscillating frequency and the gene transfer rate. The oscillating frequency was varied, and the other conditions were the same as those of the gene injection, described above.
[0000]
TABLE 3
Oscillating frequency (kHz)
17
19
20
Transfer rate
40%
50%
45%
[0043] When the apparatus according to the present invention is used for gene transfer into cells, a preferred oscillating frequency and oscillating intensity may depend on the type of the cell.
[0044] Because three ultrasonic beams are emitted to intersect with one another in the present invention, uniform disruption can be performed even in continuous processing of a sample solution. | A vacuum disruption apparatus with triple variable intersecting ultrasonic beams, capable of disrupting a great number of cells efficiently without chemical loading. The apparatus includes a vacuum disruption vessel for containing and sealing a sample solution having living cells to be disrupted; at least three ultrasonic generation units for emitting ultrasonic beams toward the vacuum disruption vessel; and an ultrasonic modulation unit for varying the intensities and frequencies of ultrasonic from the ultrasonic generation units. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This is a Divisional Application of U.S. Ser. No. 14/353,529, filed on Apr. 23, 2014, which is herein incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to a method of producing graphene using a metal catalyst.
BACKGROUND OF THE INVENTION
[0003] Graphene is attracting a great deal of attention because of its excellent properties. With respect to graphene, professors Geim and Novoselov at the University of Manchester first succeeded in separating atomic layers from graphite using scotch tape in the year 2004 and were awarded the Nobel Prize for their discovery of graphene in the year 2010. In the year 2010, a roll-to-roll transfer technique of manufacturing large-area graphene having an area of 30 inches was reported, and technologies enabling graphene to be industrially applied have been continuously developed. For industrial application, graphene is required to be formed uniformly as a single layer. In the prior art, the use of general copper foils suffers from a problem in that multilayer graphene is present as islands or an epitaxial graphene layer or epitaxial graphene layers do not easily grow.
[0004] In the manufacturing of graphene electrodes, the surface energy state of a metal catalyst is important for the epitaxial growth of monolayer graphene. This is because the atomic packing density of a metal varies depending on the orientation of the metal and because factors, including dislocation density, stacking fault energy, twins and impurities, which influence the surface energy of the catalyst, influence the reaction with the gaseous molecules or atoms to be adsorbed. Particularly, when a metal has low solubility or low reactivity with the element to be adsorbed, it barely acts as a catalyst. For example, copper is frequently used for the formation of graphene thin films and has a face-centered cubic (FCC) structure. However, the solid solubility of carbon which is adsorbed onto the surface of the catalyst copper in CVD processes at 1000° C. is 0.028 at % or less. Due to this low reactivity, it is very difficult to control the adsorption of carbon atoms during the CVD processes. If structures having different orientations are present together, the energy state will become non-uniform, and thus the adsorption rate of carbon will differ between areas. This problem results in the growth of multilayer graphene in some areas to form graphite. Thus, to uniformly grow carbon on copper to form graphene thin films, it is effective to use as a catalyst a substrate which has a uniform energy state and at the same time, has formed thereon nucleation sites on which graphene nets are to be formed. Materials capable of satisfying a uniform energy state include single crystalline materials. Many studies thereon have been conducted, and particularly, studies on the use of single crystalline hexagonal FCC metals oriented in the (111) or (100) direction (for example, the study of Hori) or on single crystalline HCP metals having a (0001) plane have been conducted (J. Phys. Chem. B., Vol. 106, No. 1 15-17, 2002, Y. Hori et al.).
[0005] However, the results of the studies did not lead to industrialization, because only single crystalline metals having a size of several tens of nm can be prepared and it is impossible to obtain large areas which are industrially applicable. In addition, for industrial application, graphene is required to be formed uniformly as single layers, but the use of general copper foils in the prior art suffers from a problem in that multilayer graphene is present as islands, because the epitaxial growth rate of graphene is low.
[0006] The present inventors have developed a method for preparing a unidirectionally oriented metal catalyst for uniformly and epitaxially growing graphene and have found that the orientation and surface energy state of a catalyst substrate, particularly step structures, have a great influence on the adsorption of carbon atoms and the growth of graphene, thereby completing the present invention.
SUMMARY OF THE INVENTION
Technical Problem
[0007] It is an object of the present invention to make the energy of a metal catalyst substrate uniform and make the surface of the catalyst substrate having unidirectionally oriented structures in order to uniformly and epitaxially grow graphene. Another object of the present invention is to provide a method for producing graphene, comprising the steps of: alloying a metal catalyst substrate to form fine step structures on the surface of the catalyst; forming step structures on the alloyed metal catalyst substrate in the atmosphere of hydrogen gas and a gas having a molecular weight higher than the atomic weight of carbon; and supplying hydrocarbon and hydrogen gases to the metal catalyst substrate.
Technical Solution
[0008] To achieve the above objects, one embodiment of the present invention provides a method of producing graphene by forming step structures on the surface of a face-centered cubic metal catalyst substrate having the (100) or (111) orientation and supplying hydrocarbon to the substrate.
[0009] In the present invention, the metal catalyst may be a face-centered cubic metal catalyst having a cold rolling reduction ratio of 85% or higher and the (100) or (111) orientation. The metal catalyst may have a thickness of 50 or less. The metal catalyst may be recrystallization-annealed in a hydrogen or reducing atmosphere, cooled and then heated in an atmosphere of methane and hydrogen to grow graphene thereon. The metal catalyst may be any one selected from the group consisting of copper, silver and gold. 95% or more of the graphene is a monolayer graphene thin film. The metal catalyst may be electroplated by a pulse wave current, and the step structure may be formed by annealing at a temperature of 600° C. to 1070° C. The pulse wave current may be applied at a ratio of current supply time: rest time of 15:85 to 85:15. The pulse wave current may have a current density of 1-10 A/dm 2 , and the metal catalyst may be a face-centered cubic metal foil obtained by plating a metal on a cathode rotating drum. The cathode rotating drum may be polished to a roughness (Ra) of Ra 0.35 or less.
[0010] In addition, the metal catalyst may be alloyed with an alloying element, and the alloying element may be any one or more selected from among period 2 to period 6 elements among group 3 to group 12 transition metal elements and group 13 to 15 elements. The step structures on the metal catalyst may be formed in the atmosphere of a gas having a molecular weight higher than the atomic weight of carbon, and the metal catalyst may be aluminum, nickel, austenitic stainless steel, silver, gold or copper. The alloying element may be any one or more transition elements which have solid solubility for hydrogen or form carbides at a temperature ranging from 600 to 1060° C. and the alloying element may be any one or more selected from among aluminum, indium, silicon, silicon, germanium, tin, antimony and bismuth. The gas having a molecular weight higher than the atomic weight of carbon may be any one or more selected from among neon, argon, krypton, nitrogen, hydrocarbon, carbon dioxide, carbon monoxide and steam (H 2 O). In the present invention, when viewing the surface energy of copper according to the crystalline structure, the (111) plane has the highest packing density and stable energy level among three simple planes, and the (100) plane is the next stable plane. In addition, in an actual measurement process, the (100) plane is also expressed as (200) and (001) depending on the measurement direction and position, but these can all be regarded as the same orientation.
[0011] In the present invention, the (110) plane has an open structure between two parallel arrangements of atoms, and thus is unstable compared to the (111) or (100) plane and has a structure on which a graphene net is difficult to form. For this reason, it is not suitable to use the (110) plane as a catalyst for forming a graphene mono layer.
[0012] As used herein the term “electrodeposited copper foil” refers to a copper thin film made by an electroplating process, but is limited thereto. In the present invention, the electrodeposited copper foil is prepared by carrying out electrolysis in electrolyte solution bath and electrodepositing and/or electroplating the copper ion of the plating solution onto the drum surface. Examples of the electrodeposited copper foil include a general electrodeposited copper foil having a shiny side, which is smoothly deposited on the drum surface, and a matte side opposite thereto, and a plated copper foil obtained by depositing a copper thin film on a copper foil by the electroplating process.
[0013] One embodiment of the present invention is directed to a method of making a copper foil. This method is carried out using a foil making system comprising: a container to which electrolyte solution containing copper ions is continuously supplied; a drum, a part of which is dipped and rotated in the electrolyte solution and to which a negative terminal is connected; and an anode spaced apart from the dipped part of the drum and also placed in the electrolyte solution. In this copper foil making system, an electric current is applied between the cathode rotating drum and the anode to continuously electrodeposit copper ions on the drum surface.
[0014] In one embodiment of the present invention, if the roughness (Ra) of the drum surface is more than 0.35 μm, it will be transferred to the electrodeposited copper foil so that graphene will be non-uniformly and excessively produced as multilayered area in a CVD process.
[0015] In one embodiment of the present invention, if the thickness of an oxide layer on the drum surface is less than 1 nm, the separating force of an electrodeposited copper will increase provably to damage the copper foil, and if the thickness of the oxide layer is more than 20 nm, electrolysis current density will be excessively required, resulting in decreased productivity.
[0016] In one embodiment of the present invention, the drum is made of titanium or stainless steel, which is generally used for the fabrication of electrodeposited copper foils. In addition, it may be made of carbon steel, alloy steel, non-ferrous metals, ceramic materials or composite materials. In addition, any material may be used for the drum, as long as it can coat cubic structure metal by means such as deposition, plating or spraying.
[0017] In another embodiment of the present invention, a plated copper foil is provided by pulse-current plating copper and controlling the foil to a single orientation by annealing. Also, a rolled copper foil is provided by cold-rolling a copper foil at a reduction ratio of 85% or more and controlling the foil to a single orientation by annealing. On these copper foils, graphene is easily grown.
[0018] In one embodiment of the present invention, there is provided graphene fabricated by the above method.
[0019] In the present invention, the catalyst substrate preferably has a hexagonal lattice structure having a single orientation so that uniform and epitaxial graphene is grown thereon. Importantly, the surface of the catalyst substrate is smooth when viewed macroscopically and has a step structure when viewed microscopically. The catalyst substrate preferably has the (111) and/or (100) orientation. As shown in FIGS. 3( b ) and 5 , the step types of the present invention are developed fine step from a nano unit to a micron unit. Four types of step were mainly found by the present inventors ( FIG. 1 ). The step types include paddy-field steps, ledges, ratchet steps, and multi-cube steps. The step structures were developed when supplying a gas having a mass higher than the atomic weight of carbon (12) while annealing a foil, cold-rolled at a high reduction ratio, at a temperature of 600° C. or higher.
[0020] FIG. 8 shows the atomic arrangement of coppers alone and the state of a copper alloy containing a substitutional element. FIG. 8( a ) shows the atomic arrangement of coppers, and FIGS. 8( b ) and 8( c ) show the atomic arrangements of copper alloys which contain a substitutional element having an atomic diameter larger than that of copper and a substitutional element having an atomic diameter smaller than that of copper, respectively. If there is a difference in the atomic radius as shown in FIGS. 8( b )and 8( c ) , lattice distortion (lattice strain) is present around the substitutional element and results in energy imbalance. The connection line between the atoms around the substitutional element shows this lattice distortion. This lattice distortion in a copper alloy promotes the production of dislocation in a process during which the alloy undergoes physical external stress, such as a rolling process. When a thin sheet having a large amount of this stacking fault or dislocation is annealed at high temperature in an atmosphere of a gas having a molecular weight higher than the atomic weight of carbon, atoms on the surface will move to form steps as shown in FIG. 11 . Because the step structures act as nucleation sites, they adsorb hydrocarbon to produce carbon radicals assembling as graphene nuclei. Once graphene nuclei are produced, radicals around the nuclei bind to the surrounding radicals or directly adsorb hydrocarbon to form carbon-carbon bonds, thereby growing graphene.
[0021] In one embodiment of the present invention, if the stacking fault energy of the catalyst substrate is reduced or lattice distortion increases by alloy element addition, dislocations or twins are likely to occur in the material to increase the internal energy. Thus, alloying is carried out such that step structures are easily formed during annealing. Unlike this, in metals having high stacking fault energy, dislocations attract each other and cross-slip easily occurs so as to reduce the dislocation density and thus reduce the internal energy of the material. Thus, in the present invention, when an alloying element is added to reduce the stacking fault energy, twins are likely to occur during annealing at high temperature. The twin sites have higher surface energy so that graphene growth becomes easy, and thus larger graphene crystals can be obtained. The alloying element is an element which has hydrogen solid solubility or forms carbides at a temperature of 600˜1060° C. at which graphene can be synthesized. Specifically, it is selected from among period 2 to period 6 elements among group 3 to 12 transition elements and group 13, 14 and 15 elements. The hydrogen solid solubility of elements at 1000° C. is 70.5 ppm for copper, 4.5 ppm for gold, 22.4 ppm for silver, 2.6 ppm for chromium, 1.2 ppm for molybdenum, 32.8 ppm for manganese, 186.2 ppm for cobalt, 251 ppm for iron, 562.3 ppm for nickel, 7079 ppm for rhodium, 4.7 ppm for platinum, 11879 ppm for titanium, and 85.1 ppm for aluminum. This suggests that transition metals have solid solubility for hydrogen In the case of elements other than transition metals, aluminum of group 13 has high solid solubility, and indium binds with hydrogen at high temperature to form a compound. Among group 14 and 15 elements, silicon makes carbides, and germanium, tin, antimony and bismuth form hydrogen compounds, like indium. Thus, the alloying elements descried in the present invention may mostly be added.
[0022] In one embodiment of the present invention, as the reduction ratio of a copper foil increases and the thickness of a copper foil decreases, dislocations increase, and the rotation of recrystallized grains in an annealing process can be facilitated. It was found that 95% or more of the area of a copper foil which was cold-rolled at a reduction ratio of 85% or more had the (100) orientation after annealing. Thus, in order to obtain a structure having a single orientation, a copper foil can be rolled at a reduction ratio of 85% or higher to a thickness of 50 μm or less.
[0023] Copper has low stacking fault energy, and thus when it is cold-rolled, the dislocation density thereof is increased to cause atomic migration and diffusion during annealing. Herein, the atoms migrate by an image force acting between dislocations during heating at high temperature and finally disappear while leaving step structures corresponding to Burgers vectors on the surface. As the stacking fault energy and flow stress of the catalyst copper alloy decrease and the cold reduction ratio thereof increases, dislocation movement in the material becomes more active to facilitate the formation of step structures. The step structures which are formed in atomic layer units in the Burgers vector size by this dislocation movement are formed so small even at a high temperature of 1000° C. such that they so weakly adsorb gas molecules. For this reason, in the present invention, a gas, such as argon or nitrogen, which has a molecular weight higher than the atomic weight of carbon while having low chemical reactivity with a copper foil, is supplied together with small amount of hydrogen during an annealing process, so that the gas molecules collide with the copper surface by the Brown motion even at a temperature of about 600° C. to assist in the migration of copper atoms, thereby facilitating the formation of step structures. Unlike areas in which impurity elements or alloying elements exist as compounds, step structures are distributed uniformly throughout the catalyst surface, and thus form an environment in which graphene grows epitaxially.
[0024] In one embodiment of the present invention, hydrogen serves to maintain the reducing atmosphere, and thus it is added in an amount corresponding to less than 40% of the flow rate of the gas after draw-air out for an annealing chamber. In the graphene synthesis process following the annealing process, hydrogen also serves to control the growth rate of graphene, because the decomposition rate of hydrocarbon decreases as the ratio of hydrogen increases. The flow rate of the gas is in the range of 0.1-10 sccm/μm, and it can be increased as the thickness of a copper foil increases, and it is decreased with increases in temperature and the molecular weight of the gas.
[0025] The step structures act as nucleation sites, and thus adsorb hydrocarbons to produce carbon radicals serving as graphene nuclei. Once graphene nuclei are produced, carbon radicals around the nuclei bind to the surrounding carbon radicals or directly adsorb hydrocarbon to form carbon-carbon bonds, thereby growing graphene.
Advantageous Effects
[0026] On a unidirectionally oriented metal catalyst prepared according to the present invention, graphene can be grown uniformly and epitaxially.
[0000] Moreover, a method for producing graphene according to the present invention can form monolayer graphene by epitaxially growing graphene while increasing the growth rate of graphene.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] FIG. 1 is a set of SEM photographs, wherein FIG. 1( a ) shows the rolled state of a copper foil, and wherein FIG. 1( b ) shows the state of the copper foil after recrystallization annealing.
[0028] FIG. 2( a ) shows the state of a copper foil according to the present invention, FIG. 2( b ) shows the copper foil annealed at 1000° C. in the hydrogen atmosphere, and FIG. 2( c ) shows graphene grown by supplying methane together with hydrogen to the copper foil.
[0029] FIG. 3 is a set of graphs, wherein FIG. 3( a ) shows the rolled state of a copper foil, and wherein FIG. 3( b ) shows the results of measuring the orientation of the foil by XRD after growing graphene thereon.
[0030] FIG. 4 is a graphic diagram showing the results of measurement of the Raman spectrum of monolayer graphene.
[0031] FIG. 5 shows the pulse copper plating state of pulse copper plated specimens and the results of measuring the orientation of the specimens by XRD after growing graphene thereon. FIGS. 5( a ) and 5( b ) show the results of measuring the state of a specimen obtained by plating copper on a copper foil at a ratio of 80:20 at a current density of 4.2-4.3 A/dm2 and the orientation of a structure obtained by growing graphene on the specimen at 1000° C.; FIGS. 5( c ) and 5( d ) show the results of measuring the state of a specimen obtained by plating copper on a copper foil at a ratio of 50:50 at a current density of 2.6 A/dm2 and the orientation of a structure obtained by growing graphene on the specimen at 1000° C.; and FIGS. 5( e ) and 5( f ) show the results of measuring the state of a specimen obtained by plating copper on a copper foil at a ratio of 20:80 at a current density of 1.6 A/dm2 and the orientation of a structure obtained by growing graphene on the specimen at 1000° C.
[0032] FIG. 6 is a set of optical micrographs showing graphene grown on an electrodeposited copper foil in one direction (CVD, 1050° C. for 10 min); FIG. 6( a ) shows the micrograph at 100× magnification; FIG. 6( b ) shows the micrograph at 1000× magnification.
[0033] FIG. 7 shows various steps formed when annealing a metal thin sheet in a gas atmosphere. FIG. 7( a ) is a paddy-field step; FIG. 7( b ) is a ledge step; FIG. 7( c ) is a ratchet step; and FIG. 7( d ) is a multi-cube step.
[0034] FIG. 8 is a set of schematic diagrams showing the arrangement of copper atoms and the state of carbon alloyed with a substitutional element. FIG. 8( a ) shows the atomic arrangement of coppers, and FIGS. 8( b ) and 8( c ) show the atomic arrangements of copper alloys which contain a substitutional element having an atomic diameter larger than that of copper and a substitutional element having an atomic diameter smaller than that of copper, respectively.
[0035] FIG. 9 shows the results of synthesizing graphene using copper ( FIG. 9( a ) ) and a copper alloy ( FIG. 9( b ) ) at 600° C. for 30 minutes.
[0036] FIG. 10 shows the results of synthesizing graphene using copper ( FIG. 10( a ) ) and a copper alloy ( FIG. 10( b ) ) by CVD at800° C. for 30 minutes.
[0037] FIG. 11 shows the results of synthesizing graphene using copper and various copper alloy catalysts by CVD. As a control for the graphene prepared in Example 4, copper foil was annealed at 1000° C. for 30 minutes in an atmosphere of a mixed gas of 50 sccm argon and 10 sccm hydrogen, and graphene was synthesized thereon by CVD at 1000° C. for 30 minutes in an atmosphere of a mixed gas of 15 sccm methane and 10 sccm hydrogen. The results are shown in FIG. 11( a ) . FIG. 11( b ) shows the results obtained by annealing a copper alloy foil containing 80 ppm of silver at 800° C. for 30 minutes in an atmosphere of a mixed gas of argon 20 sccm and 10 sccm hydrogen and then synthesizing graphene thereon by CVD at 1000° C. for 5 minutes in an atmosphere of a mixed gas of 20 sccm methane and 10 sccm hydrogen. FIG. 11( c ) shows the results obtained by annealing a copper alloy foil containing 40 ppm of chromium at 1000° C. for 30 minutes in atmosphere of a mixed gas of 50 sccm argon and 10 sccm hydrogen and then synthesizing graphene thereon by CVD at 800° C. for 3 minutes in an atmosphere of a mixed gas of 20 sccm methane and 10 sccm hydrogen; FIG. 11( d ) shows the results obtained using a copper alloy foil containing 200 ppm of iron under the conditions as the case of FIG. 11( c ) ; FIG. 11( e ) shows the results obtained using a copper alloy foil containing 130 ppm of cobalt under the conditions as the case of FIG. 11( c ) ; FIG. 11( f ) shows the results obtained using a copper alloy foil containing 100 ppm of nickel under the conditions as in the case of FIG. 11( c ) ; FIG. 11( g ) shows the results obtained using a copper alloy foil containing 140 ppm of silver under the conditions as the case of FIG. 11( c ) ; and FIG. 11( h ) shows the results obtained using a copper alloy foil containing 70 ppm of silicon under the conditions as the case of FIG. 11( c ) .
[0038] FIG. 12 shows the results of synthesizing graphene by CVD at 1000° C. for 1 second in an atmosphere of a mixed gas of 30 sccm methane and 10 sccm hydrogen.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0039] Hereinafter, the present invention will be described in detail with reference to examples and test examples. It is to be understood, however, that these examples are for illustrative purposes and are not intended to limit the scope of the present invention.
EXAMPLES
Example 1
[0040] Fabrication of graphene thin film on rolled copper foil Tough pitch copper foils (a purity of 99.9% or more, an oxygen content of 0.05% or less) having thicknesses of 0.5 mm and 0.2 mm were annealed, and then cold-rolled to thicknesses of 12 μm, 25 μm, 40 μm, 50 μm and 100 μm. The cold rolled foils were heated at various annealing temperatures so that 95% or more thereof was oriented in the (100) direction. It was confirmed that a graphene thin film was evenly formed on the annealed foils (see FIG. 1 ). After recrystallization, only crystal growth occurred on the foils, and thus the orientation of the foils did not change to a new orientation. Table 1 below shows the results of forming graphene layer at various reduction ratios under various heat treatment conditions.
[0000]
TABLE 1
Thickness
Thickness
Formation
of raw
after
(100)
Recrystallization
of
material
rolling
Reduction
plane
annealing
monolayer
(mm)
(μm)
ratio (%)
orientation
temperature (° C.)
graphene
Preparation
0.2
12
94
◯
200
◯
Example 1
Preparation
0.2
25
87.5
◯
600
◯
Example 2
Comparative
0.2
40
80
X
1000
X
Example 3
Comparative
0.2
50
75
X
1000
X
Example 4
Preparation
0.5
40
92
◯
600
◯
Example 5
Preparation
0.5
50
90
◯
800
◯
Example 6
Comparative
0.5
100
80
X
1000
X
Example 7
[0041] As can be seen in Table 1 above, when the foils were cold-rolled at a reduction ratio of 85% or more, 95% or more the area thereof was oriented in the (100) direction, and when the foils were recrystallization-annealed, graphene layer could be formed on the copper foils. Also, it can be seen that, when the reduction ratio is high and the thickness of the copper foil is small, the (100) orientation is easily formed. Thus, the rolled copper foil provided according to the present invention has a critical significance when it has a reduction ratio of 85% or more or a thickness of 50 μm or less.
[0042] The foils were recrystallization-annealed at various temperatures in an atmosphere of hydrogen having a flow rate of 10 sccm, followed by cooling, and the orientation thereof was measured. Then, the foils were heated to 1000° C. and maintained in an atmosphere of 15 sccm methane and 10 sccm hydrogen for 30 minutes while graphene was grown thereon by CVD. FIG. 2( a ) shows the state of a copper foil according to the present invention, FIG. 2( b ) shows the copper foil annealed at 1000° C. in a hydrogen atmosphere, and FIG. 2 ( c ) shows graphene grown by supplying methane together with hydrogen to the copper foil. In the present invention, it was found that, even when copper foils are heated at high temperatures, the development of steps thereon differ between an annealing process in which only hydrogen is supplied and an annealing process a mixed gas of methane gas and hydrogen is supplied.
[0043] FIG. 3 shows the state of the rolled foil in Preparation Example 5 and the orientation of the foil measured after forming graphene thereon. FIG. 4 shows the results of measuring the Raman spectrum of the foil after growing graphene thereon. As can be seen therein, monolayer graphene was formed on the foil.
Example 2
Fabrication of Graphene Layer on Electrodeposited Copper Plated Tough Pitch Copper Foil
[0044] 2-1: Fabrication of Electrodeposited Copper Foil by Pulse-Current Plating and Graphene Layer
[0045] Plain tough pitch copper foils were air-stirred in a solution composed of 180-330 g/L of copper sulfate pentahydride (CuSO 4 .5H 2 O), 40-120 g/L of sulfuric acid and 40-120 ppm of hydrochloric acid at a temperature of 30˜55° C. and a current density of 1-10 A/dm 2 , thereby pulse current plating the foils. The results are shown in FIG. 5 , and the pulse waveform is expressed as current supply time: rest time.
[0046] FIGS. 5( a ) and 5( b ) show the results of measuring the state of a specimen obtained by plating copper on a copper foil at a ratio of 80:20 at a current density of 4.2-4.3 A/dm 2 and the orientation of a structure obtained by growing graphene on the specimen at 1000° C.; FIGS. 5( c ) and 5( d ) show the results of measuring the state of a specimen obtained by plating copper on a copper foil at a ratio of 50:50 at a current density of 2.6 A/dm 2 and the orientation of a structure obtained by growing graphene on the specimen at 1000° C.; and FIGS. 5( e ) and 5( f ) show the results of measuring the state of a specimen obtained by plating copper on a copper foil at a ratio of 20:80 at a current density of 1.6 A/dm 2 and the orientation of a structure obtained by growing graphene on the specimen at 1000° C. As can be seen therein, in the plated state, the (200) single orientation or a mixed orientation of (111) (200) (220) orientations can appear depending on the plating conditions, but after the growth of graphene at 1000° C., only the (200) orientation appears.
[0047] Also, when the pulse current plated specimens were annealed, the mixed orientation was arranged to the (200) orientation at 600° C. or higher regardless of the plating conditions. However, even at the above current density range, the mixed orientation appeared even after annealing, when plating was carried out by a PR (pulse-reverse) method or direct current plating.
[0048] It appears that the reason why the single orientation is determined depending on the waveform of current even at the same current density is that the pulse wave shows a high atomic packing density compared to other current waves while providing epitaxial electrodeposition, and thus the mixed orientation is arranged to a single orientation by subsequent heating. With respect to another reason, in the manufacturing of general electrodeposited copper foils, plating is carried out at high current density and a high rate of about of 1 m/min, and thus the degree of disorder of deposited copper atoms is high such that the orientation thereof is difficult to rearrange to a single orientation by the introduction of heat energy during annealing.
[0049] Thus, the scope of the present invention includes pulse-plating a copper foil by stirring in a solution composed of 180-330 g/L of copper sulfate pentahydride (CuSO 4 .5H 2 O), 40-120 g/L of sulfuric acid and 40-120 ppm of hydrochloric acid at a temperature of 30˜55° C. and a current density of 1-10 A/dm 2 , and annealing the pulse-current plated copper foil at a temperature of 600° C. or higher, and also growing graphene on the plated copper foil.
[0050] 2-2: Fabrication of Electrodeposited Copper Foil and Graphene Layer
[0051] Copper scrap was dissolved in acid solution, and the solution was supplied into an opening below an anode placed in an electrolysis bath containing 250 g/l of copper sulfate (CuSO 4 H 2 O) and 80 g/l of sulfuric acid at 30° C., while an electrolysis reaction (cathode electrode current density: 8 A/dm 2 ) was induced so that a thin copper foil having a (111) orientation was electrodeposited on a titanium (Ti) rotating drum having a connector to cathode. Herein, the foil side facing the drum side was shiny, and the opposite side was matte. The drum surface was polished to a roughness (Ra) of 0-0.35 μm and anodized to form an oxide layer of 1-20 nm in order to facilitate the separation of an electrodeposited copper foil from the polished drum surface.
[0052] Copper was pulse-current plated on the electrodeposited copper foil according to the method of Example 2-1, and graphene was deposited and grown thereon by CVD. The resulting structure was observed with an optical microscope and the orientation thereof was measured by XRD (see FIGS. 5 and 6 ). As a result, it could be seen that the electrodeposited copper foil after annealing had an unidirectional orientation having the (111) or (200) orientation and that epitaxial graphene was formed on the electrodeposited copper foil produced using the drum having a surface roughness (Ra) of 0.0001-0.35 μm.
Example 3
Formation of Graphene on Copper Alloy Catalyst Substrate
[0053] A copper alloy foil containing 140 ppm of silver (see FIG. 9( b ) ) was heated at 600° C. for 30 minutes in an atmosphere of 70 sccm methane and 10 sccm hydrogen, and whether graphene was formed on the alloy foil was examined. As a control, copper (see FIG. 9( a ) ) was treated under the same conditions, and whether graphene was formed thereon was examined (see FIG. 9 ).
[0054] It can be seen that, when graphene was formed on copper, graphene islands and carbides were formed, but on the silver-containing copper alloy, graphene was epitaxially formed. However, when copper was previously annealed at 800° C. to form steps, graphene was epitaxially formed thereon.
[0055] The above copper alloy and copper had a hexagonal lattice structures having the (111) or (100) orientation after annealing, and these catalyst substrates also had the same orientation in the following examples.
[0056] Thus, it could be seen that the addition of a substitutional alloy to copper provides graphene nucleation sites and promotes the development of a step structure to suppress carbide formation and also enables the epitaxial growth of graphene.
Example 4
Examination of Effect of Formation of Step Structure
[0057] A 18 μm thick copper alloy foil containing 3.2% nickel, 1.5% silicon and 0.4% magnesium was annealed at 1000° C. for 30 minutes in an atmosphere of a mixed gas of 50 sccm argon and 10 sccm hydrogen to form steps structure, and graphene was synthesized thereon by CVD at 800° C. for 30 minutes in an atmosphere of a mixed gas of 70 sccm methane and 10 sccm hydrogen (see FIG. 10( a ) ).
[0058] As a control, a 25-μm thick copper foil containing no alloy element was annealed at 1000° C. for 30 minutes in an atmosphere of a mixed gas of 50 sccm argon and 10 sccm hydrogen to form a step structure, and graphene was synthesized thereon by CVD at 800° C. for 30 minutes in an atmosphere of a mixed gas of 70 sccm methane and 10 sccm hydrogen (see FIG. 10( b ) ).
[0059] As can be seen in FIG. 10( a ) , diamond particles were grown on multilayer graphene on the copper alloy foil, and as can be seen in FIG. 10( b ) , multilayer graphene and diamond particles were grown together on the copper foil. It could be seen that carbon radicals were rapidly produced on the copper alloy foil even at 800° C. lower than 1000-1060° C. at which graphene is conventionally synthesized by CVD. Also, it could be seen that, when a step structure is formed on a copper foil, graphene is grown thereon even at low temperature.
[0060] Thus, when a step structure is sufficiently developed, graphene can be synthesized by reducing the concentration of hydrogen gas or shortening the synthesis time.
[0061] As can be seen in FIG. 10( a ) , when the amount of the alloy is excessive, monolayer graphene can be obtained by reducing the alloy amount to 1 atom % or less or reducing the concentration of hydrocarbon and the synthesis time. As can be seen in FIG. 10( b ) , when the concentration of hydrocarbon gas is excessively high, the production of carbon radicals is faster than the growth of graphene, and thus graphene grows at the nucleation sites while triangular or rectangular plate-like carbon or wire- or particle-like carbon grows. Even in this case, monolayer graphene could be obtained by reducing the concentration of hydrocarbon or increasing the concentration of hydrogen gas during the synthesis of graphene. From this phenomenon, the present inventors could find that the formation of step structures promotes the production of carbon radicals and the growth rate of graphene, thus greatly contributing to forming monolayer graphene.
Example 5
Examination of Growth of Graphene on Catalyst Substrate Containing Various Alloying Elements
[0062] As a control for the graphene prepared in Example 4, copper foil was annealed at 1000° C. for 30 minutes in an atmosphere of a mixed gas of 50 sccm argon and 10 sccm hydrogen, and graphene was synthesized thereon by CVD at 1000° C. for 30 minutes in an atmosphere of a mixed gas of 15 sccm methane and 10 sccm hydrogen. The results are shown in FIG. 11( a ) .
[0063] Meanwhile, FIG. 11( b ) shows the results obtained by annealing a copper alloy foil containing 80 ppm of silver at 800° C. for 30 minutes in an atmosphere of a mixed gas of argon 20 sccm and 10 sccm hydrogen and then synthesizing graphene thereon by CVD at 1000° C. for 5 minutes in an atmosphere of a mixed gas of 20 sccm methane and 10 sccm hydrogen. FIG. 11( c ) shows the results obtained by annealing a copper alloy foil containing 40 ppm of chromium at 1000° C. for 30 minutes in atmosphere of a mixed gas of 50 sccm argon and 10 sccm hydrogen and then synthesizing graphene thereon by CVD at 800° C. for 3 minutes in an atmosphere of a mixed gas of 20 sccm methane and 10 sccm hydrogen; FIG. 11( d ) shows the results obtained using a copper alloy foil containing 200 ppm of iron under the conditions as the case of FIG. 11( c ) ; FIG. 11( e ) shows the results obtained using a copper alloy foil containing 130 ppm of cobalt under the conditions as the case of FIG. 11( c ) ; FIG. 11( f ) shows the results obtained using a copper alloy foil containing 100 ppm of nickel under the conditions as in the case of FIG. 11( c ) ; FIG. 11( g ) shows the results obtained using a copper alloy foil containing 140 ppm of silver under the conditions as the case of FIG. 11( c ) ; and FIG. 11( h ) shows the results obtained using a copper alloy foil containing 70 ppm of silicon under the conditions as the case of FIG. 11( c ) . As can be seen therein, the step structures were well developed and graphene was epitaxially grown. Herein, the dark areas in the graphene are separated parts to the catalyst surface, or grain boundaries or twins, which absorbed or irregularly reflected electrons because the step structures below the graphene layer changed.
[0064] In addition, it was found that, even when CVD synthesis was carried out at 1000° C. for 1 second in an atmosphere of a mixed gas of 30 sccm methane and 10 sccm hydrogen, well developed step structures and formed graphene nuclei (see FIG. 12 ).
[0065] While the invention has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the present application. | The present invention relates to a method for producing graphene on a face-centered cubic metal catalyst having a plane oriented in one direction, and more particularly to a method of producing graphene on a metal catalyst having the (100) or (111) crystal structure and a method of producing graphene using a catalyst metal foil having a single orientation, obtained by electroplating a metal catalyst by a pulse wave current and annealing the metal catalyst. The invention also relates to a method of producing graphene using a metal catalyst, and more particularly to a method of producing graphene, comprising the steps of: alloying a metal catalyst with an alloying element; forming step structures on the metal catalyst substrate in an atmosphere of a gas having a molecular weight of carbon; and supplying hydrocarbon and hydrogen gases to the substrate. On unidirectionally oriented metal catalyst prepared according to the present invention, graphene can be grown uniformly and epitaxially. Moreover, a method for producing graphene according to the present invention can form monolayer graphene by epitaxially growing graphene while increasing the growth rate of graphene. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a Section 371 of International Application No. PCT/EP2006/002550, filed Mar. 21, 2006, which was published in the German language on Nov. 2, 2006, under International Publication No. WO 200 6/114169 A1 and the disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
The invention relates to a device for fluid treatment, in particular to waste water treatment, having a circulation pump and a closed housing, in which is arranged at least one disk stack through which waste water may flow.
Such devices for waste water treatment, in which at least one disk stack, through which waste water flows, is arranged in a closed housing and in which the waste water is circulated by way of a circulation pump, is known from International Publication No. WO 02/094724 A1, for example. There, two disk stacks which mesh with one another and which many be moved relative to one another by way of a drive motor, in order to remove the biological coating growing on the surfaced sides of the disks to a desired extent, are arranged within a housing. Waste water flows radially through the disk stacks, which thereby is purified by the biological coating in the form of the microorganisms, adhering to the disks, i.e. the substances located in the waste water are broken down biologically. In order to convey the water through these biological filters, a circulation pump in the form of a centrifugal pump is provided, with which the waste water may be circulated within the biological filter, as well as being able to be delivered in and out of this.
With this known device, the disk stacks are arranged within a closed housing, wherein a drive shaft is led out to one side, via which a drive of a disk stack is effected. Pipe connections are provided at the other side, to which a circulation pump is to be connected.
The disadvantage with the designs described there, is the fact that they are not only expensive with regard to their construction, but furthermore also require a stationary assembly, since apart from the actual bio-filter, one also needs to provide the circulation pump assembly as well as the associated piping, which takes up much space and requires some effort with regard to construction.
BRIEF SUMMARY OF THE INVENTION
Against this background, it is an object of the invention, to provide a device of the known type, such that it may be constructed in a manner which is as space-saving as possible, and may be designed in an inexpensive and compact manner.
This object is achieved according to the invention by having the housing, with the disk stack located therein, and the circulation pump form a construction unit. Advantageous embodiments of the invention are specified in the following description and the drawings.
The device according to the invention for fluid treatment, in particular waste-water treatment, comprises a closed housing in which at least one disk stack is arranged through which waste water may flow, wherein the housing, with the disk stack located therein, and the circulation pump, which ensures the fluid circulation within the housing, form a construction unit.
The basic concept of the present invention is therefore to completely make do without a separate pump, and the piping between the biological filter and the pump which this requires, and instead, to design the circulation pump and the housing as a construction unit.
Thereby, advantageously at least a part of the pump is a constituent of the housing, in order in this manner, on the one hand to provide a space-saving design, and on the other hand to reduce the manufacturing costs and assembly costs compared to known devices.
Thereby, the circulation pump may either be designed in a submersing manner in the form of a submersible pump within the housing, typically into the disk stack, or only form a part of the housing, typically an end-side cover or a transverse wall. With the first solution, it is particularly advantageous for the pump to be arranged completely or at least to a great extent within the disk stack, preferably in a central cavity which is anyway only used for through-flow purposes.
A particularly inexpensive housing construction shape results if the housing is designed in a tubular manner, since then, the tubular part may be formed by a tube or a tube section, and one merely needs to provide covers or other terminating transverse walls on the end side. Basically, although a tubular housing may be manufactured by molding, i.e. as a cast part, the construction from a cut-to-size tube, in combination with end-side covers or a transverse wall, is often more favorable, since with this construction form one may also apply disk stacks of different size without special housing variants having to be provided for this. With a housing designed in a tubular manner, it is particularly favorable to arrange the centrifugal pump in or on a transverse wall or an end-side cover which may form the transverse wall. The circulation pump may thereby be integrated at least partly into the housing in a space-saving manner, and given a suitable design of the transverse wall, this may also form part of the pump or at least serve for fastening the pump.
If this transverse wall is formed by a cover closing the housing at the end-side, this has the advantage that on account of the cover, on the one hand the tubular housing is closed at the end-side, and on the other hand, the pump fastened on or in the cover may be arranged such that typically the electrical drive part is arranged outside, and the hydraulic drive part within the cover or housing. In the ideal case, one may thereby completely make do without piping, and the circulation pump may be integrated into the device in an almost ideal manner.
A further advantage of the cover arrangement is that after the removal of the cover from the housing, on the one hand the pump is well accessible, and on the other hand the disk stacks within the housing are also easily accessible. Usually, two or more disk stacks mesh with one another, for example in that one or more disk stacks are stationary and the other or several disk stacks may be moved relative to this. In any case, a drive for the rotation of at least one disk stack is necessary. This drive advantageously comprises a drive motor arranged outside the housing, so that the electrical components of the motor do not need to be sealed and insulated with respect to the fluid located in the housing. For this purpose, the motor is advantageously arranged on the cover in a direct or indirect manner, wherein the drive shaft is led in a sealed manner through the cover in which the centrifugal pump is arranged. Such an arrangement has the advantage that all electrical connections of the device are arranged at one side, and furthermore, the remaining housing may be designed in a comparatively inexpensive and simple manner.
The motor driving the pump is advantageously arranged within this cover closing the tubular housing to one side, or on this component. This arrangement too has the advantage that the motor does not come into contact with the fluid located within the housing, and all electrical connections are freely accessible from the outside.
It is particularly advantageous for the cover not only to serve for fastening the circulation pump, but also for the cover to form at least also a part of the pump housing, since in this manner a component, which is required anyway, may assume functions for the pump as well as for the housing of the device.
The cover thereby is advantageously designed of several parts, and comprises an outer cover part which closes the housing to the outside, as well as an inner cover part which closes the cover to the inside, which are connected to one another in a preferably detachable manner. The cover may assume further pump-side functions by way of this multipart construction. Furthermore, with a suitable design, one may apply components free of undercuts on account of the multipart construction, which may be manufactured inexpensively.
Advantageously here, the cover inner part is designed such that it forms the suction port of the pump. Here, with a suitable design of the device, one may for example connect a central channel leading through the disk stacks to the suction port of the pump in a direct manner within the housing, so that very direct and favorable flow conditions are achieved.
It is advantageous if an intermediate part is provided between the cover inner part and the cover outer part, the intermediate part surrounding an impeller of the pump and in which the pressure-side flow channel of the pump lies. The actual pump housing, in particular the hydraulically effective part of the pump housing, is then formed by this intermediate part. The provision of such an intermediate part is particularly favorable with regard to manufacturing technology, since then, given a suitable design, all cover components may be able to be manufactured in a comparatively simple manner, as the case may be also without undercuts. However, one may also group components together. It may therefore be advantageous to design the cover inner part and the intermediate part as one piece as a common component, which quasi forms the complete pump housing from the suction port to the pressure-side exit.
The intermediate part advantageously comprises an ejector, thus a jet pump, with which gas may be admixed to the pressure-side channel of the pump. Such gas is typically required with devices of this type, in order to control the biological/chemical process or maintain this. Such a gas, typically a gas containing oxygen, may be supplied to the fluid system without external energy by way of the ejector.
It is advantageous if the ejector comprises a first gas channel running through the cover inner part and leading into the housing, and preferably a second gas channel running through the cover outer part and leading outwards, outside the housing. Then specifically, by way of this gas channel, the upper cover inner part is connected to the inside of the housing, where a gas bubble also exists during operation of the device. At the same time, a connection to a gas reservoir, e.g., a pressurized gas bottle, is formed via the second channel from outside the housing, so that gas from the reservoir or gas from the housing may be admixed to the fluid flow, depending on the process control and requirements.
The housing with its middle longitudinal axis is arranged roughly horizontally, in order to ensure that the gas bubble is always arranged in the region which is connected to the ejector via the channel in the cover inner part, wherein the channel leading to the ejector and running through the cover inner part runs out in the housing at the top.
The cover inner part advantageously comprises a further channel which connects the inside of the housing to the pressure side of the circulation pump, wherein this channel runs out within the housing below the channel leading to the ejector and at a distance preferably below and/or next to the suction port of the pump. With such an arrangement, via the suction port of the pump, one may centrally take fluid from the middle of the disk stack and introduce it through the pressure channel into the housing again, so that this fluid to be treated flows quasi radially from the outside inwards through the disk stack or disk stacks. Thereby, by way of the arrangement of the channels to one another, one ensures that the channel leading to the ejector always runs out in the region of the gas bubble and the two other channels (suction channel and pressure channel of the pump) run out below the fluid level within the housing.
The cover according to the invention, which may preferably be formed of two, three or more components, may be manufactured in an inexpensive manner as a milled part or, with larger production numbers, also as a cast part to be manufactured in a coreless manner.
The channel arrangement in the flow direction of the pump is advantageously such that an outlet channel for gas out of the housing and an inlet opening therebehind for gas out of the reservoir run out in the pressure channel, both however preferably in front of the ejector in the flow direction.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
The foregoing summary, as well as the following detailed description of the invention, will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there are shown in the drawings embodiments which are presently preferred. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown. In the drawings:
FIG. 1 is a greatly simplified longitudinal sectional view of a part of the device according to an embodiment of the invention;
FIG. 2 is a greatly simplified longitudinal sectional view of the other part of the device shown FIG. 1 ; and
FIG. 3 is a transverse sectional view through the cover along the section III-III in FIG. 1 .
DETAILED DESCRIPTION OF THE INVENTION
The waste water treatment device represented by way of the figures comprises an essentially cylindrical housing 1 , which is formed of a tube section 2 with end covers 3 and 4 , which close the tube section 2 at the ends.
Whereas the disk-like cover 3 closing the tube section 2 on the right side and represented in FIG. 2 , is formed as one piece and in a stepped manner, so that it engages with one part into the tube section 2 and with another part lies on this at the end, the cover 4 , shown in FIG. 1 and closing the tube section 2 on the left side in the drawing, is constructed of several parts.
The cover 4 consists of an outer disk-like cover part (cover outer part) 5 forming the actual cover, as well as a likewise disk-like intermediate inner part and cover inner part 6 , which is releasably connected to the cover outer part 5 . The cover outer part 5 , just as the cover 3 , likewise comprises a section engaging in the tube section 2 , as well as a section bearing on this at the end, thus is designed in a stepped manner and provided with a seal 7 , as is also provided on the cover 3 , and seals the respective covers 3 and 4 with respect to the tube section 2 .
The fastening of the covers 3 , 4 on the tube section 2 is effected by way of a peripheral tension strap 8 , which as a flat strip is formed with two radially inwardly pointing flanks. Of these flanks, the one engaging over the tube section 2 engages into a groove 9 at the end of the tube section 2 , while the other engages over the cover 3 and 4 on the outer side and thus fixes this on the tube section 2 with a positive fit. The tension strap 8 is equipped with a tensioning device known per se, which in a first opened position extends the strap to such an extent that the flank may be pushed over the free end of the tube section 2 , and in a second closed position tensions this, bearing tightly on the outer periphery of the tube section 2 , as well as of the associated cover 3 , 4 , so that this is fixed with a non-positive and positive fit.
A disk stack, which is formed of a multitude of disks 10 arranged with a spacing next to one another, is arranged within the housing 1 . The disk stack is constructed of two sorts of disks, which in each case are arranged in an alternating manner and are designed such that, with a drive by a rack 11 provided with teeth on the other periphery, they are rotated with a different speed and about different axes, as described in detail in European patent application 04 016 525.0, which is expressly referred to inasmuch as this is concerned. There, a comparable cylinder-shaped housing, with disk stacks arranged therein and whose drive is described by way of FIG. 6 and corresponds essentially to the present application, is shown by way of example in FIG. 9 .
In any case, the disks 10 are rotatably arranged within the housing 1 , and the drive is effected via the rack 11 , which extends over essentially the whole length of the housing 1 and which engages into the outer toothings of the one of the two disk types. A tube 12 is led through central openings 20 of the disks 10 and comprises recesses, and not only serves for the removal of the fluid flowing radially inwards from the outside through the disk stack, but also as a counter bearing to the rack 12 . This tube 12 has a significantly smaller diameter than the central openings 20 in the disks 10 , so that the disks 10 of the disk stack do not roll on this tube 12 and thus do not roll about their central axis. This effect too, is described in detail in European patent application 04 016 525.0, and this is referred to inasmuch as this is concerned.
With an arrangement as specified, the housing 1 is aligned such that the housing longitudinal axis is arranged essentially horizontally. The waste water which is to be cleaned and is located within the housing 1 does not completely fill out the inside of the housing, but only up to a level 13 , and the space located above this is filled with gas. The disk stack is not only radially supported within the housing, but also axially supported. The waste water located therein is circulated such that it flows in at the outer periphery of the disk stack, flows radially past and between the disks 10 , and is led away again through the central recess 20 or the tube 12 , as is indicated in FIG. 1 by the arrow representations.
A circulation pump 14 is provided, which is integrated in the cover 4 , in order to build up the differential pressure required for the circulation or the supply and removal of the water. The circulation pump 14 is designed as a centrifugal pump and comprises an impeller 15 , which is arranged within the cover 4 , so that the cover 4 also forms the pump housing. The impeller 15 is radially surrounded by a cover intermediate part 6 b , which in the represented embodiment is designed as one piece with a cover inner part 6 a , which closes the cover intermediate part 6 b to the inside of the housing and forms the suction port 16 of the pump.
A seal 17 is provided to the inside, between the suction port 16 of the pump and the disk stack, and this seal prevents an overflow between the suction side and pressure side of the pump. A housing volute, thus a channel 18 deflecting the pressure-side flow departing radially from the impeller, and an ejector 19 , which connects thereto in the flow direction, is likewise formed within the cover intermediate part 6 b and runs into a diffuser 20 , which via a transverse recess 21 that passes through the cover inner part 6 a , is conductively connected to the inside of the housing on the other side of the seal 17 below the level 13 , are provided in the cover intermediate part 6 b formed by the component 6 .
The suction-side part of the ejector 19 forms a U-shaped channel 21 , which is represented in FIG. 3 in dashed lines and runs out in the ejector 19 at two inlets 22 . The U-shaped channel 21 is connected via a channel 23 which passes through the component 6 , to the inside of the housing, and specifically above the water level 13 , thus in the region of the gas bubble, and via a channel 23 ′ arranged in the cover outer part 5 aligned thereto, is connected to the surroundings. The channel 23 ′ is provided for connection to a conduit, which leads to a gas reservoir, here a pressurized oxygen bottle. Thus, oxygen may be supplied to the system via the channel 23 ′. Thus, in the ejector 19 during the pump operation, either oxygen from the pressurized bottle is introduced via the channel 23 ′, or gas from the housing is introduced into the pressure-side fluid flow via the channel 23 ′, and specifically by way of the U-shaped channel 21 via the inlet openings 22 .
The impeller 15 of the centrifugal pump is seated on a shaft 24 , which is driven by a drive motor 25 , which is incorporated in a recess in the cover outer part 5 and is releasably fastened there. The shaft 24 carrying the impeller 15 is sealed with respect to the motor, and the motor 25 is designed as a dry runner. However, alternatively one may also use a wet-running motor, and then the sealing to the motor is effected essentially via the canned pot.
The cover 4 in its region at the bottom in FIG. 1 comprises yet another recess for the drives of the rack 11 . For this, a shaft lead-through 29 is provided in the component 6 , and this is designed in a sealed manner. The one end of this shaft 26 is connected to the rack 11 , the other end to a coupling, via which the exit-side shaft of a worm gear 27 is connected, whose input shaft is connected to the drive shaft of a motor 28 , which via the gear 27 together with this is fastened on the cover 4 , in particular on the cover part 5 , and ensures a rotational drive of the rack 11 . As is evident from FIG. 1 , the electrical connections of the drive motor 25 and the motor 28 lie outside the housing and are spatially assigned to one another, so that the electrical supply of the device may be effected from one side.
Not only are all electrical assemblies of the device unified in the cover 4 , but also the sensor devices required for operation. Thus, a level sensor which is required for the closed-loop control of the degree of filling of the device, is arranged within a bore 30 of the component 6 , in order on the one hand to ensure that the disk stack is completely submersed in fluid, and on the other hand that adequate free space is present for the gas bubble located in the upper region of the housing. The bore 30 passes through the cover 4 , so that the sensor may be applied and is electrically connectable from the outside.
Furthermore, a bore 31 is provided in the cover outer part 5 , which passes through this and runs out in the pressure channel 18 in the flow direction in front of the ejector 19 . This bore 31 serves for integrating a pressure sensor for detecting the pressure on the pressure side of the pump. The suction-side pressure is detected by way of a tube (not shown in the drawings), which runs out in the region of the suction port of the pump and is connected via a bore 32 passing through the cover 4 . A pressure sensor is likewise provided in this tube, so that the differential pressure of the pump may be detected with the help of the two pressure sensors.
Furthermore, a threaded bore 33 , which is sealingly closed with a screw on operation, is provided in the lower region of the cover 4 . This screw serves as a volute, after whose removal the fluid may flow out of the housing 1 .
Two conduit connections, which run into recesses 34 and 35 of the cover outer part 5 , are provided on the outer side of the cover 4 , in particular of the cover outer part 5 , and these connections are not visible in the drawings. The recesses 34 and 35 pass through the cover outer part 5 in a channel-like manner and run out in the cover intermediate part 6 b within the pressure channel 18 , and specifically, seen in the flow direction, firstly the recess 35 and therebehind the recess 34 . The recess 35 serves for the removal of the water purified in the device, while the recess 34 is envisaged for the supply of the pipe water to be cleaned in the device.
Thus, with the design described above, all electrical sensor connections and conduit connections are integrated within the cover 4 or are arranged on this. The cover 4 in the previously described embodiment is formed of two components 5 and 6 , which are designed without undercuts and thus are favorable with regard to manufacturing technology, for example by milling/drilling from a disk of round material. Here, the component 6 may consist of two individual components 6 a and 6 b , which bear on one another in a sealed and firm manner.
It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims. | A device is provided for treating waste water, the device including a closed housing containing at least one stack of disks through which waste water can flow. A circulating pump is provided for pumping the fluid, the pump forming a structural unit including the housing and the stack of disks arranged therein. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a tuft yarn selection mechanism and in particular, but not exclusively, an axminster loom incorporating such a selection mechanism.
2. Related Art
When weaving on a typical gripper axminster loom the carpet normally has three weft yarns per tuft loop (three shot carpet) whereas carpet woven on other types of loom usually have two weft yarns per tuft loop (two shot carpet).
The weft yarns are inserted in succession and so a 50% increase in carpet production can be achieved on an axminster loom if two weft yarns could be inserted without loss of insertion speed.
With a conventional axminster loom the speed of operation of the tuft yarn selection mechanism is too slow to enable correct selection of tuft yarns to be achieved for a two shot operation.
A general aim of the present invention is to provide a tuft yarn selection mechanism which operates at a sufficiently high speed to enable a twoshot carpet to be produced on gripper axminster loom without loss of insertion speed.
SUMMARY OF THE INVENTION
According to one aspect of the present invention there is provided a tuft yarn selection mechanism for a gripper axminster loom, the mechanism including a plurality of yarn carriers each of which is movable to any one of a plurality of predetermined positions, each carrier guiding a plurality of tuft yarns and being arranged to present one of said yarns to a gripper when the carrier is located at a corresponding one of said predetermined positions, and a plurality of independently controllable rotary drive motors, each drive motor being drivingly connected to an associated carrier for selectively moving the associated carrier to a selected one of said predetermined positions.
Preferably, each motor is an electric motor and is electrically controlled to move the associated carrier to said selected one of said predetermined positions.
Preferably the electric motor is a stepper motor.
Preferably each carrier has associated therewith sensing means for determining the position of the carrier and providing a signal indicative of the carrier being located at a selected one of said predetermined positions.
The sensing means may be used to determine arrival of the carrier at a selected one of said positions and thereby provide a signal to control stopping of the motor. Alternatively, electronic control means may be provided which transmit to the stepper motor a sufficient number of pulses to move the carrier from one position to the selected position, the sensor being arranged to confirm correct positioning of the carrier. In the event that the carrier is not correctly positioned (eg. it has overshot slightly), the sensor is used to provide a signal which is utilised by the electronic control means to correctively re-adjust the position of the carrier.
Preferably the yarn carriers are elongate and arranged to move longitudinally between said predetermined positions.
According to another aspect of the present invention there is provided a mechanism for a gripper axminster loom, the mechanism including a plurality of yarn carriers each of which is movable to any one of a plurality of predetermined positions, each carrier guiding a plurality of tuft yarn and being arranged to present one of said yarns to a gripper when the carrier is located at a corresponding one of said predetermined positions, and a plurality of independently controllable drive motors, each drive motor being drivingly connected to an associated carrier for selectively moving the associated carrier to a selected one of said predetermined positions, each drive motor being removably mounted to enable the drive motor to be disconnected from said associated carrier.
According to another aspect of the present invention there is provided a mechanism for a gripper axminster loom, the mechanism including a plurality of yarn carriers each of which is movable to any one of a plurality of predetermined positions, each carrier guiding a plurality of tuft yarn and being arranged to present one of said yarns to a gripper when the carrier is located at a corresponding one of said predetermined positions, and a plurality of independently controllable drive motors, each drive motor being drivingly connected to an associated carrier for selectively moving the associated carrier to a selected one of said predetermined positions, monitoring means for each carrier arranged to provide a signal indicative of the position of the associated carrier, and control means responsive to said signal in order to independently control the motor associated with each carrier.
Preferably the electric motors are arranged in groups, the motors of each group being mounted upon a common support.
According to another aspect of the present invention there is provided a gripper axminster loom adapted to weave a two-shot carpet.
BRIEF DESCRIPTION OF THE DRAWINGS
Various aspects of the present invention are hereinafter described with reference to the accompanying drawings, in which:
FIG. 1 is a side view of a first embodiment according to the present invention;
FIG. 2 is an end view of the first embodiment shown in FIG. 1;
FIG. 3 is a side view of a second embodiment according to the present invention;
FIG. 4 is an end view of the second embodiment; and
FIG. 5 is an enlarged view of a motor and pinion gear shown in FIG. 3
DETAILED DESCRIPTION
A tuft yarn selection mechanism 10 according to a first embodiment shown in FIGS. 1 and 2 and includes a plurality of elongate tuft yarn carriers 12 . Each carrier 12 is provided with a plurality of yarn guides 14 to which tuft forming yarns 15 are fed.
The yarn guides 14 are spaced from one another along the length of the carrier 12 and the carrier 12 is slidably mounted in guide blocks 13 for longitudinal movement such that any one of the yarn guides 14 can be moved into registry with a gripper 16 .
The gripper 16 draws yarn 15 from a guide 14 which has been presented thereto in order to form a tuft in a known manner.
As is conventional, there is a gripper 16 for each tuft site in the loom and a yarn carrier 12 for each gripper 16 .
Accordingly across the width of the loom, there is provided a large number of yarn carriers 12 which are arranged side by side and are closely spaced. This is illustrated, in a representative manner, in FIG. 2 .
Each yarn carrier 12 is moved longitudinally by an individual rotary drive motor 6 to any one of a plurality of predetermined longitudinal positions each of which corresponds to a guide 14 being in registry with the associated gripper 16 .
Preferably each drive motor 6 is arranged to drive a pinion gear 30 which meshes with a rack 31 on the associated yarn carrier 12 . In FIG. 1, the motor 6 is preferably drivingly connected to its associated pinion gear 30 by a timing belt 33 and pulley 7 .
Preferably a sensor 40 is provided which senses the presence of individual markers 41 which correspond in number to the number of yarn guides 14 . The markers 41 are spaced along the length of the carrier 12 by the same spacing as guides 14 and so provide an indication as to the position of guides 14 .
Electronic control means (not shown) are provided which control each motor 6 in order to move its associated carrier 12 in the desired direction and by the desired distance in order to move a selected yarn guide 14 into registry with the gripper 16 .
Preferably the sensor 40 acts to provide a signal which is indicative of the carrier 12 arriving at a desired position, the signal being utilised by the control means to stop movement of the carrier 12 by arresting the motor 6 . The motor 6 then acts to temporarily hold the carrier 12 at its selected position.
The motor 6 may be a stepper motor. In such a case, the control means may act to supply a predetermined number of pulses to the stepper motor in order to move the carrier 12 from one position to another position. The sensor 40 may then be utilised to confirm that the carrier 12 is correctly positioned, and if not, enable the control means to correct positioning of the carrier.
Conveniently the markers 41 are defined by slots formed in the carrier 12 and preferably the sensor 40 comprises an optical sensor which is capable of sensing the presence of the slots.
Preferably the motors 6 and associated pinion gears 30 are arranged in groups with all motors 6 and pinion gears 30 of each group being mounted on a common support 50 , preferably in the form of a plate 51 which is removably mounted on the loom frame.
This has the advantage of enabling a faulty motor 6 to be quickly removed and replaced by removal of a plate 51 having the faulty motor 6 and replacement by a new plate 51 . With such an arrangement, the replacement of a motor 6 may be carried out without moving the carriers 12 and disturbing yarns 15 .
As seen in FIG. 1, the pinion gears 30 are spaced apart in the longitudinal direction of the carriers 12 and the plate 51 is preferably mounted so as to extend at an inclined angle laterally relative to the carriers 12 such that adjacent pinion gears 30 may engage with the racks of adjacent carriers 12 .
If the shafts 22 on which the pinion gears 30 are mounted project perpendicularly from the plate 51 , the gears 30 will have an axis of rotation which is not perpendicular to the longitudinal axis of the rack on associate carrier 12 . This misalignment can be accommodated by the provision of suitable gear teeth on the pinion gear and/or rack.
Alternatively, the shafts 22 of the pinion gears 30 may be mounted so as to project from the plate 51 at an acute angle so as to ensure that the axis of rotation of each pinion gear is perpendicular to the longitudinal axis of the rack.
The motors 6 are preferably arranged in two rows extending parallel to the longitudinal direction of the carriers.
With this arrangement, it is possible to accommodate relatively large motors 6 for driving closely spaced carriers 12 . It will be appreciated that, in each group of motors 6 , the motors 6 may be arranged in one row or in more than two rows.
A second embodiment 60 is illustrated in FIGS. 3 to 5 , wherein parts similar to those in the first embodiment are referenced by the same reference numerals
In embodiment 60 , each motor 6 is arranged to directly drive an associated pinion gear 30 via a drive gear 61 . Accordingly in the second embodiment, all motors 6 carried by the common support plate 51 are arranged in one row. The plate 51 is inclined across adjacent carriers 12 to enable individual pinion gears 30 to mesh with an associated carrier.
In embodiment 60 , sensor 40 for sensing the position of the associated carrier has been repositioned to co-operate with the teeth 37 of the associated pinion gear 30 . In this respect the sensor 40 is preferably an optical sensor which is arranged to detect the spaces between the pinion teeth 37 as the pinion gear rotates.
Accordingly, in embodiment 60 , markers 41 on each carrier 12 have been dispensed with.
Optionally, a further sensor 140 may be provided for co-operating with a marker 141 on each carrier 12 . The marker 141 is positioned along the carrier to indicate a desired reference position, preferably a mid-way position in the travel of the carrier 12 . This enables each carrier to be moved to the reference position and enables calibration of sensors 40 to be achieved.
In addition, if desired, the provision of sensor 140 in combination with marker 141 enables each carrier 12 to be moved to its mid-position prior to being moved to the next selected position of the carrier for delivering a desired yarn to the associated tuft gripper.
In the above embodiments, motors 6 are electrically powered. It will be appreciated that they may be fluid powered in which case the control means would be arranged to control flow of fluid to the motors in order to control movement of the carriers.
It will be appreciated that the carriers 12 are moved by motors which act independently of one another and independently of the main drive shaft of the loom.
It will be appreciated that by appropriate control from the control means, each carrier 12 can be individually controlled to move from one position to another selected position at any desired time within the weaving cycle and at any desired speed. It is therefore possible with the present invention to quickly and accurately position the carriers 12 in a gripper axminster loom to enable two-shot carpet to be produced. | A mechanism for a gripper Axminster loom is disclosed which includes a plurality of yarn carriers each of which is movable to any one of a plurality of predetermined positions. Each carrier guides a plurality of tuft yarn and is arranged to present one of the yarns to a gripper when the carrier is located at a corresponding one of the predetermined positions. The mechanism includes a plurality of independently controllable rotary drive motors, each of which is connected to drive an associated carrier for selectively moving the associated carrier to a selected one of the predetermined positions. | 3 |
FIELD OF THE INVENTION
The present application relates to cleaning and/or treatment compositions comprising anti-foams and methods of making and using such compositions.
BACKGROUND OF THE INVENTION
Cleaning and/or treatment compositions may employ materials that produce suds. In certain cleaning and/or treatment compositions, the level of suds is higher than desired. One manner of reducing suds is to add an antifoamer to the cleaning and/or treatment composition. Unfortunately, antifoamers may be incompatible with other compositional components or the situs that is treated thus leading to product instability. The compositions disclosed herein address in part, certain aspects of such stability issue.
SUMMARY OF THE INVENTION
The present application relates to cleaning and/or treatment compositions comprising anti-foams and methods of making and using such compositions. Such compositions encompass consumer products, cleaning and/or treatment compositions, fabric care compositions, or liquid laundry detergents that provide the desired suds profile via the addition of an antifoamer, yet are stable.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
As used herein “consumer product” means baby care, beauty care, fabric & home care, family care, feminine care, health care, snack and/or beverage products or devices intended to be used or consumed in the form in which it is sold, and not intended for subsequent commercial manufacture or modification. Such products include but are not limited to diapers, bibs, wipes; products for and/or methods relating to treating hair (human, dog, and/or cat), including, bleaching, coloring, dyeing, conditioning, shampooing, styling; deodorants and antiperspirants; personal cleansing; cosmetics; skin care including application of creams, lotions, and other topically applied products for consumer use; and shaving products, products for and/or methods relating to treating fabrics, hard surfaces and any other surfaces in the area of fabric and home care, including: air care, car care, dishwashing, fabric conditioning (including softening), laundry detergency, laundry and rinse additive and/or care, hard surface cleaning and/or treatment, and other cleaning for consumer or institutional use; products and/or methods relating to bath tissue, facial tissue, paper handkerchiefs, and/or paper towels; products and/or methods relating to oral care including toothpastes, tooth gels, tooth rinses, denture adhesives, tooth whitening; over-the-counter health care including pain relievers, pet health and nutrition, and water purification.
As used herein, the term “cleaning and/or treatment composition” includes, unless otherwise indicated, granular or powder-form all-purpose or “heavy-duty” washing agents, especially cleaning detergents; liquid, gel or paste-form all-purpose washing agents, especially the so-called heavy-duty liquid types; liquid fine-fabric detergents; hand dishwashing agents or light duty dishwashing agents, especially those of the high-foaming type; machine dishwashing agents, including the various tablet, granular, liquid and rinse-aid types for household and institutional use; liquid cleaning and disinfecting agents, including antibacterial hand-wash types, cleaning bars, mouthwashes, denture cleaners, dentifrice, car or carpet shampoos, bathroom cleaners; hair shampoos and hair-rinses; shower gels and foam baths and metal cleaners; as well as cleaning auxiliaries such as bleach additives and “stain-stick” or pre-treat types, substrate-laden products such as dryer added sheets, dry and wetted wipes and pads, nonwoven substrates, and sponges; as well as sprays and mists.
As used herein, the term “fabric care composition” includes, unless otherwise indicated, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions and combinations thereof.
As used herein, the articles “a” and “an” when used in a claim, are understood to mean one or more of what is claimed or described.
As used herein, the terms “include”, “includes” and “including” are meant to be synonymous with the phrase “including but not limited to”.
As used herein, the term “solid” means granular, powder, bar and tablet product forms. As used herein, the term “situs” includes paper products, fabrics, garments, hard surfaces, hair and skin.
As used herein, the term “heteroatom” takes its ordinary, customary meaning, and thus includes N, O, S, P, Cl, Br, and I.
Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
All percentages and ratios are calculated by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition unless otherwise indicated.
It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.
Compositions
In one aspect, a composition comprising a polymer, having a number average molecular weight of from about 200 Daltons to about 10,000,000 Daltons, from about 500 Daltons to about 10,000,000 Daltons, from about 1,000 Daltons to about 10,000,000 Daltons, or from about 1,500 Daltons to about 10,000,000 Daltons, that comprises from about 50 mol % to about 100 mol %, or from about 60 mol % to about 100 mol %, or from about 70 mol % to about 100 mol %, or from about 80 mol % to about 100 mol %, or from about 90 mol % to about 100 mol % units of Formula (I) below,
R a (R 1 O) b R 2 c SiO (4-a-b-c)/2 Formula (I)
wherein: a) each R is independently selected from: H, a monovalent, SiC-bonded, optionally substituted, aliphatic hydrocarbon radical that optionally comprises a heteroatom, or an aromatic hydrocarbon radical covalently attached to silicon via aliphatic groups, in one aspect each R is independently selected from: H, a monovalent, SiC-bonded, optionally substituted, C 1 -C 50 aliphatic hydrocarbon radical that optionally comprises a heteroatom, or a C 6 -C 16 aromatic hydrocarbon radical covalently attached to silicon via aliphatic groups; b) each R 1 is independently selected from: H, or a monovalent, optionally substituted aliphatic hydrocarbon radical, that optionally comprises a heteroatom, in one aspect each R 1 is independently selected from: H, or a monovalent, optionally substituted C 1 -C 50 aliphatic hydrocarbon radical, that optionally comprises a heteroatom; c) each R 2 is a monovalent, optionally substituted, aromatic hydrocarbon radical which is attached to the silicon atom via a carbon ring atom, in one aspect each R 2 is a monovalent, optionally substituted, C 6 -C 16 aromatic hydrocarbon radical which is attached to the silicon atom via a carbon ring atom; d) the index a is 0, 1, 2 or 3; e) the index b is 0, 1, 2 or 3; f) the index c is 0, 1, 2 or 3; and optionally a filler and a resin; with the proviso for said polymer that for each of said polymer's Formula I units the sum of indices a, b, and c is less than or equal to 3; in 1-100%, 10-60%, or 20-40% of said polymer's Formula (I) units, c is other than 0; and in at least 50% of said polymer's Formula I units the sum of indices a, b, and c is 2.
In one aspect, said polymer's number average molecular weight is from about 200 Daltons to about 10,000,000 Daltons, from about 500 Daltons to about 1,000,000 Daltons, from about 1,000 Daltons to about 500,000 Daltons, or from about 1,500 Daltons to about 100,000 Daltons.
In one aspect of said composition, for:
a) each R group of said polymer:
i) each monovalent, optionally substituted, aliphatic hydrocarbon radical that optionally comprises a heteroatom is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, decyl, dodecyl, alkenyl, cycloalkyl, 3,3,3-trifluoro-n-propyl, cyanoethyl, glycidyloxy-n-propyl, polyalkylene glycol-n-propyl, amino-n-propyl, aminoethylamino-n-propyl, and methacryloyloxy-n-propyl, ii) each aromatic hydrocarbon radical covalently attached to silicon via aliphatic groups is independently selected from benzyl, phenylethyl, or 2-phenylpropyl,
b) each R 1 group of said polymer each monovalent, optionally substituted, aliphatic hydrocarbon radical that optionally comprises a heteroatom is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, decyl, dodecyl, alkenyl, cycloalkyl, 3,3,3-trifluoro-n-propyl, cyanoethyl, glycidyloxy-n-propyl, polyalkylene glycol-n-propyl, amino-n-propyl, aminoethylamino-n-propyl, and methacryloyloxy-n-propyl, c) each R 2 group of said polymer is independently selected from phenyl, substituted phenyl, naphthyl, or anthracyl.
In one aspect of said composition, for each R 2 group of said polymer is independently selected from phenyl, toloyl, xylyl, cumyl, naphthyl or anthracyl.
In one aspect of said composition, for each R 2 group of said polymer is independently selected from phenyl or toloyl.
In one aspect of said composition, the index b is 0 or 1, and the index c is 0, 1, or 2.
In one aspect of said composition, said composition comprises a resin and a filler, said filler having a BET surface area of 20 to 1000 m 2 /g, a particle size of less than 10 μm and an agglomerate size of less than 100 μm.
In one aspect of said composition, said filler is selected from the group consisting of silica, titanium dioxide, aluminum oxide, metal soaps, quartz flour, PTFE powders, fatty acid amides, ethylenebisstearamide, or hydrophobic polyurethanes.
In one aspect of said composition said filler comprises hydrophobic, precipitated silica and/or hydrophobic, fumed silica.
In one aspect of said composition, viscosity, at a shear rate of 20 sec at 25° C., of from about 10 cPs to about 50,000 cPs and comprising from about 1% to about 60%, from about 3% to about 50%, from about 5% to about 40% or from about 8% to about 30% of a surfactant selected from the group consisting of anionic surfactant, cationic surfactant, nonionic surfactant, zwitterionic surfactant, ampholytic surfactant and mixtures thereof and optionally one or more adjuncts are selected from the group consisting of builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach, bleach activators, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, hueing agents, UV absorbers, perfume, perfume delivery systems, structure elasticizing agents, thickeners/structurants, fabric softeners, carriers, hydrotropes, processing aids and/or pigments.
In one aspect of said composition, said composition comprises an anionic surfactant.
In one aspect of said composition, said anionic surfactant is selected from the group consisting of a C 11 -C 18 alkyl benzene sulfonate surfactant; a C 10 -C 20 alkyl sulfate surfactant; a C 10 -C 18 alkyl alkoxy sulfate surfactant, said C 10 -C 18 alkyl alkoxy sulfate surfactant having an average degree of alkoxylation of from 1 to 30 and the alkoxy comprises a C 1 -C 4 chain, and mixtures thereof.
In one aspect of said composition, said one or more adjuncts are selected from the group consisting of builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach, bleach activators, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, hueing agents, UV absorbers, perfume, perfume delivery systems, structure elasticizing agents, thickeners/structurants, fabric softeners, carriers, hydrotropes, processing aids and/or pigments.
In one aspect of said composition, said composition is a antifoam composition that comprises a filler and a resin and said resin comprising units of Formula (II) below:
R 3 d (R 4 O) e SiO (4-d-e)/2 Formula (II)
wherein:
a) each R 3 is independently selected from H, a monovalent, SiC-bonded, optionally substituted, aliphatic hydrocarbon radical that optionally comprises a heteroatom, or an aromatic hydrocarbon radical covalently attached to silicon via aliphatic groups, in one aspect, each R 3 is independently selected from H, a monovalent, SiC-bonded, optionally substituted, C 1 -C 50 aliphatic hydrocarbon radical that optionally comprises a heteroatom, or a C 6 -C 16 aromatic hydrocarbon radical covalently attached to silicon via aliphatic groups; b) each R 4 is independently selected from H, or a monovalent, optionally substituted aliphatic hydrocarbon radical, that optionally comprises a heteroatom, in one aspect, each R 4 is independently selected from H, or a monovalent, optionally substituted C 1 -C 50 aliphatic hydrocarbon radical, that optionally comprises a heteroatom; c) the index d is 0, 1, 2 or 3; and d) the index e is 0, 1, 2 or 3;
with the proviso that the sum of the indices d and e is less than or equal to 3 and in less than 50% of all of the units of the Formula (II) in the organopolysiloxane resin the sum of the indices d and e is 2.
In one aspect, said composition is a consumer product.
In one aspect, said composition is a cleaning and/or treatment composition.
In one aspect, said composition is a fabric care composition.
In one aspect, said composition is a liquid laundry detergent.
In one aspect, a composition comprising any combinations of the parameters and/or characteristics disclosed above is disclosed.
Process of Making Compositions
In one aspect, a process of making the composition disclosed herein is disclosed, said process comprising combining a surfactant, optionally one or more adjunct ingredients, and from about 0.001% to about 2%, or from about 0.005% to about 1%, or from about 0.01% to about 0.75%, or from about 0.05% to about 0.5% of an anti-foam composition disclosed herein comprising a polymer having a number average molecular weight of from about 200 Daltons to about 10,000,000 Daltons, from about 500 Daltons to about 10,000,000 Daltons, from about 1,000 Daltons to about 10,000,000 Daltons, or from about 1,500 Daltons to about 10,000,000 Daltons, that comprises from about 50 mol % to about 100 mol %, or from about 60 mol % to about 100 mol %, or from about 70 mol % to about 100 mol %, or from about 80 mol % to about 100 mol %, or from about 90 mol % to about 100 mol % units of Formula (I) below,
R a (R 1 O) b R 2 c SiO (4-a-b-c)/2 Formula (I)
wherein:
a) each R is independently selected from: H, a monovalent, SiC-bonded, optionally substituted, aliphatic hydrocarbon radical that optionally comprises a heteroatom, or an aromatic hydrocarbon radical covalently attached to silicon via aliphatic groups, in one aspect, each R is independently selected from: H, a monovalent, SiC-bonded, optionally substituted, C 1 -C 50 aliphatic hydrocarbon radical that optionally comprises a heteroatom, or a C 6 -C 16 aromatic hydrocarbon radical covalently attached to silicon via aliphatic groups; b) each R 1 is independently selected from: H, or a monovalent, optionally substituted aliphatic hydrocarbon radical, that optionally comprises a heteroatom, in one aspect, each R 1 is independently selected from: H, or a monovalent, optionally substituted C 1 -C 50 aliphatic hydrocarbon radical, that optionally comprises a heteroatom; c) each R 2 is a monovalent, optionally substituted, aromatic hydrocarbon radical which is attached to the silicon atom via a carbon ring atom, in one aspect, each R 2 is a monovalent, optionally substituted, C 6 -C 16 aromatic hydrocarbon radical which is attached to the silicon atom via a carbon ring atom; d) the index a is 0, 1, 2 or 3; e) the index b is 0, 1, 2 or 3; f) the index c is 0, 1, 2 or 3; and
optionally a filler and a resin; with the proviso for said polymer that for each of said polymer's Formula I units the sum of the indices a, b, and c is less than or equal to 3; in 1-100%, 10-60%, or 20-40% of said polymer's Formula I units, c is other than 0; and in at least 50% of said polymer's Formula I units the sum of the indices a, b, and c is 2.
In one aspect, said process, said polymer's number average molecular weight is from about 200 Daltons to about 10,000,000 Daltons, from about 500 Daltons to about 1,000,000 Daltons, from about 1,000 Daltons to about 500,000 Daltons, or from about 1,500 Daltons to about 100,000 Daltons.
Method of Using of Compositions
In one aspect, a method of treating and/or cleaning a situs is disclosed, said method comprising:
a) optionally washing and/or rinsing said situs;
b) contacting said situs with any of Applicants' compositions, and
c) optionally washing and/or rinsing said situs.
In one aspect, said situs is dried either line dried and/or machine dried after said treating and/or cleaning.
Adjunct Materials
While not essential for each consumer product embodiment of the present invention, the non-limiting list of adjuncts illustrated hereinafter are suitable for use in the instant consumer products and may be desirably incorporated in certain embodiments of the invention, for example to assist or enhance performance, for treatment of the substrate to be cleaned, or to modify the aesthetics of the composition as is the case with perfumes, colorants, dyes or the like. The precise nature of these additional components, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the operation for which it is to be used. Suitable adjunct materials include, but are not limited to, solvents, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, UV absorbers, additional perfume and perfume delivery systems, structure elasticizing agents, thickeners/structurants, fabric softeners, carriers, hydrotropes, processing aids and/or pigments. In addition to the disclosure below, suitable examples of such other adjuncts and levels of use are found in U.S. Pat. Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1 that are incorporated by reference.
As stated, the adjunct ingredients are not essential for each consumer product embodiment of the present invention. Thus, certain embodiments of Applicants' compositions do not contain one or more of the following adjuncts materials: bleach activators, solvents, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic metal complexes, polymeric dispersing agents, clay and soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structure elasticizing agents, thickeners/structurants, fabric softeners, carriers, hydrotropes, processing aids and/or pigments. However, when one or more adjuncts is present, such one or more adjuncts may be present as detailed below.
Solvents—suitable solvents include, but are not limited to, water, alcohol, paraffins, glycols, glycerols, and mixtures thereof.
Builders—The compositions of the present invention can comprise one or more detergent builders or builder systems. When present, the compositions will typically comprise at least about 1% builder, or from about 5% or 10% to about 80%, 50%, or even 30% by weight, of said builder. Builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicate builders, polycarboxylate compounds, ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and carboxymethyl-oxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Chelating Agents—The compositions herein may also optionally contain one or more copper, iron and/or manganese chelating agents. If utilized, chelating agents will generally comprise from about 0.1% by weight of the compositions herein to about 15%, or even from about 3.0% to about 15% by weight of the compositions herein.
Dye Transfer Inhibiting Agents—The compositions of the present invention may also include one or more dye transfer inhibiting agents. Suitable polymeric dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. When present in the compositions herein, the dye transfer inhibiting agents are present at levels from about 0.0001%, from about 0.01%, from about 0.05% by weight of the cleaning compositions to about 10%, about 2%, or even about 1% by weight of the cleaning compositions.
Dispersants—The compositions of the present invention can also contain dispersants. Suitable water-soluble organic materials are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid may comprise at least two carboxyl radicals separated from each other by not more than two carbon atoms.
Enzymes—The compositions can comprise one or more detergent enzymes which provide cleaning performance and/or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. A typical combination is a cocktail of conventional applicable enzymes like protease, lipase, cutinase and/or cellulase in conjunction with amylase.
Enzyme Stabilizers—Enzymes for use in compositions, for example, detergents can be stabilized by various techniques. The enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions that provide such ions to the enzymes.
Fabric Hueing Agents—The composition may comprise a fabric hueing agent (sometimes referred to as shading, bluing or whitening agents). Typically the hueing agent provides a blue or violet shade to fabric. Hueing agents can be used either alone or in combination to create a specific shade of hueing and/or to shade different fabric types. This may be provided for example by mixing a red and green-blue dye to yield a blue or violet shade. Hueing agents may be selected from any known chemical class of dye, including but not limited to acridine, anthraquinone (including polycyclic quinones), azine, azo (e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo), including premetallized azo, benzodifurane and benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, formazan, hemicyanine, indigoids, methane, naphthalimides, naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenes and mixtures thereof. Suitable fabric hueing agents include dyes, dye-clay conjugates, and organic and inorganic pigments. Suitable dyes include small molecule dyes and polymeric dyes. Suitable small molecule dyes include small molecule dyes selected from the group consisting of dyes falling into the Colour Index (C.I.) classifications of Direct, Basic, Reactive or hydrolysed Reactive, Solvent or Disperse dyes for example that are classified as Blue, Violet, Red, Green or Black, and provide the desired shade either alone or in combination. In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of Colour Index (Society of Dyers and Colourists, Bradford, UK) numbers Direct Violet dyes such as 9, 35, 48, 51, 66, and 99, Direct Blue dyes such as 1, 71, 80 and 279, Acid Red dyes such as 17, 73, 52, 88 and 150, Acid Violet dyes such as 15, 17, 24, 43, 49 and 50, Acid Blue dyes such as 15, 17, 25, 29, 40, 45, 75, 80, 83, 90 and 113, Acid Black dyes such as 1, Basic Violet dyes such as 1, 3, 4, 10 and 35, Basic Blue dyes such as 3, 16, 22, 47, 66, 75 and 159, Disperse or Solvent dyes such as those described in US 2008/034511 A1 or U.S. Pat. No. 8,268,016 B2, or dyes as disclosed in U.S. Pat. No. 7,208,459 B2, and mixtures thereof. In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of C. I. numbers Acid Violet 17, Direct Blue 71, Direct Violet 51, Direct Blue 1, Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113 or mixtures thereof.
Suitable polymeric dyes include polymeric dyes selected from the group consisting of polymers containing covalently bound (sometimes referred to as conjugated) chromogens, (dye-polymer conjugates), for example polymers with chromogens co-polymerized into the backbone of the polymer and mixtures thereof. Polymeric dyes include those described in WO2011/98355, US 2012/225803 A1, US 2012/090102 A1, U.S. Pat. No. 7,686,892 B2, and WO2010/142503.
In another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of fabric-substantive colorants sold under the name of Liquitint® (Milliken, Spartanburg, S.C., USA), dye-polymer conjugates formed from at least one reactive dye and a polymer selected from the group consisting of polymers comprising a moiety selected from the group consisting of a hydroxyl moiety, a primary amine moiety, a secondary amine moiety, a thiol moiety and mixtures thereof. In still another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of Liquitint® Violet CT, carboxymethyl cellulose (CMC) covalently bound to a reactive blue, reactive violet or reactive red dye such as CMC conjugated with C.I. Reactive Blue 19, sold by Megazyme, Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product code S-ACMC, alkoxylated triphenyl-methane polymeric colourants, alkoxylated thiophene polymeric colourants, and mixtures thereof.
Preferred hueing dyes include the whitening agents found in WO 08/87497 A1, WO2011/011799 and US 2012/129752 A1. Preferred hueing agents for use in the present invention may be the preferred dyes disclosed in these references, including those selected from Examples 1-42 in Table 5 of WO2011/011799. Other preferred dyes are disclosed in U.S. Pat. No. 8,138,222. Other preferred dyes are disclosed in U.S. Pat. No. 7,909,890 B2.
Suitable dye clay conjugates include dye clay conjugates selected from the group comprising at least one cationic/basic dye and a smectite clay, and mixtures thereof. In another aspect, suitable dye clay conjugates include dye clay conjugates selected from the group consisting of one cationic/basic dye selected from the group consisting of C.I. Basic Yellow 1 through 108, C.I. Basic Orange 1 through 69, C.I. Basic Red 1 through 118, C.I. Basic Violet 1 through 51, C.I. Basic Blue 1 through 164, C.I. Basic Green 1 through 14, C.I. Basic Brown 1 through 23, CI Basic Black 1 through 11, and a clay selected from the group consisting of Montmorillonite clay, Hectorite clay, Saponite clay and mixtures thereof. In still another aspect, suitable dye clay conjugates include dye clay conjugates selected from the group consisting of: Montmorillonite Basic Blue B7 C.I. 42595 conjugate, Montmorillonite Basic Blue B9 C.I. 52015 conjugate, Montmorillonite Basic Violet V3 C.I. 42555 conjugate, Montmorillonite Basic Green G1 C.I. 42040 conjugate, Montmorillonite Basic Red R1 C.I. 45160 conjugate, Montmorillonite C.I. Basic Black 2 conjugate, Hectorite Basic Blue B7 C.I. 42595 conjugate, Hectorite Basic Blue B9 C.I. 52015 conjugate, Hectorite Basic Violet V3 C.I. 42555 conjugate, Hectorite Basic Green G1 C.I. 42040 conjugate, Hectorite Basic Red R1 C.I. 45160 conjugate, Hectorite C.I. Basic Black 2 conjugate, Saponite Basic Blue B7 C.I. 42595 conjugate, Saponite Basic Blue B9 C.I. 52015 conjugate, Saponite Basic Violet V3 C.I. 42555 conjugate, Saponite Basic Green G1 C.I. 42040 conjugate, Saponite Basic Red R1 C.I. 45160 conjugate, Saponite C.I. Basic Black 2 conjugate and mixtures thereof.
Suitable pigments include pigments selected from the group consisting of flavanthrone, indanthrone, chlorinated indanthrone containing from 1 to 4 chlorine atoms, pyranthrone, dichloropyranthrone, monobromodichloropyranthrone, dibromodichloropyranthrone, tetrabromopyranthrone, perylene-3,4,9,10-tetracarboxylic acid diimide, wherein the imide groups may be unsubstituted or substituted by C1-C3-alkyl or a phenyl or heterocyclic radical, and wherein the phenyl and heterocyclic radicals may additionally carry substituents which do not confer solubility in water, anthrapyrimidinecarboxylic acid amides, violanthrone, isoviolanthrone, dioxazine pigments, copper phthalocyanine which may contain up to 2 chlorine atoms per molecule, polychloro-copper phthalocyanine or polybromochloro-copper phthalocyanine containing up to 14 bromine atoms per molecule and mixtures thereof.
In another aspect, suitable pigments include pigments selected from the group consisting of Ultramarine Blue (C.I. Pigment Blue 29), Ultramarine Violet (C.I. Pigment Violet 15) and mixtures thereof.
The aforementioned fabric hueing agents can be used in combination (any mixture of fabric hueing agents can be used).
Catalytic Metal Complexes—Applicants' compositions may include catalytic metal complexes. One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methyl-enephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. No. 4,430,243.
If desired, the compositions herein can be catalyzed by means of a manganese compound. Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. No. 5,576,282.
Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S. Pat. Nos. 5,597,936 and 5,595,967. Such cobalt catalysts are readily prepared by known procedures, such as taught for example in U.S. Pat. Nos. 5,597,936, and 5,595,967.
Compositions herein may also suitably include a transition metal complex of a macropolycyclic rigid ligand—abbreviated as “MRL”. As a practical matter, and not by way of limitation, the compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the benefit agent MRL species in the aqueous washing medium, and may provide from about 0.005 ppm to about 25 ppm, from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm to about 5 ppm, of the MRL in the wash liquor.
Preferred transition-metals in the instant transition-metal bleach catalyst include manganese, iron and chromium. Preferred MRL's herein are a special type of ultra-rigid ligand that is cross-bridged such as 5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexa-decane.
Suitable transition metal MRLs are readily prepared by known procedures, such as taught for example in WO 00/32601, and U.S. Pat. No. 6,225,464.
Suitable thickeners/structurants and useful levels of same are described in U.S. Patent Application Publication No. 2005/0130864 A1 and U.S. Pat. Nos. 7,169,741 B2 and 7,297,674 B2. In one aspect, the thickener may be a rheology modifier. The rheology modifier may be selected from the group consisting of non-polymeric crystalline, hydroxy-functional materials, polymeric rheology modifiers which impart shear thinning characteristics to the aqueous liquid matrix of the composition. In one aspect, such rheology modifiers impart to the aqueous liquid composition a high shear viscosity, at 20 sec −1 shear rate and at 21° C., of from 1 to 7,000 cps and a viscosity at low shear (0.5 sec −1 shear rate at 21° C.) of greater than 1000 cps, or even 1,000 cps to 200,000 cps. In one aspect, for cleaning and treatment compositions, such rheology modifiers impart to the aqueous liquid composition a high shear viscosity, at 20 sec −1 and at 21° C., of from 50 to 3,000 cps and a viscosity at low shear (0.5 sec −1 shear rate at 21° C.) of greater than 1,000 cps, or even 1,000 cps to 200,000 cps. Viscosity according to the present invention is measured using an AR 2000 rheometer from TA instruments using a plate steel spindle having a plate diameter of 40 mm and a gap size of 500 μm. The high shear viscosity at 20 sec −1 and low shear viscosity at 0.5 sec −1 can be obtained from a logarithmic shear rate sweep from 0.1 sec −1 to 25 sec −1 in 3 minutes time at 21° C. Crystalline hydroxyl functional materials are rheology modifiers which form thread-like structuring systems throughout the matrix of the composition upon in situ crystallization in the matrix. Polymeric rheology modifiers are selected from the group consisting of polyacrylates, polymeric gums, other non-gum polysaccharides, and combinations of these polymeric materials.
Generally, the rheology modifier will comprise from about 0.01% to about 1% by weight, from about 0.05% to about 0.75% by weight, or even from about 0.1% to about 0.5% by weight, of the compositions herein.
Structuring agents which are especially useful in the compositions of the present invention comprises non-polymeric (except for conventional alkoxylation), crystalline hydroxy-functional materials which can form thread-like structuring systems throughout the liquid matrix when they are crystallized within the matrix in situ. Such materials can be generally characterized as crystalline, hydroxyl-containing fatty acids, fatty esters or fatty waxes. In one aspect, rheology modifiers include crystalline, hydroxyl-containing rheology modifiers include castor oil and its derivatives. In one aspect, rheology modifiers may include hydrogenated castor oil derivatives such as hydrogenated castor oil and hydrogenated castor wax. Commercially available, castor oil-based, crystalline, hydroxyl-containing rheology modifiers include THIXCIN™ from Rheox, Inc. (now Elementis).
Other types of rheology modifiers, besides the non-polymeric, crystalline, hydroxyl-containing rheology modifiers described heretofore, may be utilized in the liquid detergent compositions herein. Polymeric materials which provide shear-thinning characteristics to the aqueous liquid matrix may also be employed.
Suitable polymeric rheology modifiers include those of the polyacrylate, polysaccharide or polysaccharide derivative type. Polysaccharide derivatives typically used as rheology modifiers comprise polymeric gum materials. Such gums include pectine, alginate, arabinogalactan (gum Arabic), carrageenan, gellan gum, xanthan gum and guar gum.
If polymeric rheology modifiers are employed herein, a preferred material of this type is gellan gum. Gellan gum is a heteropolysaccharide prepared by fermentation of Pseudomonaselodea ATCC 31461. Gellan gum is commercially marketed by CP Kelco U.S., Inc. under the KELCOGEL tradename.
A further alternative and suitable rheology modifier include a combination of a solvent and a polycarboxylate polymer. More specifically the solvent may be an alkylene glycol. In one aspect, the solvent may comprise dipropylene glycol. In one aspect, the polycarboxylate polymer may comprise a polyacrylate, polymethacrylate or mixtures thereof. In one aspect, solvent may be present, based on total composition weight, at a level of from 0.5% to 15%, or from 2% to 9% of the composition. In one aspect, polycarboxylate polymer may be present, based on total composition weight, at a level of from 0.1% to 10%, or from 2% to 5%. In one aspect, the solvent component may comprise mixture of dipropylene glycol and 1,2-propanediol. In one aspect, the ratio of dipropylene glycol to 1,2-propanediol may be 3:1 to 1:3, or even 1:1. In one aspect, the polyacrylate may comprise a copolymer of unsaturated mono- or di-carbonic acid and C 1 -C 30 alkyl ester of the (meth)acrylic acid. In another aspect, the rheology modifier may comprise a polyacrylate of unsaturated mono- or di-carbonic acid and C 1 -C 30 alkyl ester of the (meth)acrylic acid. Such copolymers are available from Noveon Inc under the tradename Carbopol Aqua 30®. In the absence of rheology modifier and in order to impart the desired shear thinning characteristics to the liquid composition, the liquid composition can be internally structured through surfactant phase chemistry or gel phases.
UV Absorbers—in certain consumer product embodiments of the present invention, the photo-responsive encapsulates of the present invention may be stabilized against premature release by exposure to light of a sufficient wavelength during storage by incorporation of a suitable UV-absorbing ingredients into the composition. Any suitable UV-absorbing composition may be employed, but particularly preferred are those which do not impart an unpleasant color or odor to the composition, and which do not adversely affect the rheology of the product. Non-limiting examples of UV-absorbing ingredients include avobenzone, cinoxate, ecamsule, menthyl anthranilate, octyl methoxycinnamate, octyl salicylate, oxybenzone, sulisobenzone, and combinations thereof. Other suitable UV-absorbing ingredients are disclosed in U.S. Pat. No. 6,159,918, which is incorporated herein by reference. Applicants have surprisingly found that the use of such UV-absorbing ingredients do not compromise the light-activated performance of encapsulates of the present invention. Without wishing to be bound by theory, it is believed that in many consumer product applications, e.g., cleaning compositions including laundry detergents, shampoos and body washes, the UV absorbing ingredient is washed down the drain while the encapsulates of the present invention are retained in an efficacious amount on the surface of interest where they are available to release their contents on subsequent exposure to light of a sufficient wavelength. In other cleaning compositions or leave-on consumer products, e.g., floor cleaning compositions, drapery and upholstery refreshers, body lotions, and hair styling products, it is believed that the UV-absorbing ingredients dry down to a thin film after application, allowing the encapsulates of the present invention to sit atop or extend above the film. This allows and efficacious amount of light of the desired wavelength to reach the encapsulates and effect the release of the benefit agents.
EXAMPLES
Silicone Antifoam Agent A
Silicone antifoam agent A was prepared by charging a 100 ml flask equipped with a stirrer with 22.75 g of a copolymer having a molecular weight of approximately 35,300 and comprising, 83-85 mole % dimethylsiloxane groups, 15-17 mole % diphenylsiloxane groups, terminated with a vinyl group 1 , and 6 g of an organosiloxane resin 2 having trimethyl siloxane units and SiO 2 units in a M/Q ratio of about 0.65/1 to 0.67/1 dissolved in 2-ethylhexyl stearate 3 . The mixture was stirred until complete incorporation of the resin mixture. Then 2.25 g of precipitated silica 4 and 0.75 g of fumed silica 5 was added and the mixture stirred until complete incorporation of the silica was achieved.
Silicone Antifoam Agent B
Silicone antifoam agent B was prepared by charging a 100 ml flask equipped with a stirrer with 18.2 g of a copolymer having a molecular weight of approximately 35,300 and comprising 83-85 mole % dimethylsiloxane groups, 15-17 mole % diphenylsiloxane groups, terminated with a vinyl group 1 , 4.6 g of a polydimethylsilloxane, trimethylsiloxy terminated, having a molecular weight of approximately 62,700 1 and 6 g of an organosiloxane resin 2 having trimethyl siloxane units and SiO 2 units in a M/Q ratio of about 0.65/1 to 0.67/1, dissolved in 2-ethylhexyl stearate (50% resin). The mixture was stirred until complete incorporation of the resin mixture. Then 2.25 g of precipitated silica 5 and 0.75 g of fumed silica 5 was added and the mixture stirred until complete incorporation of the silica was achieved.
Silicone Antifoam Agent C
Silicone antifoam agent C was prepared by charging a 100 ml flask equipped with a stirrer with 18.2 g of a copolymer having a viscosity of approximately 500 cSt (25° C.) and comprising 38-42 mole % dimethylsiloxane groups and 58-62 mole % phenylmethylsiloxane groups, trimethylsiloxy terminated 1 , 4.6 g of a polydimethylsiloxane, trimethylsiloxy terminated, having a molecular weight of approximately 62,700, and 6 g of an organosiloxane resin 2 having trimethyl siloxane units and SiO 2 units in a M/Q ratio of about 0.65/1 to 0.67/1 dissolved in 2-ethylhexyl stearate 3 (50% resin). The mixture was stirred until complete incorporation of the resin mixture. Then 2.25 g of precipitated silica 4 and 0.75 g of fumed silica 5 was added and the mixture stirred until complete incorporation of the silica was achieved.
1 Supplied by Gelest Inc., Morrisville, Pa. 2 Supplied by Wacker Silicones, Adrian, Mich. under the trade name Belsil 803 3 Supplied by Aldrich Chemicals, Milwaukee, Wis. 4 Available from Evonik Degussa Corporation, Parsippany, N.J. 5 Available from Evonik Degussa Corporation, Parsippany, N.J.
Formulation Example 1
Liquid Detergent Fabric Care Compositions
Liquid detergent fabric care composition 1A-1E are made by mixing together the ingredients listed in the proportions shown:
Ingredient (wt %)
1A
1B
1C
1D
1E
C 12 -C 15 alkyl polyethoxylate
20.1
16.6
14.7
13.9
8.2
(1.8) sulfate 1
C 11.8 linear alkylbenzene
—
4.9
4.3
4.1
8.2
sulfonc acid 2
C 16 -C 17 branched alkyl
—
2.0
1.8
1.6
—
sulfate 1
C 12 alkyl trimethyl
2.0
—
—
—
ammonium chloride 4
C 12 alkyl dimethyl amine
0.7
0.6
—
—
oxide 5
C 12 -C 14 alcohol 9 ethoxylate 3
0.3
0.8
0.9
0.6
0.7
C 15 -C 16 branched alcohol -7
—
—
—
—
4.6
ethoxylate 1
1,2 Propane diol 6
4.5
4.0
3.9
3.1
2.3
Ethanol
3.4
2.3
2.0
1.9
1.2
C 12 -C 18 Fatty Acid 5
2.1
1.7
1.5
1.4
3.2
Citric acid 7
3.4
3.2
3.5
2.7
3.9
Protease 7 (32 g/L)
0.42
1.3
0.07
0.5
1.12
Fluorescent Whitening
0.08
0.2
0.2
0.17
0.18
Agent 8
Diethylenetriamine
0.5
0.3
0.3
0.3
0.2
pentaacetic acid 6
Ethoxylated polyamine 9
0.7
1.8
1.5
2.0
1.9
Grease Cleaning Alkoxylated
—
—
1.3
1.8
—
Polyalkylenimine Polymer 10
Zwitterionic ethoxylated
—
1.5
—
—
0.8
quaternized sulfated
hexamethylene diamine 11
Hydrogenated castor oil 12
0.2
0.2
0.12
0.3
Copolymer of acrylamide and
0.3
0.2
0.3
0.1
0.3
methacrylamidopropyl
trimethylammonium
chloride 13
Antifoam of any of
0.2
0.1
0.2
0.2
0.2
Examples A-C (mixtures
thereof may also be used)
Water, perfumes, dyes,
to 100%
to 100%
to 100%
to 100%
to 100%
buffers, solvents and other
pH 8.0-8.2
pH 8.0-8.2
pH 8.0-8.2
pH 8.0-8.2
pH 8.0-8.2
optional components
Formulation Example 2
Liquid or Gel Detergents
Liquid or gel detergent fabric care compositions 2A-2E are prepared by mixing the ingredients listed in the proportions shown:
Ingredient (wt %)
2A
2B
2C
2D
2E
C 12 -C 15 alkyl polyethoxylate (3.0)
8.5
2.9
2.9
2.9
6.8
sulfate 1
C 11.8 linear alkylbenzene sulfonic acid 2
11.4
8.2
8.2
8.2
1.2
C 14 -C 15 alkyl 7-ethoxylate 1
—
5.4
5.4
5.4
3.0
C 12 -C 14 alkyl 7-ethoxylate 3
7.6
—
—
—
1.0
1,2 Propane diol
6.0
1.3
1.3
6.0
0.2
Ethanol
—
1.3
1.3
—
1.4
Di Ethylene Glycol
4.0
—
—
—
—
Na Cumene Sulfonate
—
1.0
1.0
0.9
—
C 12 -C 18 Fatty Acid 5
9.5
3.5
3.5
3.5
4.5
Citric acid
2.8
3.4
3.4
3.4
2.4
Protease (40.6 mg/g/) 7
1.0
0.6
0.6
0.6
0.3
Natalase 200 L (29.26 mg/g) 14
—
0.1
0.1
0.1
—
Termamyl Ultra (25.1 mg/g) 14
0.7
0.1
0.1
0.1
0.1
Mannaway 25 L (25 mg/g) 14
0.1
0.1
0.1
0.1
0.02
Whitezyme (20 mg/g) 14
0.2
0.1
0.1
0.1
—
Fluorescent Whitening Agent 8
0.2
0.1
0.1
0.1
—
Diethylene Triamine Penta Methylene
—
0.3
0.3
0.3
0.1
Phosphonic acid
Hydroxy Ethylidene 1,1 Di
1.5
—
—
—
—
Phosphonic acid
Zwitterionic ethoxylated quaternized
2.1
1.0
1.0
1.0
0.7
sulfated hexamethylene diamine 11
Grease Cleaning Alkoxylated
—
0.4
0.4
0.4
—
Polyalkylenimine Polymer 10
PEG-PVAc Polymer 15
0.9
0.5
0.5
0.5
—
Hydrogenated castor oil 12
0.8
0.4
0.4
0.4
0.3
Borate
—
1.3
—
—
1.2
4 Formyl Phenyl Boronic Acid
—
—
0.025
—
—
Antifoam of any of the Examples A-C.
0.4
0.3
0.3
0.2
0.3
Water, perfumes, dyes, buffers,
to 100%
to 100%
to 100%
to 100%
to 100%
neutralizers, stabilizers and other
pH 8.0-8.2
pH 8.0-8.2
pH 8.0-8.2
pH 8.0-8.2
pH 8.0-8.2
optional components
1 Available from Shell Chemicals, Houston, TX.
2 Available from Huntsman Chemicals, Salt Lake City, UT.
3 Available from Sasol Chemicals, Johannesburg, South Africa
4 Available from Evonik Corporation, Hopewell, VA.
5 Available from The Procter & Gamble Company, Cincinnati, OH.
6 Available from Sigma Aldrich chemicals, Milwaukee, WI
7 Available from Genencor International, South San Francisco, CA.
8 Available from Ciba Specialty Chemicals, High Point, NC
9 600 g/mol molecular weight polyethylenimine core with 20 ethoxylate groups per —NH and available from BASF (Ludwigshafen, Germany)
10 600 g/mol molecular weight polyethylenimine core with 24 ethoxylate groups per —NH and 16 propoxylate groups per —NH. Available from BASF (Ludwigshafen, Germany).
11 Described in WO 01/05874 and available from BASF (Ludwigshafen, Germany)
12 Available under the tradename ThixinR from Elementis Specialties, Highstown, NJ
13 Available from Nalco Chemicals, Naperville, IL.
14 Available from Novozymes, Copenhagen, Denmark.
15 PEG-PVA graft copolymer is a polyvinyl acetate grafted polyethylene oxide copolymer having a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6000 and the weight ratio of the polyethylene oxide to polyvinyl acetate is about 40 to 60 and no more than 1 grafting point per 50 ethylene oxide units. Available from BASF (Ludwigshafen, Germany).
Formulation Example 3
Rinse-Added Fabric Care Compositions
Rinse-Added fabric care compositions 3A-3D are prepared by mixing together ingredients shown below:
Ingredient
3A
3B
3C
3D
Fabric Softener Active 1
16.2
11.0
16.2
—
Fabric Softener Active 2
—
—
—
5.0
Cationic Starch 3
1.5
—
1.5
—
Polyethylene imine 4
0.25
0.25
—
—
Quaternized polyacrylamide 5
—
0.25
0.25
Calcium chloride
0.15
0.
0.15
—
Ammonium chloride
0.1
0.1
0.1
—
Antifoam of any of the Examples
0.1
0.1
0.1
0.1
A-C
Perfume
0.85
2.0
0.85
1.0
Perfume microcapsule 6
0.65
0.75
0.65
0.3
Water, suds suppressor,
to 100%
to 100%
to 100%
to 100%
stabilizers, pH control agents,
pH = 3.0
pH = 3.0
pH = 3.0
pH = 3.0
buffers, dyes & other optional
ingredients
1 N,N di(tallowoyloxyethyl)-N,N dimethylammonium chloride available from Evonik Corporation, Hopewell, VA.
2 Reaction product of fatty acid with Methyldiethanolamine, quaternized with Methylchloride, resulting in a 2.5:1 molar mixture of N,N-di(tallowoyloxyethyl) N,N-dimethylammonium chloride and N-(tallowoyloxyethyl) N-hydroxyethyl N,N-dimethylammonium chloride available from Evonik Corporation, Hopewell, VA.
3 Cationic starch based on common maize starch or potato starch, containing 25% to 95% amylose and a degree of substitution of from 0.02 to 0.09, and having a viscosity measured as Water Fluidity having a value from 50 to 84. Available from National Starch, Bridgewater, NJ
4 Available from Nippon Shokubai Company, Tokyo, Japan under the trade name Epomin 1050.
5 Cationic polyacrylamide polymer such as a copolymer of acrylamide/[2-(acryloylamino)ethyl]tri-methylammonium chloride (quaternized dimethyl aminoethyl acrylate) available from BASF, AG, Ludwigshafen under the trade name Sedipur 544.
6 Available from Appleton Paper of Appleton, WI
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm”.
All documents cited in the Detailed Description of the Invention are, in relevant part, incorporated herein by reference; the citation of any document is not to be construed as an admission that it is prior art with respect to the present invention. To the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention. | The present application relates to cleaning and/or treatment compositions comprising anti-foams and methods of making and using such compositions. Such compositions encompass consumer products, cleaning and/or treatment compositions, fabric care compositions, or liquid laundry detergents that provide the desired suds profile via the addition of an antifoamer, yet are stable. | 1 |
TECHNICAL FIELD
[0001] The present invention relates to a parallel flow type of heat exchanger which is arranged at the front in an engine room of a vehicle and which is provided with porous tubes constituted by inner fin tubes.
BACKGROUND ART
[0002] In a heat exchanger which is applied to a refrigerant condenser of an air-conditioning system for automobile use, a structure which is comprised of a plurality of porous tubes which are fabricated by extrusion and are inserted at their two sides into header plates of header tanks at predetermined intervals and which is provided with outer fins for heat dissipation use between the porous tubes and other porous tubes has been employed. However, in recent years, due to the demand for reducing costs of heat exchangers, the most costly parts, the porous tubes, are being fabricated by, instead of extrusion, sheet forming for bending belt-shaped sheet members to form tubes and providing inner fins at the insides so as to simplify the method of production, lighten the weight, and reduce the costs.
[0003] Porous tubes which are obtained by sheet forming for bending belt-shaped sheet members to form tubes and providing inner fins at the insides are called “inner fin tubes”. A heat exchanger which employs such inner fin tubes is disclosed in PLT 1. The biggest advantages of production of inner fin tubes by sheet forming of belt-shaped sheet members are the ease of reducing weight by suitably setting the sheet thickness and the greater degree of freedom of shaping than the extrusion method and therefore the enlarged heat conduction area etc. and consequent ability to improve the heat exchange performance of the heat exchanger.
[0004] A heat exchanger which uses the inner fin tubes which are shown in PLT 1 etc. is for use for air-conditioning systems for vehicular use. Its configuration is shown simplified in FIG. 1 . The heat exchanger 1 is provided with a core part 2 , entry side header tank 3 , and exit side header tank 4 which are brazed together. The core part 2 is comprised of a plurality of inner fin tubes 10 and a plurality of outer fins 20 alternately stacked and reinforcing members constituted by side plates 25 at the end parts at the two sides in the stacking direction (up-down direction in figure). In the heat exchanger 1 , the air which is blown through the core part 2 is used to cool the refrigerant which flows through the insides of the inner fin tubes 10 .
[0005] At the insides of the entry side header tank 3 and exit side header tank 4 , in this example, separators 26 are provided. At the two end parts, caps 23 and 24 which close the opening parts of the header tanks are brazed. The insides of the entry side header tank 3 and exit side header tank 4 are separated by the separators 26 into a plurality of spaces. Further, the entry side header tank 3 has an inflow port 21 for the refrigerant, while the exit side header tank 4 has an outflow port 22 for the refrigerant. Further, the refrigerant which flows from the inflow port 21 to the inside of the heat exchanger 1 flows through the insides of the entry side header tank 3 and exit side header tank 4 which are separated by the separators 26 and the insides of the inner fin tubes 10 as shown by the broken lines and discharged from the outflow part 22 . Note that, the number of the inner fin tubes 10 and the number of the separators 26 which are shown in FIG. 1 are examples and do not show the numbers and flow paths of refrigerant in an actual heat exchanger 1 .
[0006] FIG. 2 explains the configuration of the inside of an inner fin tube 10 of the heat exchanger 1 which is shown in FIG. 1 and the flow path of refrigerant which flows through the inside of it. The inner fin tube 10 is comprised of a tube 11 formed with a cross-section wave-shaped inner fin 12 inserted in it. The tube 11 is a tube member with a horizontal cross-section of a flat shape (shape close to oval shape) perpendicular to the longitudinal direction (flow path direction of refrigerant) obtained by bending a thin (for example thickness 0.2 mm) aluminum belt-shaped sheet member.
[0007] Specifically, the tube 11 is comprised of a belt-shaped sheet member with a center part which is bent into an arc to form a curved end part 11 a and with parallel parts 11 p which extend from this curved end part 11 a to form a swaged part 11 b at the end part at the opposite side from the curved end part 11 a of the parallel parts 11 p. At this time, the two end parts of the belt-shaped sheet member are made different in lengths from the curved end part 11 a for swaging at the swaged part 11 b. The inner fin 12 , like the tube 11 , is formed in a wave shape by rolling a thin (for example thickness 0.1 mm) aluminum belt-shaped sheet and providing flat plate parts 15 and 16 at the two end parts. The bent parts 14 of the wave parts of the inner fin 12 are brazed at the inside wall surface 13 of the tube 11 , while the end part of the flat plate part 16 is brazed to the inside wall surface 14 of the curved end part 11 a. On the other hand, the end part of the flat plate part 15 of the inner fin 12 is joined with the tube 11 by swaging at the swaged part 11 b.
[0008] FIG. 3 shows the state of a header tank of the heat exchanger 1 which is shown in FIG. 1 , for example, the exit side header tank 4 , to which the inner fin tubes 10 which are shown in FIG. 2 are connected. The exit side header tank 4 is formed by a header plate 41 through which the inner fin tubes 10 are inserted and a tank plate 42 which are joined together. The front end parts of the inner fin tubes 10 are inserted through the header plate 41 and stick out into the space inside the exit side header tank 4 . FIG. 4 is a view of the exit side header tank 4 which is shown in FIG. 3 as seen from the arrow L direction. The header plate 41 and the tank plate 42 are provided with a brazing material between them. The front end parts of the inner fin tubes 10 which are inserted into the header plate 41 are brazed to the header plate 41 by the brazing material which is arranged between the header plate 41 and the tank plate 42 .
CITATIONS LIST
Patent Literature
[0009] PLT 1: Japanese Patent Publication No. 2007-125590A
SUMMARY OF INVENTION
Technical Problem
[0010] However, if brazing the front end parts of the inner fin tubes 10 to the header plates 41 by brazing material which is arranged between the header plates 41 and the tank plates 42 , there was the problem that the brazing material of the header plates 41 flows into the inner fin tubes 10 and melts the tubes. Further, as shown in FIG. 5 , there was the problem that at the portions of the header tanks (here, the entry side header tank 3 ) provided with the separators 26 , the brazing material flows into the header plates 31 through the separators 26 and flows into
[0011] the inner fin tubes 10 to melt the tubes. Here, tube melting will be explained in detail. FIG. 6 shows the vicinity of a swaged part 11 b of an inner fin tube 10 which is normally brazed. The tube 11 has parallel parts 11 p. The belt-shaped sheet member is bent at points at the same lengths from the not shown curved end part whereby slanted parts 11 c are formed. The slanted parts 11 c are bent at the parts of the belt-shaped sheet member which abut against each other. Between the long end part 11 e and the short end part 11 f of the belt-shaped sheet member, a flat plate part 15 of an inner fin 12 is sandwiched. In that state, the end part 11 e of the belt-shaped sheet member is folded back to the end part 11 f side to form the swaged part 11 b. In this example, the end part 15 a of the flat plate part 15 sticks out from the short end part 11 f of the belt-shaped sheet member and is bent around the short end part 11 f side of the belt-shaped sheet member by the long end part 11 e of the folded back belt-shaped sheet member.
[0012] Further, the long end part 11 e and one slanted part 11 c of the belt-shaped sheet member are brazed together by a brazing material 51 , while the flat plate part 15 of the inner fin 12 and the inside surfaces of the slanted parts 11 c are brazed together by the brazing material 52 . Further, the bent parts 14 of the inner fin 12 and the inner wall surface 13 of the tube 11 are brazed by the brazing material 53 . FIG. 7 shows the swaged part 11 b of the inner fin tube 10 which is shown in FIG. 6 and shows the state where tube melting 5 occurs. If tube melting 5 occurs, the tube 11 is reduced in thickness, a hole is formed in the tube 11 at the part of the tube melting 5 , and refrigerant leaks out.
[0013] FIG. 8 shows another example of an inner fin tube 10 . The inner fin tube 10 has an inner fin 12 inside of it. The tube 11 is swaged and closed by the swaged part 11 b. FIG. 9 shows the state where tube melting 6 and 7 occurs at the swaged part 11 b of the inner fin tube 10 which is shown in FIG. 8 . In this way, even if the shape of the inner fin tube differs, there was the problem that if brazing material is arranged at the header tank side, at the time of brazing of the inner fin tube, the brazing material passes through the header plate to flow into the inner fin tube causing tube melting.
[0014] Inflow of brazing material to the inner fin tube occurs due to the step difference at the swaged part of the tube which is formed by the bent sheet, so up to now measures have been taken such as welding together the swaged part or reducing the step difference at the swaged part. However, each of these measures leads to increased cost. Further, special steps are required where the brazing temperature has to be strictly managed. Insufficient measures have been taken against the flow of brazing material to the inside of the inner fin tube.
[0015] The present invention, in consideration of the above problem, provides a heat exchanger which is brazed after tubes are assembled into the header tanks wherein tube melting at the time of attachment of the tubes to the header tanks can be prevented and productivity can be improved.
Solution to Problem
[0016] To solve the above problem, the present invention provides a heat exchanger ( 1 ) which has a plurality of tubes ( 11 ) which are provided with refrigerant passages inside them and a pair of header tanks ( 3 , 4 ) to which end parts of the tubes ( 11 ) are brazed, wherein brazing materials ( 8 ) which are used for brazing to the header tanks ( 3 , 4 ) are arranged at the outer circumferential surfaces of the tubes ( 11 ), and the base materials of the metal sheet members which form the header tanks ( 3 , 4 ) are exposed at the inner circumferential surfaces and outer circumferential surfaces of the header tanks ( 3 , 4 ).
[0017] According to the heat exchanger of the present invention, the brazing material which is necessary for brazing a tube and a header tank is supplied from the outer circumferential surface of the tube, so tube melting at the time of brazing is prevented, and the heat exchanger is improved in productivity.
[0018] Further, reference notations attached above are examples which show the correspondence with specific examples of the later explained embodiments.
BRIEF DESCRIPTION OF DRAWINGS
[0019] FIG. 1 is a front view which shows the streamlined configuration of a heat exchanger of the comparative art.
[0020] FIG. 2 is a perspective view which shows an inner fin tube which is used at the heat exchanger which is shown in FIG. 1 .
[0021] FIG. 3 is a partial perspective view of a heat exchanger which shows the state where inner fin tubes which are shown in FIG. 2 are connected to a header plate of a header tank of the heat exchanger which is shown in FIG. 1 .
[0022] FIG. 4 is a cross-sectional view of the header tank which is shown in FIG. 3 as seen from an arrow L direction.
[0023] FIG. 5 is a partial perspective view which shows the state where the brazing material of the tank plate flows into the header plate through a separator and the brazing material flows into an inner fin tube.
[0024] FIG. 6 is a partial enlarged cross-sectional view which shows a swaged part of an inner fin tube which is normally brazed.
[0025] FIG. 7 is a partial enlarged cross-sectional view which shows the state where tube melting occurs at the swaged part of the inner fin tube which is shown in FIG. 6 .
[0026] FIG. 8 is a cross-sectional view which shows another example of an inner fin tube.
[0027] FIG. 9 is a partial enlarged cross-sectional view which shows the state where tube melting occurs at the swaged part of the inner fin tube which is shown in FIG. 8 .
[0028] FIG. 10 is a cross-sectional view of an inner fin tube of a first embodiment of the present invention.
[0029] FIG. 11 is a partial enlarged cross-sectional view which shows a part of a swaged part of the inner fin tube of FIG. 10 .
[0030] FIG. 12A is a cross-sectional view of a brazing material-free header plate and tank plate which are used for an inner fin tube and heat exchanger of the first embodiment of the present invention, FIG. 12B is a cross-sectional view of a modification of the first embodiment where there is a sacrificial material at the outside of the header plate of the brazing material-free header plate and tank plate which are shown in FIG. 12A , FIG. 12C is a partial perspective view of a heat exchanger which shows an embodiment of providing a brazing material at one surface of a separator of an entry side and exit side header tank which is provided with a brazing material-free header plate and tank plate, FIG. 12D is a cross-sectional view of an embodiment where the entry side and exit side header tanks are one-piece bodies and have cross-sections of circular shapes, FIG. 12E is a cross-sectional view of an embodiment where the entry side and exit side header tanks are one-piece bodies and have cross-sections of oval shapes, FIG. 12F is a cross-sectional view of an embodiment where the entry side and exit side header tanks are one-piece bodies and have cross-sections of irregular shapes, and FIG. 12G is an enlarged view of a principal part X of FIG. 12B .
[0031] FIG. 13 is an assembled perspective view of a header plate and a brazing material-free separator which is used for the same which shows a second embodiment of the present invention.
[0032] FIG. 14 is an assembled perspective view of a header plate and a brazing material-free separator which is used for the same which shows a modification of the second embodiment of the present invention.
[0033] FIG. 15 is a side cross-sectional view and front view of a first specific example of a separator of a third embodiment of the present invention.
[0034] FIG. 16 is a side cross-sectional view and front view of a second specific example of a separator of a third embodiment of the present invention.
[0035] FIG. 17 is a front view of a third specific example of a separator of a third embodiment of the present invention.
[0036] FIG. 18 is a front view of a fourth specific example of a separator of a third embodiment of the present invention.
[0037] FIG. 19 is a front view of a fifth specific example of a separator of a third embodiment of the present invention.
[0038] FIG. 20 is a front view of a sixth specific example of a separator of a third embodiment of the present invention.
DESCRIPTION OF EMBODIMENTS
[0039] Below, referring to the drawings, embodiments of the present invention will be explained. In the embodiments, parts which are configured the same are assigned the same reference notations and explanations will be omitted. Parts of the embodiments of the present invention which are the same in configuration as the comparative art forming the basis of the present invention are assigned the same reference notations and explanations are omitted.
[0040] FIG. 10 shows an inner fin tube 10 of a first embodiment of the present invention. Further, FIG. 11 shows a part X of FIG. 10 enlarged. An inner fin tube 10 is comprised of a belt-shaped sheet member which is folded back to hold an inner fin 12 inside of it. The belt-shaped sheet member is formed by thin (for example thickness 0.2 mm) aluminum. It is folded back into an arc shape at a portion at slightly different distances from the two end parts to form a curved end part 11 a. The belt-shaped sheet member is folded back until becoming parallel to form parallel parts 11 p. The two end parts of the belt-shaped sheet member are bent at portions of the same distance from the curved end part 11 a to form predetermined lengths of slanted parts 11 c, then are further bent so that the two end parts become parallel.
[0041] The belt-shaped sheet member is folded back as explained above to form the flat tube 11 . At the inside, an inner fin 12 is housed whereby a flat shaped flow path of the medium is formed. The inner fin 12 is formed into a wave shape by rolling a thin (for example thickness 0.1 mm) aluminum belt-shaped sheet member in the same way as the tube 11 . At the two end parts, flat plate parts 15 and 16 are provided. The bent parts 14 of the wave shaped parts of the inner fin 12 are brazed to the inside wall surface 13 of the tube 11 . The end part of the flat plate part 16 is also brazed to the inside wall surface 13 of the curved end part 11 a. On the other hand, the end part of the other flat plate part 15 of the inner fin 12 is sandwiched between the two end parts bent to become parallel.
[0042] The two end parts 11 e and 11 f of the belt-shaped sheet member which sandwich the flat plate part 15 of the inner fin 12 in the first embodiment become longer at the end part 11 e than the end part 11 f. Accordingly, the end part 11 e is folded back to the end part 11 f side in a state sandwiching the flat plate part 15 and the end part 11 f and is swaged to join them whereby the swaged part 11 b is formed. In the first embodiment, a brazing material 8 is arranged (clad) at the outer surface as a whole at the thus formed inner fin tube 10 . The amount of this brazing material 8 becomes an amount which is required for brazing the inner fin tube 10 to the entry side and exit side header tanks 3 and 4 when inserting and brazing the two end parts of the inner fin tube 10 , as shown in FIG. 3 , to the entry side and exit side header tanks 3 and 4 .
[0043] In this case, the inner circumferential surfaces N and outer circumferential surfaces S of the header plates 31 and 41 which form the entry side header tank 3 and the exit side header tank 4 , as shown in FIG. 12A , are made brazing material-free. That is, the metal sheet members which form the header plates 31 and 41 are made sheet members with the base material exposed (bare materials) and can be made single layer members with no brazing material. By this configuration, the brazing material which is used when joining the inner fin tube 10 to the entry side and exit side header tanks 3 and 4 is supplied from the sufficient amount of brazing material 8 which was clad at the outer surface of the inner fin tube 10 (see FIG. 10 and FIG. 11 ). The brazing material is not present at the tank plates 32 and 42 , so the brazing material no longer flows from the tank plates 32 and 42 to the inner fin tube 10 and the tube melting of the inner fin tube 10 no longer occurs. As a result, the stability at the time of brazing the inner fin tube 10 is improved and the scope of application of the brazing temperature can be broadened.
[0044] As explained above, the brazing material which flows to the inside of the inner fin tube 10 is a sufficient amount of brazing material 8 which is clad over the entire outer surface of the inner fin tube 10 . For this reason, the amount of the brazing material which is supplied to the brazing part of the inner fin tube 10 becomes sufficient, and the brazing fillet of the inner fin tube 10 can be made larger. Further, a fillet commensurate with the amount of brazing material of the part itself is formed and the brazeability of parts other than the inner fin tube 10 is also improved.
[0045] Here, consider the case of the comparative art where the brazing material which is at the entry side and exit side header tanks 3 and 4 flows into the inner fin tube 10 and where the brazing material which is at the entry side and exit side header tanks 3 and 4 and the brazing material of the inner fin tube 10 are connected. In this case, the size of the fillet radius of the fillet which is formed at the inner fin 12 and the size of the fillet radius which is formed at the tank plate 32 and header plate 31 become substantially equal. However, in this case, the amounts of brazing material at the entry side and exit side header tanks 3 and 4 are small, so the size of the fillet radius of the tank plate 32 and header plate 31 ends up becoming the same 0.1 mm or so as the fillet radius of the fillet which is formed at the inner fin 12 . That is, sometimes the size of the fillet radius which is formed at the tank plate 32 and the header plate 31 is extremely small and the gap at the part requiring brazing cannot be filled resulting in leakage.
[0046] As opposed to this, if making the inner circumferential surfaces N and outer circumferential surfaces S of the header plates 31 and 41 brazing material-free, the connection of the brazing material of the fillet which is formed between the tank plate 32 and header plate 31 and the brazing material of the fillet 52 or 53 which is formed at the inner fin 12 can be broken. As a result, it is possible to form a large fillet at the joint of the tank plate 32 and header plate 31 or the joint of the tank plate 32 and a cap 24 . That is, it is possible to form a large fillet of the fillet radius 0.3 mm to 0.6 mm or so which can inherently be obtained at the joint of the tank plate 32 and header plate 31 or the joint of the tank plate 32 and a cap 24 , the gap can be easily filled, and the brazeability can be improved. Note that, the “size of the fillet radius” which is referred to here envisions the case of using the generally widely used brazing material with 10 wt % of amount of Si.
[0047] Further, the surface of the inner fin tube 10 sometimes has an anticorrosion layer or sacrificial brazing material on which the brazing material layer is superposed arranged on it, but by making the header plates 31 and 41 brazing material-free, it is possible to prevent the inflow of brazing material from the entry side and the exit side header tanks 3 and 4 , so the flow of brazing material to the surface of the inner fin tube 10 is also prevented. The brazing material ends up obstructing the action of the anticorrosion layer, so by preventing the flow of brazing material to the surface of the inner fin tube 10 , it is possible to improve the corrosion resistance of the inner fin tube 10 .
[0048] Further, it is possible to use as the material of the header plates 31 and 41 a metal material which does not contain a brazing material and provide the inner circumferential surfaces N or outer circumferential surfaces S of the header plates 31 and 41 with a low potential anticorrosion layer constituted by a sacrificial material. FIG. 12B shows an embodiment which provides the outer circumferential surfaces S of the header plates 31 and 41 with a sacrificial material (anticorrosion layer) 9 . In this case, as shown in FIG. 12G , as the header plates 31 and 41 , the surfaces of the metal sheet members (for example, comprised of aluminum alloy etc.) at the inner circumferential surface N sides may be made states with the base materials 311 and 411 exposed and the surfaces of the metal sheet members at the outer circumferential surface S sides of the header plates 31 and 41 may be made states with the surfaces of the base materials 311 and 411 clad by the sacrificial material 9 . Furthermore, as shown in FIG. 12C , the header plates 31 and 41 are made brazing material-free, but one or both surfaces of the separators 26 may be provided with the brazing material 8 . In FIG. 12C , the brazing material 8 are shown shaded.
[0049] Still further, the inner circumferential surfaces N and outer circumferential surfaces S of the entry side and exit side header tanks 3 and 4 may be made brazing material-free even in the case where the entry side and exit side header tanks 3 and 4 are single-piece pipes 30 not split into header plates 31 and 41 and tank plates 32 and 42 . Further, the single-piece pipes 30 which are used for the entry side and exit side header tanks 3 and 4 are effective regardless of their cross-sectional shapes such as the circular shape which is shown in FIG. 12D , the oval shape which is shown in FIG. 12E , and the irregular shape which is shown in FIG. 12F . Further, even when the entry side and exit side header tanks 3 and 4 are formed by single-piece pipes 30 , the materials which form the tanks may be exposed single layer types and may be provided at least at one of the inner circumferential surfaces N and outer circumferential surfaces S of the pipes 30 with a low potential sacrificial material (anticorrosion layer) 9 . In the entry side and exit side header tanks 3 and 4 which are shown from FIG. 12D to FIG. 12F , the inner circumferential surface N of the pipe 30 which is shown in FIG. 12E is provided with the sacrificial material 9 , while the outer circumferential surface S of the pipe 30 which is shown in FIG. 12F is provided with the sacrificial material 9 .
[0050] Note that, in the entry side and exit side header tanks 3 and 4 which are shown from FIG. 12D to FIG. 12F as well, the outer circumferential surface S of the pipe 30 which is shown in FIG. 12E may be provided with the sacrificial material and the inner circumferential surface N of the pipe 30 which is shown in FIG. 12F may be provided with the sacrificial material 9 needless to say. Whether the sacrificial material 9 is provided at the inner circumferential surface N of the pipe 30 or is provided at the outer circumferential surface S does not depend on the shape and structure of the pipe 30 . Further, both of the inner circumferential surface N and the outer circumferential surface S of the pipe 30 may be provided with the sacrificial material 9 .
[0051] FIG. 13 shows a second embodiment of the heat exchanger of the present invention. In the second embodiment, the entry side header plate 31 and the exit side header plate 41 are made brazing material-free, and the separator 26 which is attached as a partition wall at the inside of the entry side header tank 3 and the exit side header tank 4 is made brazing material-free. The separator 26 of the second embodiment is used in the case of a structure where the header plates 31 and 41 have holes 33 and 43 (hole 33 at entry side header tank 3 and hole 43 at exit side header tank 4 ). That is, the metal sheet member which forms the separator 26 is made the exposed sheet member (bare material) where no brazing material is provided.
[0052] In the case of this arrangement, the header plates 31 and 41 and the separator 26 are brazing material-free, but brazing material which is arranged at the tank plates 32 and 42 is supplied, whereby the header plates 31 and 41 and the separator 26 can be brazed. Tank brazing material flows through the fine clearances between the separator 26 and header plates 31 and 41 whereby these are brazed together. In this case, as the brazing material of the tank plates 32 and 42 , a brazing material with an amount of Si of 6 wt % or more is suitable.
[0053] FIG. 14 shows a modification of the separator 26 of the second embodiment of the present invention which is shown in FIG. 13 . The separator 26 of the modification is used in the case of a structure with grooves 34 and 44 at the two sides of the header plates 31 and 41 (groove 34 at entry side header tank 3 and groove 44 at exit side header tank 4 ). In the modification of the second embodiment as well, the metal sheet member which forms the separator 26 is made the exposed sheet member (bare material) where no brazing material is provided. Further, in the modification of the second embodiment, the holes at the header plates 31 and 41 at the joining sides with the inner fin tubes are eliminated, and grooves 34 and 44 are provided for attachment of the separator 26 at the two sides of the header plates 31 and 41 . For this reason, the flow paths of inflow of the brazing material from the outsides of the header plates 31 and 41 are cut.
[0054] If, in this way, making the metal sheet member which forms the separator 26 a sheet member with the base material exposed and not providing a brazing material, that is, making it brazing material-free, it is possible to cut the flow paths of brazing material to the header plates 31 and 41 resulting in a further reduction in the occurrence of tube melting.
[0055] FIG. 15 to FIG. 17 show the configurations of separators 26 of a third embodiment of the heat exchanger of the present invention. The figures give cross-sectional views and front views of separator 26 . The third embodiment provides the two surfaces of the separator 26 with structures for holding the brazing material in the case where the two surfaces of the entry side header tank 3 or exit side header tank 4 are provided with brazing material and thereby prevents the inflow of the brazing material to the inner fin tubes 10 .
[0056] FIG. 15 shows a first specific example of the separator 26 . A separator 26 of the same type as the separator 26 which was explained in FIG. 13 is shown. In the first specific example of the separator 26 , the two surfaces of the separator 26 are provided with a plurality of parallel grooves 27 . FIG. 16 shows a second specific example of the separator 26 . A separator 26 of the same type as the separator 26 which was explained in FIG. 13 is shown. In the second specific example of the separator 26 , the two surfaces of the separator 26 are provided with a plurality of circular depressions 28 which are regularly arranged to the top and bottom and the left and right. These depressions 28 serve as brazing reservoirs in which melted brazing material is held. The depressions 28 may also be provided irregularly arranged. FIG. 17 shows a third specific example of the separator 26 . A separator 26 of the same type as the separator 26 which was explained in FIG. 13 is shown. In the third specific example of the separator 26 , the two surfaces of the separator 26 are provided with a plurality of oval depressions 29 which are regularly arranged to the top and bottom and the left and right. Oval depressions 29 may also be provided irregularly arranged.
[0057] If in this way providing the two surfaces of the separator 26 with grooves or holes, even if the two surfaces of the entry side header tank 3 and the exit side header tank 4 are provided with brazing material, the excess brazing material can be held at the grooves or holes and flow of excess brazing material to the header plate side can be prevented. As a result, excess brazing material no longer flows into the inner fin tubes and tube melting can be prevented.
[0058] FIG. 18 to FIG. 20 show fourth to sixth specific examples of the separator 26 of the third embodiment of the heat exchanger of the present invention. In the fourth specific example which is shown in FIG. 18 , the two surfaces of the separator 26 are provided at a slant with grooves 35 which cut the brazing material flow paths. The grooves 35 are provided at the separator 26 asymmetrically. The grooves 35 may also be ribs. In the fifth specific example which is shown in FIG. 19 , the two surfaces of the separator 26 are provided with grooves 36 which cut the brazing material flow path at an angle symmetrically with respect to the centerline of the separator 26 . The grooves 36 may also be ribs. In the sixth specific example which is shown in FIG. 20 , the two surfaces of the separator 26 are provided with not only the grooves 36 which were explained in the fifth example, but also ribs 37 which cut the brazing material flow paths at an angle symmetrically with respect to the centerline of the separator 26 . The ribs 37 may also be grooves.
[0059] The brazing material which causes tube melting flows to an inner fin tube through a brazing part of a separator 26 and an inside of a tank. Therefore, as shown in the first to the sixth specific examples, by providing the two surfaces of the separator 26 with grooves 36 or ribs 37 , it is possible to reduce or delay the amount of brazing material which flows from the inside of the tank through the separator 26 to the inner fin tube. That is, the grooves 36 or ribs 37 which are provided at the two surfaces of the separator 26 can extend the flow paths from the inside of the tank to the inner fin tube and can increase the time it takes for the brazing material to reach the inner fin tube due to the large flow resistance of the brazing material. As a result, it is possible to reduce the temperature difference from the core part before the brazing material reaches the inner fin tube, so tube melting is reduced.
[0060] In the embodiments which were explained above, the type and thickness of the brazing material which was actually used was a brazing material with a 4 wt % to 5 wt % amount of Si and with a clad rate of 20% (since the sheet thickness t was 0.2 mm, the film thickness was 40 μm). However, in the present invention, as the brazing material which is clad at the tube surface, a usually used 10 wt % brazing material is also possible. The invention is effective even for a tube provided with a clad rate 10% (film thickness 20 μm) or so brazing material. That is, the invention is effective even for a tube with an amount of Si of the brazing material 8 at the tube surface of 3.5 wt % to 10 wt %. However, the amount of the brazing material at the tube surface is preferably 3.5 wt % to 7.5 wt %.
[0061] As explained above, in the present invention, there is provided a heat exchanger which employs tubes which were produced by sheet bending wherein the brazing materials which are required at the time of brazing the tubes are supplied from the outer circumferential surfaces of the tubes, so tube melting at the time of brazing the tubes to the header tanks is prevented and the productivity of the heat exchanger is improved. Further, by making the separators which are provided at the inside of the header tanks brazing material-free or by providing the separators with structures for holding the brazing materials, tube melting at the time of brazing the tubes to the header tanks is prevented. Further, by combining the above-mentioned first to third embodiments, it is possible to further reduce the tube melting at the time of brazing the tubes to the header tanks.
[0062] Note that, in the above-mentioned embodiments, examples of using tubes with inner fins at their insides as the tubes which were brazed to the header plates were explained, but it is also possible to use tubes in which no inner fins are arranged. In particular, if the tubes which are brazed to the header plates are tubes of structures comprised of sheet members which are folded back and are superposed at their two end parts, the brazing materials are sucked in at the superposed parts due to the capillary phenomenon, so the brazing materials easily pool near the superposed parts, but it is possible to prevent tube melting by application of the present invention.
[0063] Further, in the above-mentioned embodiments, the example of use of aluminum as the material of the inner fin tubes and inner fins was explained, but in all of the above embodiments, it is possible to use aluminum alloy as the material of the inner fin tubes and inner fins. | A heat exchanger which employs porous tubes wherein tube melting at the time of attaching the porous tubes to the header tanks is prevented, the heat exchanger provided with an entry header tank which has an inflow port, an exit header tank which has an outflow port, and a plurality of tubes having passages for refrigerant flowing between the entry header tank and the exit header tank, the tubes being porous tubes which are formed by bending or rolling from flat sheets and being brazed at the two end parts to the entry header tank and exit header tank, wherein the outer surfaces of the tubes are provided with brazing materials which are used for brazing to the entry header tank and exit header tank and wherein the inner surface and outer surface of the entry header tank and exit header tank are made brazing material-free. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] Not applicable.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not applicable.
BACKGROUND OF THE INVENTION
[0003] 1. Field of the Invention
[0004] The present invention relates generally to making computer systems more user-friendly. In particular, the present invention relates to a method for conveniently restoring the default basic input/output system (“BIOS”) parameter settings from a nonvolatile memory in a computer.
[0005] 2. Description of Related Art
[0006] Personal computers include a basic input/output system (“BIOS”) stored in nonvolatile memory. The BIOS is a set of instructions which are executed to conduct the system initialization and to provide control of low level functions in the computer. Normally, the nonvolatile memory is an electrically-erasable read-only memory (“EEPROM”) chip, which the BIOS to be updated through software control. This is commonly called a “flash” BIOS. Under normal circumstances, the BIOS ROM is permanent and there is normally no need to deal with it.
[0007] In addition to the BIOS ROM, most conventional computer systems include a small CMOS memory and real time clock (“RTC”) unit. This component keeps track of the time and date, and stores BIOS configuration parameters when the computer was turned off, so that this information is readily available when the computer is turned back on. To preserve this information while the computer is off, this component also includes a low-power, long life battery.
[0008] The acronym CMOS stands for “Complementary Metal Oxide Semiconductor”, and generally refers to one type of technology used to make semiconductor devices (i.e., integrated circuits) such as processors, chipset chips, DRAM, etc. Devices constructed using CMOS technology advantageously require very little power compared to other semiconductor technologies. Consequently, CMOS technology is a natural choice for implementing the memory and RTC unit so that the amount of power required from the battery is minimal, and the battery would last a longer. This memory came to be called just “CMOS”, since in the early days of personal computer development most parts of the computer did not use CMOS. Although modem processors are typically made entirely with CMOS technology, “CMOS” by itself usually still refers to the BIOS settings memory.
[0009] The information stored by the CMOS memory typically includes the type of floppy disk drive, hard disk settings, the amount of memory, clock speeds, wait states, passwords, initial boot drive selection, and other configuration parameters. The BIOS directs the processor to retrieve information to make the power-on configuration process more efficient. The CMOS used to be relatively small, about 64 or 128 bytes. As the complexity of computers has increased, the number of configuration parameters has increased. To keep pace with the increased number of parameters, the CMOS has been expanded (e.g., to 2048 bytes) to allow storage of additional parameters such as power management configuration parameters and resource assignments for Plug and Play systems. The increased number of parameters has increased the likelihood of an incorrect parameter being present, whether due to faulty user entry or to corruption of the memory contents. This is of utmost concern since the presence of an error in CMOS may render the computer unbootable, and this error may not be rectified by simply re-booting the computer due to the nonvolatile nature of the CMOS memory.
[0010] Since it in not uncommon for computer systems to develop incorrect or corrupted CMOS data, system designers have developed some techniques to clear CMOS memory. Certain few versions of BIOS will clear the CMOS settings if the <Insert> key on the keyboard is held down by the user while the computer is performing its boot process. More commonly, computer manufacturers provide a jumper on the “motherboard” (the main circuit board in the computer) that connects the battery to the CMOS memory. To clear the CMOS memory, the user must unplug the computer, open the case, locate the jumper and remove the jumper and thereby disconnect the battery from the CMOS memory. Without power, the CMOS memory will eventually lose all the stored information. This time period may be relatively lengthy because stray capacitance in the system may need to completely discharge before the CMOS memory clears. To speed up the process, some manufacturers provide a second jumper setting to ground the positive power supply input to the CMOS memory. In this case, the jumper is moved from a setting to the second setting, left there for 30 seconds, and then replaced to the first setting. Grounding the positive power supply input discharges any stray capacitance at a much higher rate.
[0011] Most computer users find it undesirable, if not frustrating, to open the computer case, to locate a jumper on the motherboard, to remove and replace the jumper, to close the computer case, and reprogram the BIOS settings. Further, if the user calls for technical assistance, it is very difficult for a computer support person to guide a novice user through this process over the telephone. Providing a CMOS-memory-restoration feature through BIOS detection of a keypress may become infeasible as the multitude of alternative input devices and new keyboard configurations become popular. Pointer devices, speech recognition, and touch-sensitive screens may supplant the standard keyboard and require BIOS software to access CMOS prior to detecting the key-press that indicates the contents of CMOS should be ignored and erased. Consequently, a convenient way of restoring CMOS is desired.
SUMMARY OF THE INVENTION
[0012] Accordingly, there is provided herein a method of leveraging a multi-function power switch to provide a CMOS-restoration functionality. In one embodiment, the method for restoring CMOS parameter values in a computer having a multi-function power button includes (a) pressing the power button for a predetermined time delay while the computer is performing a power-on self test (“POST”), thereby placing the computer in an OFF state; and (b) momentarily pressing the power button to turn on the computer. Pressing the power button for four seconds preferably invokes a power button override function. The power button function unconditionally forces the computer to a “soft-off” state. The BIOS is preferably configured to determine if the power-override function was invoked during the POST in the previous boot-up, and if so, to replace the CMOS parameter values with backup parameter values before proceeding with the current boot-up. The CMOS parameter values are preferably backed up only if they have changed and the BIOS has successfully completed the POST procedure with the changed values. This ensures that the backup values will allow the computer to boot when CMOS parameter restoration is needed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] A better understanding of the present invention can be obtained when the following detailed description of the preferred embodiment is considered in conjunction with the following drawings, in which:
[0014] [0014]FIG. 1 shows a computer system;
[0015] [0015]FIG. 2 is a functional block diagram of the computer system of FIG. 1;
[0016] [0016]FIG. 3 is a flowchart of a BIOS implementation that provides the desired CMOS restoring feature; and
[0017] [0017]FIG. 4 illustrates a method for restoring a computer's CMOS parameters.
[0018] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the drawings and detailed description thereto are not intended to limit the invention to the particular form disclosed, but on the contrary, the is to cover all modifications, equivalents and alternatives falling within the spirit and scope of the present invention as defined by the appended claims.
[0019] In addition, certain terms are used throughout the following description and claims to refer to particular system components. This document does not intend to distinguish between components that differ in name but not function. In the following discussion and in the claims, the terms “including” and “comprising” are used in an open-ended fashion, and thus should be interpreted to mean “including, but not limited to . . . ”. Also, the term “couple” or “couples” is intended to mean either an indirect or direct electrical connection. Thus, if a first device couples to a second device, that connection may be through a direct electrical connection or through an indirect electrical connection via other devices and connections.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0020] Turning now to the figures, FIG. 1 shows a computer system 100 in accordance with the preferred embodiment comprising a computer chassis 102 coupled to a display device 104 and a user input device 106 . The computer chassis 102 preferably has a power button 108 and may also have a power indicator 110 such as a light emitting diode (“LED”). When the power button 108 is momentarily pressed, power indicator 110 illuminates and computer system 100 boots up. Momentarily pressing power button 108 a second time preferably places the computer system 100 in a reduced-power state.
[0021] At this point, a brief discussion of reduced-power states is warranted. Many computer system manufacturers have implemented a variety of reduced-power states for purposes such as conserving battery power, allowing fast boot-up, providing remote access, and extending life. A standard known as the Advanced Configuration and Power Management Interface Specification (“ACPI”) has been promulgated by Intel, Microsoft, and Toshiba to standardize the management of these states. Revision 1.0 of this standard defines user-initiated events to request the operating system to transition to a reduced-power state. Among the events defined there is momentarily pressing the power button, which causes a transition from the working state to a preferred reduced-power state configured by the user. Significantly, however, is another event in which pressing the power button for four seconds causes an unconditional transition to a “SOFT-OFF” state (the SOFT OFF state is distinguished from a mechanical off state only by the presence of power to the power management circuitry). This event is defined to allow a user to force a reboot if the computer locks up or becomes unstable. Without this event, the user might be unable to force a reboot without physically unplugging the system.
[0022] [0022]FIG. 2 illustrates an exemplary architecture of computer system 100 . Although the system 100 can be implemented with many other architectures, the embodiment shown in FIG. 2 is presented to aid in explaining the operation of a preferred embodiment. Computer system 100 includes a CPU 202 coupled to a bridge logic device 206 via a CPU bus. The bridge logic device 206 is sometimes referred to as a “North bridge” for no other reason than it often is depicted at the upper end of a computer system drawing. The North bridge 206 also couples to a main memory array 204 by a memory bus, and may further couple to a graphics controller 208 via an accelerated graphics port (“AGP”). The North bridge 206 couples CPU 202 , memory 204 , and graphics controller 208 to the other peripheral devices in the system through a primary expansion bus (“BUS A”) which may be implemented as a peripheral component interconnect (“PCI”) bus or an extended industry standard architecture (“EISA”) bus. Various components that comply the communications protocol and electrical requirements of BUS A may reside on this bus, such as an audio device 214 , a IEEE 1394 interface device 216 , and a network interface card (“NIC”) 218 . These components may be integrated onto the motherboard or they may be plugged into expansion slots 210 that are connected to BUS A.
[0023] If other secondary expansion buses are provided in the computer system, as is typically the case, another bridge logic device 212 is used to couple the primary expansion bus (“BUS A”) to a secondary expansion bus (“BUS B”). This bridge logic 212 is sometimes referred to as a “South bridge” reflecting its location vis-á-vis the North bridge 206 in a typical computer system drawing. An example of such bridge logic is described in U.S. Pat. No. 5,634,073, assigned to Compaq Computer Corporation. Various components that comply with the bus protocol of BUS B may reside on this bus, such as hard disk controller 222 , Flash ROM 224 , and Super I/O controller 226 . Slots 220 may also be provided for plug-in components that comply with the protocol of BUS B. Flash ROM 224 stores the system BIOS that is executed by CPU 202 during system initialization.
[0024] The Super Input/Output (“Super I/O”) controller 226 typically interfaces to input/output devices such as a keyboard 106 , a mouse 232 , a floppy disk drive 228 , a parallel port, a serial port, and sometimes a power controller 230 and various other input switches such as a power switch 108 and a suspend switch 109 . In one embodiment, the Super I/O controller 226 includes control registers (“REGS”) for configuring the input/output devices and for reporting their status. The Super I/O controller 226 preferably has the capability to handle power management functions such as reducing or terminating power to components such as the floppy drive 228 , and blocking the clock signals that drive components such as the bridge devices 206 , 212 thereby a sleep mode in the expansion buses. The Super I/O controller 226 may further assert System Management Interrupt (“SMI”) to indicate special conditions pertaining to input/output activities such as sleep mode.
[0025] Super I/O controller 226 may include battery-backed CMOS memory for storing BIOS configuration parameters for system 100 , and may further include a counter/timer and a Real Time Clock (“RTC”). The counter/timer may be used to track the activities of certain components such as the hard disk 222 and the primary expansion bus, and induce a sleep mode or reduced power mode after a predetermined time of inactivity. The Super I/O controller 226 may also induce a low-power suspend mode if the suspend switch 109 is pressed, in which the power is completely shut off to all but a few selected devices. Exempted devices might include the Super I/O controller 226 itself and NIC 218 . When Super I/O controller 226 senses a power switch closure, it asserts a system POWER_ON signal and initiates system boot-up. During system boot-up, the CPU 202 retrieves the BIOS from Flash ROM 224 and executes the BIOS. The BIOS stores system configuration parameters in CMOS, and retrieves these parameters to initialize and configure various system components to place the system in readiness for operation by a user.
[0026] During system initialization, the BIOS typically provides the user an opportunity to enter a “setup” program, in which the various system configuration parameters may be viewed and modified by the user. In order that the user might be provided with an easy-to-use interface, the setup program doesn't run until after the user input device 106 and the display device 104 have been initialized. Other components may also be configured by the BIOS prior to the execution of the setup program. Consequently, it is entirely possible for an incorrect configuration parameter prevent the system from being properly configured, to prevent the system from booting and to prevent the user from accessing the setup program whereby the situation might be rectified. In these circumstances, it is desirable to restore the parameters to a set of values known to work properly. Typically this is done by removing the power from the CMOS memory, either by removing the battery while the computer is unplugged, or by disconnecting a jumper. When power is restored to the CMOS memory, a “CMOS invalid” bit is automatically set (typically in one of the Super I/O controller's control registers) to indicate that a loss of power has occurred. The BIOS examines this bit before using any of the configuration parameters from the CMOS memory, and if the bit is set, the BIOS uses default values to boot the computer and may automatically run the setup program to prompt the user for new parameter settings. The BIOS may then reset the “CMOS invalid” bit once new configuration parameters are stored in memory.
[0027] The effort involved in opening the case, locating, removing, and replacing the jumper, and then reprogramming the CMOS parameters is substantial, particularly for a novice unfamiliar with internal computer components and motherboards in particular. Accordingly, FIG. 4 shows a new method for restoring a computer's CMOS memory. A user, suspecting that the computer is failing to boot because of an incorrect CMOS parameter, presses and holds the power button for four seconds, as indicated by block 402 . This may be done while the computer is trapped in the POST. Alternatively, this may be done just after the computer is turned on from a “soft-off” state, but before it has exited the POST. In either case, a “POST in progress” bit will be set, and a “Power Button Override” bit will be set, and the computer will be returned to the “soft-off” power state. These bits may be provided in power control registers in the south bridge. as indicated by block 404 , the user presses the power button momentarily to turn the computer back on. The computer will automatically restore the CMOS parameters from a backup copy in response to the “Power Button Override” and “POST in progress” bits being set.
[0028] [0028]FIG. 3 shows a flowchart of one BIOS implementation of this restoration procedure. Execution of the BIOS by the CPU is initiated by assertion of a system RESET signal, as indicated by block 302 . In block 304 , the BIOS initializes the “CMOS Restore” bit to zero, and in block 306 the BIOS retrieves the value of the “Power Button Override” bit from the power register. In block 308 , the BIOS determines if the “Power Button Override” bit is clear. If yes, then execution passes to block 314 . Otherwise, the BIOS checks to see if the “POST in progress” bit is clear. If yes, then execution passes to block 314 . Otherwise, the BIOS sets the “CMOS Restore” bit to 1 in block 312 , and execution passes to block 314 . In block 314 , the “POST in progress” bit is set to 1. In block 316 , the BIOS checks to see if the “CMOS Restore” bit is set. If yes, then in block 318 the BIOS restores the CMOS settings from a backup copy. Block 320 indicates the normal POST that is performed by the BIOS. If the POST completes successfully, then in block 322 , the BIOS checks to see if the CMOS parameters have changed (e.g., if the user has entered new values via the setup program). If yes, then in block 324 the new parameters are copied to backup memory locations. In block 326 , the “POST in progress” bit is cleared, and in block 328 , the BIOS initiates execution of the operating system.
[0029] It is noted that the power button 108 is multifunctional, and that this procedure extends the functionality of the power button. Pressing power button 108 momentarily toggles the computer between its working state and its reduced power state. Pressing and holding the power button for 4 seconds will force the computer into a “soft-off” state. Pressing and holding the button for 4 seconds while the computer is in a POST state will additionally cause the computer to automatically restore backup settings to CMOS parameters during the next boot-up sequence.
[0030] It is noted that one of ordinary skill in the art, upon reviewing this disclosure, will recognize a number of variant implementations of this CMOS restoring procedure. The above discussion is not intended to exclude such recognizable variations, and it is intended that the following claims be interpreted to embrace all such variations and modifications. | A method for easily restoring CMOS parameters in a computer having a multi-function power button is provided. In one embodiment, the method for restoring CMOS parameter values in a computer includes (a) pressing the power button for a predetermined time delay while the computer is performing a power-on self test (“POST”), thereby placing the computer in an OFF state; and (b) momentarily pressing the power button to turn on the computer. Pressing the power button for four seconds preferably invokes a power button override function. The power button override function unconditionally forces the computer to a “soft-off” state. The BIOS is preferably configured to determine if the power-override function was invoked during the POST in the previous boot-up, and if so, to replace the CMOS parameter values with backup parameter values before proceeding with the current boot-up. The CMOS parameter values are preferably backed up only if they have changed and the BIOS has successfully completed the POST procedure with the changed values. This ensures that the backup values will allow the computer to boot when CMOS parameter restoration is needed. | 6 |
BACKGROUND
1. Field Of The Invention
The invention relates to a regulating apparatus on a self-propelled harvester having a mowing bar which is swivelable by hydraulic control in a vertically adjustable manner and transversely to the direction of travel, and which has ground scanners on the sides, the ground clearance signals of which are supplied to a control apparatus to regulate a swiveling motion transverse to the direction of travel.
2. The Prior Art
German Pat. No. DE-A 35 22 699 discloses a self-propelled harvester with a mowing bar disposed on the front and having the scanners scanning the contour of the ground; the signals of the scanners swivel the mowing bar transversely or longitudinally of the travel direction, by hydraulic control.
German Pat. No. DE-A 32 30 330 also discloses a self-propelled harvester having a mowing bar swivelable by hydraulic control by means of a ground pressure sensor in order to adjust the cutting height.
A combined harvester and thresher is also known from German Pat. No. DE-C 33 32 763 having an inclination sensor, which serves to effect hydraulic control of an actuation device of a top sifter, for the sake of uniform distribution of the harvest in a feeder and cleaning and apparatus that swivels back and forth.
These known harvesters have the disadvantage that the regulating apparatus for swiveling the mowing bar, the cutting height adjustment means, and the harvest distribution means operate completely independently of one another, so that the different time constants of the adjusting circuit can result in disruptive coupling vibrations; especially when moving at high speed and over soft and/or bumpy ground, this does not allow uniformly short cutting and carries the risk that the harvester may become bogged down or the mowing beam may be damaged.
BRIEF SUMMARY OF THE INVENTION
It is the object of the invention to disclose a self-propelled harvester with a high harvesting yield and a uniform short cutting height, even over steeply sloping, soft, bumpy ground.
The object is attained by providing that the difference between the ground clearance signals is utilized for regulating the swiveling, and the mean value of the ground clearance signals serves an actual-value component for regulating a cutting height of the mowing bar.
Advantageous embodiments are defined by the dependent claims.
It has proved to be particularly advantageous to dispose a plurality of ground scanners in groups, on both sides of the mowing bar, and to perform the regulation with respect to the maximum deflection of the various groups; in this way furrows running longwise with the direction of travel do not affect regulation, and the mowing mechanism blades are prevented from sinking in too deep.
It has also proved to be advantageous in regulating the cutting height to obtain the actual signal predominantly from a ground pressure signal of the mowing bar and to a small extent, for instance up to approximately 20%, from the mean value of the ground scanners, and to incorporate the ground pressure in a predetermined operating range elastically in a spring, thereby preventing fluctuations in the cutting height adjustment resulting from relatively small bumps in the ground.
The comparators of the regulators are provided with a hysteresis that precludes an overload of the hydraulic adjusting members when the ground has closely-spaced bumps. The adjusting members are additionally secured by thermal safety switches against destruction from an overload.
Since in the operating region of a harvester, there may also be obstacles that exceed a given stubble height, such as rocks, ditches, animals, and so forth, an oversteer option in the regulation is provided, in which the originally specified setpoint value of the cutting height is maintained, and thus need not be reset once the obstacle is overcome. The oversteer scanners are advantageously suitable for long-term manual operation as well, so that emergency operation is possible even if the regulating apparatus is absent or defective.
Advantageously, the inclination sensor that serves to regulate the sifter apparatus can be used instead of the ground scanners to regulate the lateral swiveling of the mowing bar, for instance if one of the ground scanners is damaged or if a relatively high stubble height is specified, making scanning of the ground unnecessary. If a ground scanning means is always provided, then conversely the inclination sensor becomes unnecessary, and the sifter apparatus is regulated with the differential signal of the ground scanners.
Particularly advantageously, the regulating apparatus may be embodied by a microprocessor, because in it the actual values entered relating to a particular specified operating region can be evaluated in a simple manner. Moreover, the particular hysteresis range and the idle time of the set-point/actual-value comparison is suitably specified and varied as needed. These specifications and variations of the regulating characteristic effected thereby are advantageously derived from the incident reactions of the regulating apparatus, for instance from the periodicity or from the proximity to the limit load, and moreover are optimally ascertained as a function of operating conditions such as travel speed, ground roughness, cutting height, and so forth. This makes it advantageously simple to achieve a proportional-integral-differential regulating characteristic with dynamic parameter adaptation.
The entry by the operator of the set-point value for the cutting height and other operating parameters for the regulating characteristic can simply be performed by monitoring the timing of operating contacts, without using analog transducers.
The function of the regulating circuits is advantageously monitored continuously by monitoring the reaction time and by monitoring the scanner and transducer signals as to their position in the particular operating range; in the case of a malfunction, there is automatic recourse to an auxiliary function. The actual-value potentiometers are dimensioned with respect to the specified mechanical adjustment range in such a way that the associated electrical adjustment range does not encompass the entire operating range from 0 to 100% of the supply voltage, but only a partial range of approximately 5% to 95%. If the measured actual values are nevertheless outside this adjusting range, then a malfunction is occurring, such as a break in a line or damage to the mechanical scanning or coupling members, and this can be monitored and recognized, whereupon the associated transducer potentiometer is eliminated from the further evaluation. The particular operating range of the scanners and transducers is detected automatically and stored in memory for the purpose of monitoring and evaluation. Sporadic malfunctions are detected statistically and made available for sampling.
Advantageous embodiments are shown in FIGS. 1 through 6.
Brief Description of the Drawings
FIG. 1 is a perpective view in detail of a harvester, seen in X-ray fashion;
FIG. 2 shows a further detail of a feature of a ground scanner;
FIG. 3 shows a regulator circuit of the analog type;
FIG. 4 is a block circuit diagram of a digital control apparatus;
FIG. 5 is a flow chart of a controlled system;
FIG. 6 shows a flow chart of an adaptation function.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 shows a self-propelled harvester (1) having a mowing bar (2), which is swivelable and within narrow limits is adjustable in height by means of hydraulic swivels (20, 21) about the center axis of the harvester (1). The hydraulic cylinders of the swivels (20, 21) are connected in series via a coupling line (HK). They are acted upon in alternation for swiveling via control valves at the mirror-symmetrically arranged connections (CD). The mowing bar (2) is also swivelable in height about a swivel axis (32) by means of parallel-connected hydraulic cylinders (30, 31). Elastic ground scanners (40, 41; 42, 43) are disposed on both side walls (10, 11) and coupled in pairs, each pair to one scanner potentiometer (46, 47), via a rotationally supported coupling shaft (44, 45). The elasticity of the ground scanners (40, 41; 42, 43) adapts them to an average ground level. The parallel disposition of hoops via the shafts (44, 45) spaced apart by a distance that is suitably greater than the typical track width of a tire of an agricultural machine and greater than the width of a furrow, the maximum ground height is reported, and a tire track, furrow or small hole does not affect the outcome.
The swiveling and height of the mowing bar (2) with respect to the vehicle is reported by a height potentiometer (33). The ground pressure is also signalled by means of a ground pressure potentiometer (34), which is adjusted in accordance with the deformation of the support springs (35) of the hydraulic cylinders (30, 31). Alternatively, the ground pressure can also be obtained by means of a pressure pickup from the hydraulic line (A) of the hydraulic cylinders (30, 31). The grain lifter and mechanisms for feeding in the harvested grain are shown in only rudimentary form. The harvested material is fed through the feed shaft (50) into the thresher, where the sifter apparatus (not shown) is disposed. Located on it are a pendulum-actuated position sensor for the vehicle (1) and a sifter drive that is hydraulically adjustable in a controlled manner. FIG. 2 shows a detail of a different kind of ground scanner embodiment on the support of a flexible cutter bar (2). Scanner skids (40A, 41A) are swivelably supported on guide arms (48), and their swiveled position is transmitted by scanner arms (49) to the connecting shaft (44A), the rotational angle of which is transmitted via a transmission rod (46B) to the potentiometer (46A).
FIG. 3 shows a schematic regulating circuit (ST). The scanning and ground pressure potentiometer (46, 47, 34) and electromechanical hydraulic valves (VL, VR; VT, VH) for the hydraulic cylinders of the swivels (20, 21) and for raising and lowering with the hydraulic cylinders to adjust the cutting height are connected to an electronic control unit (ST). From a control panel, a cutting height transducer (SG) also leads to the control unit (ST), and control contacts (KT, KH; KL, KR) that are connected in parallel with the control outputs of the control unit are disposed on the control panel. These contacts enable oversteering of the regulating apparatus by hand, for instance to overcome obstacles in the travel path or in turning the vehicle, and also enable purely manual operation, for instance if the regulating apparatus is absent or defective.
The control unit (ST) is made by analog technology. It includes comparators (V1, V2) with hysteresis, the outputs of which act upon the valves (VT, VH; VL, VR) via amplifiers. The first comparator (V1) is connected at one input to the ground pressure set-point value transducer (SG), and at its second input an actual signal is supplied via an adding resistor network, which comprises a first resistor (R1) and two resistors (R10, R10A), of equal size and approximately ten times higher resistance; of these, the first resistor is connected to the ground pressure signal (SB), which is emitted by the ground pressure potentiometer (34), and the other resistors (R10, R10A) are connected to the ground clearance signals (SR, SL) of the ground scanners (46, 47). In this way the raising and lowering takes place substantially as a function of the ground pressure on the pan of the mowing bar, and to a certain fractional extent of approximately 20% by means of the summing signal of the height scanner, which indicates the average cutting height. The assumption here is that the network resistors (R1, R10, R10A) are large compared with the potentiometer resistors. The valves (VH, VT) connect the cylinder connection (A) to the oil pressure line or the return line (HD, RL).
The ground clearance signals (FR, FL) are evaluated differentially in the second comparator (V2), with the output signals of which the swiveling to the left and right is controlled via four-way valves (VW1, VW2). These valves respectively connect the oil pressure line (HD) and the return line (RL) to one of the two connections (C, D) of the two swivels (20, 21)--see FIG. 1 in alternation. The swivels (20, 21) are each coupled at one end to an oil communication line (HK), so that raising one side lowers the other, and vice versa, and so swiveling takes place while the average position and a favorable cross section of the feed chute (50) are maintained; FIG. 1.
The comparator inputs are provided with integration elements to suppress interference, and the comparator outputs lead via mutual shutoff elements, which prevent the control contacts from being inadvertently switched on simultaneously, even if an oversteering actuation of the control contacts (KT, KH; KL, KR) occurs.
FIG. 4 is a block circuit diagram of a digital control unit (STD), which is compatible with the analog control unit (ST) in FIG. 3 but includes additional functions. The contacts (KT, KH, KR, KL), the valves (VT, VH, VL, VR) and the signal transducers (SG, SB, SL, SR) are identical. All the operating elements are disposed on a control panel. In addition, thermal safety switches (TT, TH, TL, ZR, TRR, TRL) are shown, by way of which the voltage supply to the various valves is carried. Also shown are the elements provided for regulating the riddle sifter. For this purpose, the undercarriage inclination transducer (FNG) and position transducer for the riddle sifter actuation, namely the riddle sifter transducer (RSG), are provided. To enable controllable swiveling of the mowing bar even without ground scanning, a cutting mechanism inclination transducer (SNG) is also disposed on one of the swivels (21); see FIG. 1. Moreover, the height potentiometer (33), which emits a height position signal (SH) for the vertical swiveling of the cutting mechanism about its swivel axis on the undercarriage, is carried to the input. A further height signal (SV) from a further potentiometer is optionally also supplied to the control unit (STD), which via a control shaft extending over the entire mowing mechanism transmits the position of the uppermost of all the ground scanners (40-43) at a given time by means of pickups. A scanner (TE) on the operating apparatus is also provided, by means of which either the pickup of the actual signal for the ground pressure (SB) from the ground pressure potentiometer (34) or the pickup of the vertical position signal (SH) from the height potentiometer (33), optionally in combination with the height signal (SV), is determined. The regulation of ground pressure or vertical position is signalled to the operator by the operation indicator lamps (LV, LL). The transducer signals are carried via a controllable multiplexer (MPX) to an analog/digital converter (AD), the digital signals of which are processed under program control. The course of the program is controlled as a function of time by means of a clock (CL). The specified values are input via a keyboard (TA). The standardized actual values, for instance the ground pressure or the cutting mechanism height, are displayed on a display device (AA).
The program includes various subroutines, which perform various special functions. The regulation subroutine performs the function equivalent to that performed by the analog regulator, in that the signals are continuously selected, digitized and stored in memory in succession via the multiplexer (MVX). After that, the additive combining of the ground pressure signal value (SB) with the fractions of the left and right scanner signal value (SL, SR) and the comparison with the set-point value (SG) are performed, taking a hysteresis threshold into account. Depending on whether the signal exceeds this hysteresis threshold or drops below it, the valve adjustment raising or lowering signal is then emitted.
A comparison of the scanning signals taking a threshold value (SL, SR) is also performed, whereupon the control signal for swiveling to the right or the left is emitted depending on whether the signal exceeds the threshold, or fails to attain it.
In addition, the undercarriage inclination value (FNS) is compared with the riddle sifter signal value (RSG), taking a given hysteresis threshold into account, and as a function thereof if the threshold is exceeded or if the signal fails to attain it, the riddle sifter valve (VRL, VRR) adjusting to the left or right is actuated.
Moreover, a monitoring program of the digital input signals is performed cyclically, with which, as applicable, an actuation of a control contact (KT, KH, KL, KR) in the currentless state of the valves (VT, VH, VL, VR) is detected, and in the state where the valves do have current, their voltage supply via the thermal safety contacts (TT, TH, TL, TR, TRR, TRL) is detected by measurement of the residual voltage of the output switching amplifiers. In the event that a short circuit should be present at the output side, the measurement of the residual voltage of the output amplifiers and their monitoring with respect to an upper and lower threshold value provides further overload protection for the switch amplifiers at the outputs, in that an immediate shutoff takes place if there is an excessively high voltage loss with respect to the upper threshold value. The state without or with current is in each case briefly established during the signal evaluation, that is, at approximately 1% of the cycling time and correspondingly briefly with respect to the valve switching time, so that this does not affect the operating state. If one of the control contacts (KT, KH, KR, KL) is found to have been actuated, then the complementary valve in each case, which would direct a swiveling in reverse of that effected by the control contact, is either not switched on, if it is off, or is switched off, if it is on. The actuation of the control contacts, which primarily serve to oversteer the regulating apparatus, which is necessary to overcome obstacles or in turning, is evaluated in a further program feature such that the chronological sequence of actuation is analyzed, and the outcome of analysis triggers a control function. For instance, a brief succession of two short actuations can be utilized to effect the retention of the setpoint value, which in response to renewed brief key actuations is supplied to or withdrawn again from the regulator in alternation. This makes a great simplification in operation attainable, and analog transducers can be omitted. The set-point transducer (SG), as well, can be replaced or omitted in this way.
An advantageous program embodiment comprises the simulation of the thermal load on the valves by continuous accumulation of the various ON times, with appropriate reduction by a fraction corresponding to the accumulated value, the fraction representing the continuing cooling process. As a function of the thus-formed load value, if the exceeding of a specified load threshold value is ascertained, a shutoff of the associated valve takes place. However, preferably the attainment of the threshold value is prevented, by reducing the actuation frequency of the valve by increasing the associated hysteresis threshold, or specifying a longer switch idle time, the greater the load value ascertained. This also tends to prevent control deviations. Other load variables as well, such as the hydraulic temperature, can be measured or calculated and used as functional variables that determine the hysteresis values or the idle time.
By means of an autocorrelation analysis of the ON and OFF times of the adjusting signals over a plurality of switching events, undesired deviations are recognized, and a digital value is generated that is equivalent in magnitude to a possibly occurring periodicity, and this digital value is utilized to vary the hysteresis and/or idle time, which prevents control deviations from forming.
Another advantageous program comprises continuous monitoring of the operating ranges of the signal transducers (SR, SL, SD, SNG, FNG, RSG), resulting in an automatic adaptation of the actual values to the prevailing operating range, thereby making external zero-point adjustment unnecessary and providing for a continuous function monitoring, which is particularly important for the ground scanners because of the danger that their feelers may bend or break.
FIG. 5 is a flow chart for a monitoring subroutine of this kind, which is performed for the various signals, for which purpose actual-value and final-value memories are furnished. In the first step, the pickup of a first measured value (I1) takes place; in the comparison step, which is the second program step, the measured value is compared with the set-point value (SW), minus the hysteresis value (HW). If the threshold has not been exceeded, then the associated valve is switched off in the next step; otherwise, in step 3, it is switched on. Next, in step 4, a timing program for an idle time (T1) of the adjusting means is run, which suffices for adjustment by a differential value (DW). In step 5, a further measurement of the second measured value (I2) then takes place, the difference of which from the first measured value (I1) is compared quantitatively with the differential value (DW). If the adjustment was not in accordance with expectations, then a variation via the threshold was not attained, and so the second measured value is compared in the seventh step with the stored final value (IE). If that value is not attained, then in the eighth step the new, lower second measured value (I2) is stored in memory as the new final value (IEN); however, if it has been attained, then this case of a regulation up to the range threshold is output to a display and to a statistical evaluation means or stored in memory.
In both cases, a shutoff of a valve takes place, and the program is exited. If in the sixth step the differential value (DW) was exceeded or attained, then subsequently the second measured value (I2) is likewise compared with the final value (IE), and if that value has not been attained the subroutine is exited; otherwise, in an eighth step, a second idle time program (T2) is run through, after which, in step 9, a third measured value (I3) is measured, which is compared in step 10 with the final value (IE). If that final value is still valid, then the valve is switched off and the program is exited; however, if it has been exceeded, then the new, higher value is stored in memory as the new final value (IEN).
For regulation in the other direction, a corresponding program having the other final value is run through. The evaluation of the various measured values takes place in each case in the range between the respective lower and upper final value, so that the measurement potentiometers should be operated in a middle range, and the particular location of the measurement range will not affect the regulation.
Instead of the potentiometer type of measured value transducers, other transducers, such as those using ultrasound, may be used, even if their signal level deviates from the typical potentiometer signal levels, because the jointly running evaluation of the final value in each case results in an automatic adaptation of the measurement range.
A further advantageous program feature is that the signal of the undercarriage inclination transducer (FNG) is used for regulating the swiveling of the mowing bar. This is advantageous if a relatively high cutting height is selected and ground scanners cannot be used. If the soil is loose, it can be assumed that an undercarriage inclination will come about from sinking into the earth on one side or running into a longitudinal furrow or tire track groove. Thus a counterswiveling of the mowing bar is helpful. For this reason, from the undercarriage inclination, a set-point value for the swiveling regulator is derived, to which the cutting mechanism inclination signal (SNG) of a transducer is supplied as an actual value, this signal for instance signalling the adjustment of one swivel (21).
A further option for simplifying the mechanical ground scanning is that instead of a connecting shaft for two parallel scanner skids, with this shaft emitting the higher of the two levels to a potentiometer by its rotation, one potentiometer is disposed on each skid, and their signals are compared, preferably after the digital conversion, and then used as the respective higher signal for actual value formation.
An advantageous program feature shown in FIG. 6 provides a three-point regulation with a proportional-integral-differential characteristic and dynamic adaptation of the regulating parameters. In a first step of comparison of the actual value (X) with the set-point value (W), taking a hysteresis (H) into account, it is ascertained whether the actual value has fallen below the set-point value. In that case, the adjusting member (Y) that suitably operates in the opposite direction is activated in the second step.
In a third step, the variation over time (DX) of the actual value (X) is compared with a second comparison value (W2). If the variation is less, the subroutine is ended; otherwise, in a fourth step, an integral value (IX) of the actual value (X), which is continuously formed as a summation value of the variations (DX) over a given integration period, is compared with a third comparison value (W3), and if that value is exceeded, then in a fifth step the adjusting member (Y) is deactivated. If in the first comparison step the set-point value (W) having the hysteresis (H) was exceeded by the actual value (X), then in a second comparison step it is checked whether the set-point value (W) itself is exceeded; if that is the case, then the adjusting element (Y) is deactivated in step 3. In a fourth step, checking of the variation (DX) as to whether it has dropped below the second comparison value (W2) is done, and if that is the case, then in a fifth step a comparison of the integral value (IX) with the third comparison value (W3) takes place, and if the value has dropped below it the adjusting element (Y) is activated, after which the program is ended. In all the alternative comparison outputs not pursued, as well, the program cycle is ended.
Another simple option for dynamic adaptation comprises varying the hysteresis in proportion to the actual speed value.
The adaptation of the regulation behavior can be performed very favorably by varying the integration time. To this end, the load values ascertained in the other subroutine, and a vehicle speed signal (FGS)--see FIG. 4--as well can be used, which is supplied by the vehicle control system or a suitable transducer to the control unit (STD). The frequency of switchover of the adjusting elements is advantageously cyclically accumulated in a memory, from which an operating state signal (BZS) is derived and output to the undercarriage control and/or to the operator.
The various subroutines shown are activated cyclically in a known manner by a master program and performed, being supplied with the various parameters such as comparison values, threshold values and so forth of the regulators, transducers and so forth. The exceeding of threshold values, or relatively long persistance in the vicinity of the threshold value, the occurrence of unauthorized operating states, as well as the time in service and switching frequency of components subject to wear, such as valves and so forth, are suitably statistically detected and can be read out for maintainance purposes. | A positional regulation of a mowing mechanism is effected in terms of height as a function of a ground pressure signal (SB) and in terms of swiveling in the transverse direction as a function of lateral ground clearance signals (SL, SR), the adjusting signals being carried to hydraulic valves (VT, VH; VL, VR).
The goal is to increase the accuracy and freedom from fluctuation in the course of the mowing mechanism cutting height.
The ground clearance signals (SL, SR) are used in proportion with the ground pressure signal (SB) for vertical position regulation. A linkage of these signals (SL, SR, SB) with further transducer signals and a method for automatic adaptation of the regulating characteristic by varying the hystereses and idle times of the regulators (V1, V1) is disclosed.
The regulating apparatus is used in harvesting and threshing combines when low-height crops are to be mowed and when the ground is bumpy and soft. | 0 |
[0001] The present invention relates to novel compounds which are serotonin reuptake inhibitors and as such effective in the treatment of for example depression and anxiety.
BACKGROUND OF THE INVENTION
[0002] Selective serotonin reuptake inhibitors (hereinafter referred to as SSRIs) have become first choice therapeutics in the treatment of depression, certain forms of anxiety and social phobias, because they are effective, well tolerated and have a favourable safety profile compared to the classic tricyclic antidepressants.
[0003] However, clinical studies on depression indicate that non-response to SSRIs is substantial, up to 30%. Another, often neglected, factor in antidepressant treatment is compliance, which has a rather profound effect on the patient's motivation to continue pharmacotherapy.
[0004] First of all, there is the delay in therapeutic effect of SSRIs. Sometimes symptoms even worsen during the first weeks of treatment. Secondly, sexual dysfunction is a side effect common to all SSRIs. Without addressing these problems, real progress in the pharmacotherapy of depression and anxiety disorders is not likely to happen.
[0005] In order to cope with non-response, psychiatrists sometimes make use of augmentation strategies. Augmentation of antidepressant therapy may be accomplished through the co-administration of mood stabilizers such as lithium carbonate or triiodothyronin or by the use of electroshock.
[0006] The effect of combined administration of a compound that inhibits serotonin reuptake and a 5-HT 1A receptor antagonist has been evaluated in several studies (Innis et al. Eur. J. Pharmacol. 1987, 143, 1095-204 and Gartside Br. J. Pharmacol. 1995, 115, 1064-1070, Blier et al. Trends in Pharmacol. Science 1994, 15, 220). In these studies, it was found that 5-HT 1A receptor antagonists would abolish the initial brake on 5-HT neurotransmission induced by the serotonin reuptake inhibitors and thus produce an immediate boost of 5-HT transmission and a rapid onset of therapeutic action.
[0007] Several patent applications have been filed, which cover the use of a combination of a 5-HT 1A antagonist and a serotonin reuptake inhibitor for the treatment of depression (see e.g. EP-A2-687472 and EP-A2-714663).
[0008] Another approach to increase terminal 5-HT would be through blockade of the 5-HT 1B autoreceptor. Microdialysis experiments in rats have indeed shown that increase of hippocampal 5-HT by citalopram is potentiated by GMC 2-29, an experimental 5-HT 1B receptor antagonist.
[0009] Several patent applications covering the combination of an SSRI and a 5-HT 1B antagonist or partial agonist have also been filed (WO 97/28141, WO 96/03400, EP-A-701819 and WO 99/13877).
[0010] It has previously been found that the combination of a serotonin reuptake inhibitor with a compound having 5-HT 2c antagonistic or inverse agonistic effect (compounds having a negative efficacy at the 5-HT 2C receptor) provides a considerable increase in the level of 5-HT in terminal areas, as measured in microdialysis experiments (WO 01/41701). This would imply a shorter onset of antidepressant effect in the clinic and an augmentation or potentiation of the therapeutic effect of the serotonin reuptake inhibitor (SRI).
[0011] The present invention provides compounds which are serotonin reuptake inhibitors for the treatment of affective disorders such as depression, anxiety disorders including general anxiety disorder and panic disorder and obsessive compulsive disorder. Some of the compounds also have a combined effect of serotonin reuptake inhibition and 5-HT 2C receptor modulation, which according to WO01/41701 would imply a faster onset of anti-depressant activity.
[0012] A few of the compounds embraced by the present invention have previously been described in WO 01/49681 and in WO02/59108 However, the compounds of WO01/49681 are not disclosed as having any therapeutic or biological activity. The compounds of WO02/59108 are disclosed as intermediates in the synthesis of compounds different from the compounds of the present invention with a terapeutic activity as melanocortin receptor agonists. One compound, 1-(2-phenoxyphenyl)-piperazine, embraced by the present invention, is disclosed in U.S. Pat. No. 4,064,245 as being useful in the treatment of metabolic disorders.
SUMMARY OF THE INVENTION
[0013] The present invention provides compounds of the general formula I
[0000]
[0000] wherein
Y is N, C or CH;
[0014] X represent O or S;
m is 1 or 2;
p is 0, 1, 2, 3, 4, 5, 6, 7 or 8;
q is 0, 1, 2, 3 or 4;
s is 0, 1, 2, 3, 4 or 5;
[0015] The dotted line represents an optional bond;
[0016] Each R 1 is independently selected from the group represented by C 1-6 -alkyl, or two R 1 attached to the same carbon atom may form a 3-6-membered spiro-attached cyclo-alkyl;
[0017] Each R 2 is independently selected from the groups represented by halogen, cyano, nitro, C 1-6 -alk(en/yn)yl, C 1-6 -alk(en/yn)yloxy, C 1-6 -alk(en/yn)ylsulfanyl, hydroxy, hydroxy-C 1-6 -alk(en/yn)yl, halo-C 1-6 -alk(en/yn)yl, halo-C 1-6 -alk(en/yn)yloxy, C 3-8 -cycloalk(en)yl, C 3-8 -cycloalk(en)yl-C 1-6 -alk(en/yn)yl, acyl, C 1-6 -alk(en/yn)yloxycarbonyl, C 1-6 -alk(en/yn)ylsulfonyl, or —NR x R y ;
[0018] Each R 3 is independently selected from a group represented by halogen, cyano, nitro, C 1-6 -alk(en/yn)yl, C 1-6 -alk(en/yn)yloxy, C 1-6 -alk(en/yn)ylsulfanyl, hydroxy, hydroxy-C 1-6 -alk(en/yn)yl, halo-C 1-6 -alk(en/yn)yl, halo-C 1-6 -alk(en/yn)yloxy, C 3-8 -cycloalk(en)yl, C 3-8 -cycloalk(en)yl-C 1-6 -alk(en/yn)yl, C 1-6 -alk(en/yn)ylsulfonyl, aryl, C 1-6 -alk(en/yn)yloxycarbonyl, acyl, —NR x CO—C 1-6 -alk(en/yn)yl, CONR x R y or NR x R y ;
[0000] or two adjacent R 3 substituents together form a heterocycle fused to the phenyl ring selected from the group consisting of
[0000]
[0000] wherein W is O or S, and R′ and R″ are hydrogen or C 1-6 -alkyl:
or two adjacent R 3 substituents together form a fused heteroaromatic system containing one, two or three heteroatoms,
wherein each R x and R y is independently selected from the group represented by hydrogen, C 1-6 -alk(en/yn)yl, C 3-8 -cycloalk(en)yl, C 3-8 -cycloalk(en)yl-C 1-6 alk(en/yn)yl, or aryl; or R x and R y together with the nitrogen to which they are attached form a 3-7-membered ring which optionally contains one further heteroatom;
or an acid addition salt thereof.
[0019] The invention also provides compounds as above provided that the compound is not 1-(2-phenoxyphenyl)-piperazine;
[0020] The invention also provides compounds as above provided that the compound is not 1-[2-(2-Methoxyphenoxy)phenyl]piperazine, 1-[2-(2,6-dimethoxyphenoxy)phenyl][1,4]-diazepane, 1-{2-[3-(dimethylamino)phenoxy]phenyl}piperazine, 1-[2-(4-methylphenoxy)phenyl]piperazine, 1-[2-(3-methylphenoxy)phenyl]piperazine, 1-[2-(3-chlorophenoxy)phenyl]piperazine, 1-[2-(3-methoxyphenoxy)phenyl]piperazine and 1-(2-phenoxyphenyl)-piperazine;
[0021] The invention provides a compound according to the above for use as a medicament.
[0022] The invention provides a pharmaceutical composition comprising a compound according to the above or a pharmaceutically acceptable acid addition salt thereof and at least one pharmaceutically acceptable carrier or diluent.
[0023] The invention provides the use of a compound according to the above or a pharmaceutically acceptable acid addition salt thereof for the preparation of a medicament for the treatment of affective disorders, such as depression, anxiety disorders including general anxiety disorder and panic disorder and obsessive compulsive disorder.
[0024] The invention provides a method for the treatment of an affective disorder, including depression, anxiety disorders including general anxiety disorder and panic disorder and obsessive compulsive disorder in a living animal body, including a human, comprising administering a therapeutically effective amount of a compound according to the above or a pharmaceutically acceptable acid addition salt thereof.
DETAILED DESCRIPTION OF THE INVENTION
[0025] Preferred embodiments of the invention are wherein p is 0;
[0026] Preferred embodiments of the invention are wherein m is 1 or 2;
[0027] Preferred embodiments of the invention are R 2 is trifluoromethyl, or C 1-6 -alkyl;
[0028] Preferred embodiments of the invention are wherein R 3 is selected from the group consisting of halogen, C 1-6 -alkoxy, C 1-6 -sulfanyl, C 1-6 -alkyl, hydroxy or trifluoromethyl;
[0029] Particularly preferred embodiments of the invention are wherein the compound of the invention is any of the following:
1-[2-(2-Trifluoromethylphenylsulfanyl)phenyl]piperazine, 1-[2-(4-Bromophenylsulfanyl)phenyl]piperazine, 1-{2-[4-(Methylsulfanyl)phenylsulfanyl]phenyl}piperazine, 1-[2-(4-Hydroxyphenylsulfanyl]phenyl}piperazine, 1-[2-(2,4-Dimethylphenylsulfanyl)phenyl]piperazine, 1-[2-(3,5-Dimethylphenylsulfanyl)phenyl]piperazine, 1-[2-(2,6-Dimethylphenylsulfanyl)phenyl]piperazine, 1-[2-(2,5-Dimethylphenylsulfanyl)phenyl]piperazine, 1-[2-(2-Trifluoromethylphenylsulfanyl)phenyl][1,4]-diazepane,
[0039] 1-[2-(3-Methylphenylsulfanyl)phenyl][1,4]-diazepane,
1-[2-(4-Butylphenoxy)phenyl]piperazine, 1-[2-(4-Methoxyphenoxy)phenyl]piperazine, 2-(4-Methylphenylsulfanyl)phenyl-1-piperazine, 1-[2-(4-Chlorophenylsulfanyl)phenyl]-piperazine, 1-[2-(4-Methoxyphenylsulfanyl)-4-chlorophenyl]piperazine, 1-[2-(4-Methoxyphenylsulfanyl)-4-methylphenyl]piperazine, 1-[2-(4-Methoxyphenylsulfanyl)-5-methylphenyl]piperazine, 1-[2-(4-Fluorophenylsulfanyl)-5-methylphenyl]piperazine, 1-[2-(4-Methoxyphenylsulfanyl)-5-trifluoromethylphenyl]piperazine, 1-[2-(4-Chlorophenylsulfanyl)phenyl]-3-methylpiperazine, 1-[2-(4-Chlorophenylsulfanyl)phenyl]-3,5-dimethylpiperazine, 4-[2-(4-Methylphenylsulfanyl)phenyl]-3,6-dihydro-2H-pyridine, 4-[2-(4-Methoxyphenylsulfanyl)phenyl]-3,6-dihydro-2H-pyridine or 4-[2-(4-Methylphenylsulfanyl)phenyl]piperidine
or a pharmaceutically acceptable acid addition salt thereof.
Definition of Substituents
[0054] Halogen means fluoro, chloro, bromo or iodo.
[0055] The expression C 1-6 -alk(en/Yn)yl means a C 1-6 -alkyl, C 2-6 -alkenyl or a C 2-6 -alkynyl group. The expression C 3-8 -cycloalk(en)yl means a C 3-8 -cycloalkyl- or cycloalkenyl group.
[0056] The term C 1-6 alkyl refers to a branched or unbranched alkyl group having from one to six carbon atoms inclusive, including but not limited to methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-2-propyl and 2-methyl-1-propyl.
[0057] Similarly, C 2-6 alkenyl and C 2-6 alkynyl, respectively, designate such groups having from two to six carbon atoms, including one double bond and one triple bond respectively, including but not limited to ethenyl, propenyl, butenyl, ethynyl, propynyl and butynyl.
[0058] The term C 3-8 cycloalkyl designates a monocyclic or bicyclic carbocycle having three to eight C-atoms, including but not limited to cyclopropyl, cyclopentyl, cyclohexyl, etc.
[0059] The term C 3-8 cycloalkenyl designates a monocyclic or bicyclic carbocycle having three to eight C-atoms and including one double bond.
[0060] In the term C 3-8 -cycloalk(en)yl-C 1-6 -alk(en/yn)yl, C 3-8 -cycloalk(en)yl and C 1-6 -alk(en/yn)yl are as defined above.
[0061] The terms C 1-6 -alk(en/yn)yloxy, C 1-6 alk(en/yn)ylsulfanyl, hydroxy-C 1-6 -alk(en/yn)yl, halo-C 1-6 -alk(en/yn)yl, halo-C 1-6 -alk(en/yn)yloxy, C 1-6 -alk(en/yn)ylsulfonyl etc. designate such groups in which the C 1-6 -alk(en/yn)yl are as defined above.
[0062] As used herein, the term C 1-6 -alk(en/yn)yloxycarbonyl refers to groups of the formula C 1-6 -alk(en/yn)yl —O—CO—, wherein C 1-6 -alk(en/yn)yl are as defined above.
[0063] As used herein, the term acyl refers to formyl, C 1-6 -alk(en/yn)ylcarbonyl, arylcarbonyl, aryl-C 1-6 -alk(en/yn)ylcarbonyl, C 3-8 -cycloalk(en)ylcarbonyl or a C 3-8 -cycloalk (en)yl-C 1-6 -alk(en/yn)yl-carbonyl group.
[0064] The term 3-7-membered ring optionally containing one further heteroatom as used herein refers to ring systems such as 1-morpholinyl, 1-piperidinyl, 1-azepinyl, 1-piperazinyl, 1-homopiperazinyl, 1-imidazolyl, 1-pyrrolyl or pyrazolyl, all of which may be further substituted with C 1-6 -alkyl.
[0065] The heterocycles formed by two adjacent R 3 substituents and fused to the parent ring may together form rings such as 5-membered monocyclic rings such as 3H-1,2,3-oxathiazole, 1,3,2-oxathiazole, 1,3,2-dioxazole, 3H-1,2,3-dithiazole, 1,3,2-dithiazole, 1,2,3-oxadiazole, 1,2,3-thiadiazole, 1H-1,2,3-triazole, isoxazole, oxazole, isothiazole, thiazole, 1H-imidazole, 1H-pyrazole, 1H-pyrrole, furan or thiophene and 6-membered monocyclic rings such as 1,2,3-oxathiazine, 1,2,4-oxathiazine, 1,2,5-oxathiazine, 1,4,2-oxathiazine, 1,4,3-oxathiazine, 1,2,3-dioxazine, 1,2,4-dioxazine, 4H-1,3,2-dioxazine, 1,4,2-dioxazine, 2H-1,5,2-dioxazine, 1,2,3-dithiazine, 1,2,4-dithiazine, 4H-1,3,2-dithiazine, 1,4,2-dithiazine, 2H-1,5,2-dithiazine, 2H-1,2,3-oxadiazine, 2H-1,2,4-oxadiazine, 2H-1,2,5-oxadiazine, 2H-1,2,6-oxadiazine, 2H-1,3,4-oxadiazine, 2H-1,2,3-thiadiazine, 2H-1,2,4-thiadiazine, 2H-1,2,5-thiadiazine, 2H-1,2,6-thiadiazine, 2H-1,3,4-thiadiazine, 1,2,3-triazine, 1,2,4-triazine, 2H-1,2-oxazine, 2H-1,3-oxazine, 2H-1,4-oxazine, 2H-1,2-thiazine, 2H-1,3-thiazine, 2H-1,4-thiazin, pyrazine, pyridazine, pyrimidine, 4H-1,3-oxathiin, 1,4-oxathiin, 4H-1,3-dioxin, 1,4-dioxin, 4H-1,3-dithiin, 1,4-dithiin, pyridine, 2H-pyran or 2H-thiin.
[0066] The term aryl refers to carbocyclic, aromatic systems such as phenyl and naphtyl.
[0067] The acid addition salts of the invention are preferably pharmaceutically acceptable salts of the compounds of the invention formed with non-toxic acids. Exemplary of such organic salts are those with maleic, fumaric, benzoic, ascorbic, succinic, oxalic, bis-methylenesalicylic, methanesulfonic, ethanedisulfonic, acetic, propionic, tartaric, salicylic, citric, gluconic, lactic, malic, mandelic, cinnamic, citraconic, aspartic, stearic, palmitic, itaconic, glycolic, p-aminobenzoic, glutamic, benzenesulfonic and theophylline acetic acids, as well as the 8-halotheophyllines, for example 8-bromotheophylline. Exemplary of such inorganic salts are those with hydrochloric, hydrobromic, sulfuric, sulfamic, phosphoric and nitric acids.
[0068] Further, the compounds of this invention may exist in unsolvated as well as in solvated forms with pharmaceutically acceptable solvents such as water, ethanol and the like. In general, the solvated forms are considered equivalent to the unsolvated forms for the purposes of this invention.
[0069] Some of the compounds of the present invention contain chiral centres and such compounds exist in the form of isomers (i.e. enantiomers). The invention includes all such isomers and any mixtures thereof including racemic mixtures.
[0070] Racemic forms can be resolved into the optical antipodes by known methods, for example, by separation of diastereomeric salts thereof with an optically active acid, and liberating the optically active amine compound by treatment with a base. Another method for resolving racemates into the optical antipodes is based upon chromatography on an optically active matrix. Racemic compounds of the present invention can also be resolved into their optical antipodes, e.g. by fractional crystallization of d- or l-(tartrates, mandelates or camphorsulphonate) salts. The compounds of the present invention may also be resolved by the formation of diastereomeric derivatives.
[0071] Additional methods for the resolution of optical isomers, known to those skilled in the art, may be used. Such methods include those discussed by J. Jaques, A. Collet and S. Wilen in “Enantiomers, Racemates, and Resolutions”, John Wiley and Sons, New York (1981).
[0072] Optically active compounds can also be prepared from optically active starting materials.
Pharmaceutical Compositions
[0073] The pharmaceutical formulations of the invention may be prepared by conventional methods in the art. For example: Tablets may be prepared by mixing the active ingredient with ordinary adjuvants and/or diluents and subsequently compressing the mixture in a conventional tabletting machine. Examples of adjuvants or diluents comprise: corn starch, potato starch, talcum, magnesium stearate, gelatine, lactose, gums, and the like. Any other adjuvants or additives usually used for such purposes such as colourings, flavourings, preservatives etc. may be used provided that they are compatible with the active ingredients.
[0074] Solutions for injections may be prepared by dissolving the active ingredient and possible additives in a part of the solvent for injection, preferably sterile water, adjusting the solution to desired volume, sterilising the solution and filling it in suitable ampules or vials. Any suitable additive conventionally used in the art may be added, such as tonicity agents, preservatives, antioxidants, etc.
[0075] The pharmaceutical compositions of this invention or those which are manufactured in accordance with this invention may be administered by any suitable route, for example orally in the form of tablets, capsules, powders, syrups, etc., or parenterally in the form of solutions for injection. For preparing such compositions, methods well known in the art may be used, and any pharmaceutically acceptable carriers, diluents, excipients or other additives normally used in the art may be used.
[0076] Conveniently, the compounds of the invention are administered in unit dosage form containing said compounds in an amount of about 0.01 to 100 mg. The total daily dose is usually in the range of about 0.05-500 mg, and most preferably about 0.1 to 50 mg of the active compound of the invention.
[0077] The compounds of the invention are prepared by the following general methods:
[0000] a) Deprotection or cleavage from a polymer support of a compound with formula II
[0000]
[0000] wherein Z represents
[0000]
[0000] and R 1 , R 2 , R 3 , m, p, q, s, X, Y and the dotted line are as described above, and R′″ is a tert-butyl, methyl, ethyl, allyl or benzyl group or R′″OCO 2 is a solid supported carbamate group, such as the Wang resin-based carbamate linker.
b) Chemical transformation of a compound with formula III
[0000]
[0000] wherein R 1 , R 2 , m, p, q, Y and the dotted line are as described above, to the corresponding diazonium compound, and subsequently reacting with a compound HXZ, wherein X and Z are as defined above.
c) Reacting a compound with formula IV
[0000]
[0000] wherein R 2 , R 3 , X, s and q are as described above with an alkylating agent of formula (Cl—(CH 2 ) m+1 )NH(CH 2 ) 2 Cl or (Br—(CH 2 ) m+1 )NH(CH 2 ) 2 Br wherein m are as defined above.
d) Reacting a compound with formula V
[0000]
[0000] wherein R 2 , R 3 , X, s and q are as described above and G is a bromine or iodine atom with a compound of formula VI
[0000]
[0000] wherein R 1 , m and p are as defined above.
e) Dehydrating and optionally simultaneously deprotecting a compound of formula VII
[0000]
[0000] wherein R 1 , R 2 , R 3 , X, m, p, q and s are as described above and R is either a hydrogen atom or a BOC group.
f) Hydrogenate the double bond in a compound of formula VIII
[0000]
[0000] wherein R 1 , R 2 , R 3 , X, m, p, q and s are as described above.
[0078] The deprotection according to method a) was performed by standard techniques, known to the persons skilled in the art and detailed in the textbook Protective Groups in Organic Synthesis T. W. Greene and P. G. M. Wuts, Wiley Interscience, (1991) ISBN 0471623016.
[0079] Starting materials of formula II wherein R′″=tert-Bu were prepared according to the procedure as outlined below. Fluoronitrobenzene derivatives were reacted with phenols or thiophenols according to the procedure of Sawyer et al. J. Org. Chem. 1998, 63, 6338 followed by reduction using standard procedures known to the persons skilled in the art. This includes reduction to the corresponding aniline using a metal hydride salt such as sodium borohydride in conjunction with palladium on carbon catalyst in an alcoholic solvent or reduction using a metal chloride salt such as zinc chloride or tin chloride. The resulting aniline was then converted to a properly substituted 3,5-diketopiperazine in a modification of the procedure of Kruse et al. Recl. Tray. Chim. Pays - Bas 1998, 107, 303 using N-butyloxycarbonyliminodiacetic acid. The 3,5-diketopiperazine derivative was then reduced with for example borane to the corresponding BOC protected piperazine, which was then deprotected to the piperazine in situ.
[0000]
[0080] The compounds shown in formula II, wherein Y═CH and the optional double bond is reduced, were prepared from their tertiary alcohol precursors VII wherein R is a BOC group, by a modified Barton reduction in a similar manner as described in Hansen et al. Synthesis 1999, 1925-1930. The intermediate tertiary alcohols were prepared from the corresponding properly substituted 1-bromo-phenylsulfanylbenzenes or their corresponding ethers by metal-halogen exchange followed by addition of an appropriate electrophile of the formula IX in a similar manner as described in Palmer et al. J. Med. Chem. 1997, 40, 1982-1989. The properly substituted 1-bromo-phenylsulfanylbenzenes were prepared in a similar manner as described in the literature by reaction of properly substituted thiophenols with properly substituted aryliodides according to Schopfer and Schlapbach Tetrahedron 2001, 57, 3069-3073 Bates et al., Org. Lett. 2002, 4, 2803-2806 and Kwong et al. Org. Lett. 2002, 4, (in press). The corresponding substituted 1-bromo-phenoxybenzenes may be prepared as described by Buck et al. Org. Lett. 2002, 4, 1623-1626.
[0000]
[0081] The cleavage from a polymer support, such as from the Wang resin based carbamate linker, according to method a) was performed according to literature known procedures (Zaragoza Tetrahedron Lett. 1995, 36, 8677-8678 and Conti et al. Tetrahedron Lett. 1997, 38, 2915-2918).
[0082] The starting material of formula II may also be prepared according to the methods described in patent application WO 01/49681. The diamines were either commercially available or synthesised by methods known to chemists skilled in the art. Iron-complexes, like η 6 -1,2-dichlorobenzene-η 5 -cyclopentadienyliron(II) hexafluorophosphate and substituted analogues were synthesised according to literature known procedures (Pearson et al. J. Org. Chem. 1996, 61, 1297-1305) or synthesised by methods known to chemists skilled in the art.
[0000]
[0083] The diazotation followed by reaction with a compound HXZ according to the method b) was performed by addition of the diazonium salt of the corresponding aniline to a solution of sodium salt of a thiophenol or a phenol in an aqueous suspension of copper. The starting material of formula III was prepared as outlined in the following. A fluoronitrobenzene derivative was reacted with a piperazine derivative in a solvent such as DMF, NMP or other dipolar aprotic solvent containing an organic base such as triethylamine to afford the orthonitophenylpiperazine derivative. The intermediate orthonitrophenylpiperazine was subsequently reduced using standard procedures as stated above to give the starting material of formula III.
[0084] The reaction of a compound of formula IV with an alkylating agent of formula (Cl —(CH 2 ) m+1 )NH(CH 2 ) 2 Cl or (Br—(CH 2 ) m+1 )NH(CH 2 ) 2 Br as its hydrobromide or hydrochloride salt, wherein m is as defined above was performed in a similar manner as described in Sircar et al. J. Med. Chem. 1992, 35, 4442-4449. Starting materials of formula IV were prepared as described above for starting materials of formula II.
[0085] The reaction of a compound of formula V with a diamine of formula VI in method d) was performed in a similar manner as described in Nishiyama et al. Tetrahedron Lett. 1998, 39, 617-620. The starting material of formula V was prepared in a similar manner as described in Schopfer et al. Tetrahedron 2001, 57, 3069-3073.
[0086] The dehydration reaction and optional simultaneous deprotection of a compound of formula VII in method e) was performed in a similar manner as described in Palmer et al J. Med. Chem. 1997, 40, 1982-1989. The starting material of formula VII wherein R═H was prepared from a compound of formula VII wherein R is a BOC group (see above) by deprotection with hydrochloric acid in methanol. Compounds of formula VII wherein R=BOC, may be prepared as described in Palmer et al. J. Med. Chem. 1997, 40, 1982-1989.
[0087] The reduction of the double bond according to method f) was generally performed by catalytic hydrogenation at low pressure (<3 atm.) in a Parr apparatus, or by using reducing agents such as diborane or hydroboric derivatives as produced in situ from NaBH 4 in trifluoroacetic acid in inert solvents such as tetrahydrofuran (THF), dioxane, or diethyl ether. The starting material of formula VIII was prepared from II as described in method a).
EXAMPLES
[0088] Analytical LC-MS data were obtained on a PE Sciex API 150EX instrument equipped with IonSpray source and Shimadzu LC-8A/SLC-10A LC system. Column: 30×4.6 mm Waters Symmmetry C18 column with 3.5 μm particle size; Solventsystem: A=water/trifluoroacetic acid (100:0.05) and B=water/acetonitrile/trifluoroacetic acid (5:95:0.03); Method: Linear gradient elution with 90% A to 100% B in 4 min and with a flow rate of 2 mL/min. Purity was determined by integration of the UV (254 nm) and ELSD trace. The retention times (RT) are expressed in minutes. Preparative LC-MS-purification was performed on the same instrument. Column: 50×20 mm YMC ODS-A with 5 μm particle size; Method: Linear gradient elution with 80% A to 100% B in 7 min and with a flow rate of 22.7 mL/min. Fraction collection was performed by split-flow MS detection.
[0089] 1 H NMR spectra were recorded at 500.13 MHz on a Bruker Avance DRX500 instrument or at 250.13 MHz on a Bruker AC 250 instrument. Deuterated methylenchloride (99.8% D), chloroform (99.8% D) or dimethyl sulfoxide (99.8% D) were used as solvents. TMS was used as internal reference standard. Chemical shift values are expressed in ppm-values. The following abbreviations are used for multiplicity of NMR signals: s=singlet, d=doublet, t=triplet, q=quartet, qui=quintet, h=heptet, dd=double doublet, dt=double triplet, dq=double quartet, tt=triplet of triplets, m=multiplet and b=broad singlet.
[0090] For ion-exchange chromatography, the following material was used: SCX-columns (1 g) from Varian Mega Bond Elute, Chrompack cat. No. 220776. Prior to use, the SCX-columns were pre-conditioned with 10% solution of acetic acid in methanol (3 mL). For de-complexation by irradiation, a ultaviolet light source (300 W) from Philipps was used. As starting polymer supports for solid phase synthesis, Wang-resin (1.03 mmol/g, Rapp-Polymere, Tuebingen, Germany) was used.
Preparation of Intermediates
η 6 -1,2-Dichlorobenzene-η 5 -cyclopentadienyliron(II) hexafluorophosphate
[0091] Ferrocene (167 g), anhydrous aluminium trichloride (238 g) and powdered aluminium (24 g) were suspended in 1,2-dichlorobenzene (500 mL) and heated to 90° C. in a nitrogen atmosphere for 5 h with intensive stirring. The mixture was cooled to room temperature and water (1000 mL) was added carefully in small portions while cooling on an ice bath. Heptane (500 mL) and diethylether (500 mL) were added, and the mixture was stirred at room temperature for 30 minutes. The mixture was extracted with diethylether (3×300 mL). The aqueous phase was filtered, and aqueous ammonium hexafluorophosphate (60 g in 50 mL water) was added in small portions under stirring. The product was allowed to precipitate at room temperature. After 3 hours the precipitate was filtered off, washed intensively with water and dried in vacuo (50° C.) to give 81 g (21%) of the title compound as a light yellow powder. 1 H NMR (D 6 -DMSO): 5.29 (s, 5H); 6.48 (m, 2H); 7.07 (m, 2H).
Preparation of Polystyrene-Bound Amines
4-[(piperazin-1-yl)carbonyloxymethyl]phenoxymethyl polystyrene
[0092] 4-[(4-Nitrophenoxy)carbonyloxymethyl]phenoxymethyl polystyrene (267 g, 235 mmol) was suspended in dry N,N-dimethylformamide (2 L). N-Methylmorpholine (238.0 g, 2.35 mol) and piperazine (102.0 g, 1.17 mol) were added and the mixture was stirred at room temperature for 16 h. The resin was filtered off and washed with N,N-dimethylformamide (2×1 L), tetrahydrofuran (2×1 L), water (1×500 mL), methanol (2×1 L), tetrahydrofuran (2×1 L) and methanol (1×1 L). Finally, the resin was washed with dichloromethane (3×500 mL) and dried in vacuo (25° C., 36 h) to yield an almost colourless resin (240.0 g).
[0093] The following polystyrene bound diamines were prepared analogously:
4-[(1,4-Diazepan-1-yl)carbonyloxymethyl]phenoxymethyl polystyrene
Preparation of resin-bound η 6 -aryl-η 5 -cyclopentadienyliron(II) hexafluorophosphates
4-({-4-[η 6 -(2-Chlorophenyl)-η 5 -cyclopentadienyliron(II)]piperazin-1-yl}carbonyloxymethyl)phenoxymethyl polystyrene hexafluorophosphate (Intermediate for 1a-1 h and 1k-1l)
[0094] 4-[(piperazin-1-yl)carbonyloxymethyl]phenoxymethyl polystyrene (115.1 g, 92 mmol) was suspended in dry tetrahydrofuran (1.6 L), and η 6 -1,2-dichlorobenzene-η 5 -cyclopentadienyliron(II) hexafluorophosphate (76.0 g, 184 mmol) was added followed by potassium carbonate (50.9 g, 368 mmol). The reaction mixture was stirred at 60° C. for 16 h. After cooling to room temperature, the resin was filtered off and washed with tetrahydrofuran (2×500 mL), water (2×250 mL), tetrahydrofuran (2×500 mL), water (2×250 mL), methanol (2×250 mL), dichloromethane (2×250 mL) and methanol (2×250 mL). Finally, the resin was washed with dichloromethane (3×500 mL) and dried in vacuo (25° C., 36 h) to yield a dark orange resin (142 g).
[0095] The following polystyrene bound iron-complex was prepared analogously:
4-({4-[η 6 -(2-Chloro-phenyl)-η 5 -cyclopentadienyliron(II)]-[1,4]-diazepan-1-yl}carbonyloxymethyl)phenoxymethyl polystyrene hexafluorophosphate (Intermediate for 1i and 1j)
Preparation of Further Intermediates 1-tert-Butoxycarbonyl-4-[2-(4-methylphenylsulfanyl)phenyl]piperidin-4-ol
[0097] A solution of BuLi (2.5 Min hexane, 12.0 ml, 30 mmol) was slowly added to a stirred solution of 1-bromo-2-(4-methylphenylsulfanyl)benzene (30 mmol) in dry THF (75 ml) under Argon at −78° C. The solution was stirred for 10 min before 4-oxo-piperidine-1-carboxylic acid tert-butyl ester (5.98 g, 30 mmol) was added in one portion. The solution was allowed to warm up to room temperature and then stirred for 3 h. Saturated aqueous NH 4 Cl (150 ml) was added and the solution was extracted with ethylacetate (150 ml). The organic phase was washed with brine, dried (MgSO 4 ) and the solvent was evaporated in vacuo. Crude 1 was purified by flash chromatography on silica gel (eluent: Ethylacetat/heptane 20:80) to produce the target compound as a white foam. LC/MS (m/z) 399.3 (MH + ); RT=3.82; purity (UV, ELSD): 98%, 100%; yield: 5.02 g (42%). 1-tert-Butyloxycarbonyl-4-[2-(4-methylphenylsulfanyl)phenyl]-3,5-dioxopiperazine (Intermediate for 2a)
[0098] 2-(4-Methylphenylsulfanyl)aniline (2.9 g, 13.5 mmol) was dissolved in dry THF (200 mL) and placed under a nitrogen atmosphere. N-(tert-butylocycarbonyl)iminodiacetic acid (4.7 g, 20.2 mmol) and carbonyl diimidazole (4.2 g, 40.4 mmol) were added to the solution and the reaction was refluxed for 60 hours. The reaction mixture was cooled to room temperature and ethyl acetate (500 mL) was added. The resulting solution was then washed with 2 N NaHCO 3 (2×200 mL), 2 N HCl (2×200 mL) and saturated sodium chloride solution (100 mL) and the solvents evaporated in vacuo. Yield 6.0 g, 107%, 1 H NMR (CDCl 3 ) 1.5 (s, 9H); 2.32 (s, 3H); 4.4-4.6 (m, 4H); 7.02-7.18 (m, 3H); 7.2-7.45 (m, 5H).
[0099] The following 3,5 diketopiperazine derivatives were prepared in an analogous fashion:
1-tert-Butyloxycarbonyl-4-[2-(4-chlorophenylsulfanyl)phenyl]-3,5-dioxopiperazine (Intermediate for 2b) 1-tert-Butyloxycarbonyl-4-[2-(4-methoxyphenylsulfanyl)-4-chlorophenyl]-3,5-dioxopiperazine (Intermediate for 2c) 1-tert-Butyloxycarbonyl-4-[2-(4-methoxyphenylsulfanyl)-4-methylphenyl]-3,5-dioxopiperazine (Intermediate for 2d) 1-tert-Butyloxycarbonyl-4-[2-(4-methoxyphenylsulfanyl)-5-methylphenyl]-3,5-dioxopiperazine (Intermediate for 2e) 1-tert-Butyloxycarbonyl-4-[2-(4-fluorophenylsulfanyl)-5-methylphenyl]-3,5-dioxopiperazine (Intermediate for 2f) 1-tert-Butyloxycarbonyl-4-[2-(4-methoxyphenylsulfanyl)-5-trifluoromethylphenyl]-3,5-dioxopiperazine (Intermediate for 2 g)
2-(3-Methylpiperazin-1-yl)phenylamine (intermediate for 3a)
[0106] Fluoronitrobenzene (7.1 g, 50 mmol) was dissolved in DMF (100 mL) containing triethylamine (10 g, 100 mmol) and placed under a nitrogen atmosphere. To the solution was added 2-methyl-piperazine (5.5 g, 55 mmol). The reaction was heated to 80° C. for 16 hours. The reaction was allowed to cool to room temperature before the solvent was reduced to half volume in vacuo. Ethyl acetate (200 mL) and ice-water (250 mL) were added to the solution and the product was extracted with diethyether (2×200 mL). The aqueous phase was saturated with sodium chloride and extracted with ethyl acetate (2×200 mL). The organic phases were combined, washed with saturated brine, dried over magnesium sulfate, filtered and the filtrate was concentrated in vacuo. The product (10.5 g) was dissolved in ethanol (250 mL). Palladium on charcoal catalyst (10% w/w, 2.2 g) was added to the solution and the solution was hydrogenated in a Parr apparatus at 3 bar for 3 hours. The solution was filtered and the solvents evaporated in vacuo to give the aniline product. Yield (8.0 g, 83%)
[0107] The following intermediates were prepared in an analogous fashion:
2-(3,5-Dimethylpiperazin-1-yl)phenylamine (intermediate for 3b)
Compounds of the Invention
Example 1
1a, 1-[2-(2-Trifluoromethylphenylsulfanyl)phenyl]piperazine
[0109] To a solution of 2-trifluoromethylthiophenol (1.75 g, 9.8 mmol) in a 1:1 mixture of tetrahydrofuran/dimethylformamide (30 mL), sodium hydride (7.4 mmol, 60% in mineral oil) was carefully added at room temperature (Caution: Generation of hydrogen). The mixture was stirred for an additional 30 min after the generation of hydrogen had ceased. Subsequently, 4-({4-[η 6 -(2-chloro-phenyl)-η 5 -cyclopentadienyliron(II)]piperazin-1-yl}carbonyloxymethyl)phenoxymethyl polystyrene hexafluorophosphate (3.5 g, 2.45 mmol) was added and the mixture was stirred at 55° C. for 12 h. After cooling to room temperature, the resin was filtered off and washed with tetrahydrofuran (2×50 mL), tetrahydrofuran/water (1:1) (2×50 mL), N,N-dimethylformamide (2×50 mL), water (2×50 mL), methanol (3×50 mL), tetrahydrofuran (3×50 mL), and subsequently with methanol and tetrahydrofuran (each 50 mL, 5 cycles). Finally, the resin was washed with dichloromethane (3×50 mL) and dried in vacuo (25° C., 12 h) to yield a dark orange resin. The thus obtained resin and a 0.5 M solution of 1,10-phenanthroline in 3:1 mixture of pyridine/water (20 mL) was placed in light-transparent reactor tube. The suspension was agitated by rotation under irradiation with visible light for 12 h. The resin was filtered and washed with methanol (2×25 mL), water (2×25 mL) and tetrahydrofuran (3×25 mL) until the washing solutions were colourless (approx. 5 cycles) and the irradiation procedure was repeated until decomplexation was complete (approx. 5 cycles). After the decomplexation was completed, the resin was washed with dichlormethane (3×25 mL) and dried in vacuo (25° C., 12 h) to obtain a light brown resin. 100 mg (77 μmol) of the thus obtained resin were suspended in a 1:1 mixture of trifluoroacetic acid and dichlormethane (2 mL) and stirred at room temperature for 2 h. The resin was filtered off and washed with methanol (1×0.5 mL) and dichloromethane (1×0.5 mL). The filtrates were collected and the volatile solvents evaporated in vacuo. The crude product was purified by preparative LC-MS and subsequently by ion-exchange chromatography. LC/MS (m/z) 339 (MH + ); RT=2.39; purity (UV, ELSD): 92%, 100%; overall yield: 1 mg (4%).
[0110] The following arylpiperazines and aryl[1,4]diazepanes were prepared analogously:
[0111] 1b, 1-[2-(4-Bromophenylsulfanyl)phenyl]piperazine: LC/MS (m/z) 350 (MH + ); RT=2.46; purity (UV, ELSD): 75%, 92%; yield: 2 mg (7%).
[0112] 1c, 1-{2-[4-(Methylsulfanyl)phenylsulfanyl]phenyl}piperazine: LC/MS (m/z) 317 (MH + ); RT=2.39; purity (UV, ELSD): 91%, 100%; yield: 2 mg (8%).
[0113] 1d, 1-[2-(4-Hydroxyphenylsulfanyl]phenyl}piperazine: LC/MS (m/z) 287 (MH + ); RT=1.83; purity (UV, ELSD): 84%, 100%; yield: 3 mg (13%).
[0114] 1e, 1-[2-(2,4-Dimethylphenylsulfanyl)phenyl]piperazine: LC/MS (m/z) 299 (MH + ); RT=2.48; purity (UV, ELSD): 95%, 100%; yield: 4 mg (17%).
[0115] 1f, 1-[2-(3,5-Dimethylphenylsulfanyl)phenyl]piperazine: LC/MS (m/z) 299 (MH + ); RT=2.51; purity (UV, ELSD): 96%, 100%; yield: 5 mg (21%).
[0116] 1g, 1-[2-(2,6-Dimethylphenylsulfanyl)phenyl]piperazine: LC/MS (m/z) 299 (MH + ); RT=2.42; purity (UV, ELSD): 97%, 100%; yield: 4 mg (17%).
[0117] 1h, 1-[2-(2,5-Dimethylphenylsulfanyl)phenyl]piperazine: LC/MS (m/z) 299 (MH + ); RT=2.46; purity (UV, ELSD): 97%, 100%; yield: 1 mg (4%).
[0118] 1i, 1-[2-(2-Trifluoromethylphenylsulfany)phenyl]-[1,4]-diazepane: LC/MS (m/z) 353 (MH + ); RT=2.46; purity (UV, ELSD): 70%, 96%; yield: 1 mg (4%).
1j, 1-[2-(3-Methylphenylsulfanyl)phenyl]-[1,4]-diazepane: LC/MS (m/z) 299 (MO; RT=2.44; purity (UV, ELSD): 76%, 93%; yield: 1 mg (4%).
[0120] 1k, 1-[2-(4-Butylphenoxy)phenyl]piperazine: LC/MS (m/z) 311 (MH + ); RT=2.77; purity (UV, ELSD): 91%, 100%; yield: 4 mg (17%).
[0121] 1l, 1-[2-(4-Methoxyphenoxy)phenyl]piperazine: LC/MS (m/z) 285 (MH + ); RT=2.08; purity (UV, ELSD): 93%, 100%; yield: 4 mg (18%)
Example 2
2a, 2-(4-Methylphenylsulfanyl)phenyl-1-piperazine hydrochloride
[0122] 1-tert-Butyloxycarbonyl-4-[2-(4-methylphenylsulfanyl)phenyl]-3,5-dioxo-piperazine (5.5 g, 13 mmol) was dissolved in dry THF (50 mL) and placed under a nitrogen atmosphere. Borane tetrahydrofuran complex (50 mmol, 1.0 M) in tetrahydrofuran was added and the reaction was refluxed for ten minutes. Excess borane was quenched by the addition of an excess of ethyl acetate and the reaction was refluxed for a further 20 minutes. The reaction was allowed to cool to room temperature before hydrogen chloride dissolved in methanol (50 mL, 4 M) was added and the reaction was refluxed for 4.5 hours. The reaction was allowed to cool to room temperature and the reaction was concentrated in vacuo. The compound was crystallised from the gum residue by the addition of ether/methanol solution. The crystalline solid was filtered and washed with ether/methanol (1:1) to give a white crystalline solid. Yield (2.0 g, 47%) 1 H NMR (D 6 -DMSO) 2.35 (s, 3H); 3.18 (br s, 8H); 6.68 (d, 2H); 7.02 (m, 1H); 7.18 (m, 1H); 7.3-7.5 (m, 4H); MS (MH + ) 285.
[0123] The following compounds were prepared in an analogous fashion:
[0124] 2b, 1-[2-(4-chlorophenylsulfanyl)phenyl]piperazine LC-MS (m/z) 305.1 (MH + ) RT=2.46 purity (UV, ELSD) 71%, 91% yield 0.096 g, 100%
[0125] 2c, 1-[2-(4-methoxyphenylsulfanyl)-4-chlorophenyl]piperazine LC-MS (m/z) (MH + ) 335.2 RT=2.38 purity (UV, ELSD) 98%, 100% yield 0.22 g, 62%
[0126] 2d, 1-[2-(4-methoxyphenylsulfanyl)-4-methylphenyl]piperazine LC-MS (m/z) (MH + ) 315.1 RT=2.33 purity (UV, ELSD) 97%, 100% yield 0.21 g, 56%
[0127] 2e, 1-[2-(4-methoxyphenylsulfanyl)-5-methylphenyl]piperazine LC-MS (m/z) (MH + ) 315.2 RT=2.38 (UV, ELSD) 98 %, 100% yield 2.3 g, 58%
[0128] 2f, 1-[2-(4-fluorophenylsulfanyl)-5-methylphenyl]piperazine LC-MS (m/z) (MH + ) 303.2 RT=2.46 (UV) 98% yield 2.1 g, 62%
[0129] 2g, 1-[2-(4-Methoxyphenylsulfanyl)-5-trifluoromethylphenyl]piperazine LC-MS (m/z) (MH + ) 369 RT=2.50 (UV, ELSD) 96%, 100% yield 0.54 g, 31%
Example 3
3a, 1-[2-(4-Chlorophenylsulfanyl)phenyl]-3-methylpiperazine
[0130] 2-(3-Methylpiperazin-1-yl)phenylamine (0.96 g, 5 mmol) was dissolved in 30 mL water containing sulfuric acid (0.28 mL, 5.2 mmol) and the solution was cooled to 0° C. and sodium nitrite (0.36 g, 5.2 mmol) was added. The reaction was stirred for 30 minutes before the pH of the reaction was adjusted to pH 7 with sodium acetate. The diazonium salt solution was then added dropwise to a solution of 4-chlorothiophenol in a suspension of copper (0.3 g, 5 mmol) in 2 M NaOH (4 mL). After addition, the reaction mixture was heated to 60° C. for 30 minutes before being allowed to cool to room temperature and ethyl acetate (10 mL) was added. The reaction mixture was filtered and the layers were separated. The aqueous layer was extracted with ethyl acetate (2×10 mL). The combined organic phases were dried (MgSO 4 ) and volatile solvents evaporated in vacuo. The crude product was purified by flash chromatography using silica gel, eluting with ethyl acetate/methanol/ammonia 96:3:1. The pure product was isolated as a colourless oil. Yield (0.18 g, 11%) 1H NMR (CDCl 3 , 500 MHz) 1.12 (d, 3H); 2.6-2.72 (br m, 2H); 3.0-3.15 (m, 5H); 6.9 (m, 2H); 7.08 (d, 1H); 7.15 (m, 1H); 7.25-7.35 (m, 4H); MS (MH + ) 319.1.
[0131] The following compound was prepared in an analogous fashion:
[0132] 3b, 1-[2-(4-Chlorophenylsulfanyl)phenyl]-3,5-dimethylpiperazine LC-MS (m/z) (MH)+333.1 RT=2.29 (UV, ELSD) 83%, 100% yield 0.54 g, 31%.
Example 4
4a, 4-[2-(4-Methylphenylsulfanyl)phenyl]-3,6-dihydro-2H-pyridine
[0133] Concentrated aq hydrochloric acid (10 ml) was added to a stirred solution of 1-tert-butoxycarbonyl-4-[2-(4-methylphenylsulfanyl)phenyl]piperidin-4-ol (0.84 g, 2.1 mmol) in acetic acid (30 mL). The solution was boiled under reflux overnight, cooled to room temperature and then stirred in an ice bath. An aqueous solution of NaOH (9.1 M, 40 mL) was slowly added and the unclear solution was extracted with ethyl acetate (2×40 ml). The combined organic phases were dried (MgSO 4 ) and the solvents evaporated in vacuo. The crude material (0.48 g) was dissolved in ethyl acetate (3.2 mL) at 50° C. and a solution of oxalic acid (0.11 g) in EtOH (3.2 mL) was slowly added. The target compound was collected as a white oxalic salt. 1 H (DMSO-d 6 ) δ 7.3-7.2 (m, 7H); 7.15 (m, 1H); 7.00 (m, 1H); 5.6 (d, 1H); 3.7 (d, 2H); 3.25 (t, 2H); 2.6 (m, 2H); 2.3 (s, 3H). LC/MS (m/z) 282.2 (MH + ); RT=2.24; purity (UV, ELSD): 99%, 100%; yield: 0.31 g (40%).
[0134] The following derivative was prepared analogously:
[0135] 4b, 4-[2-(4-Methoxyphenylsulfanyl)phenyl]-3,6-dihydro-2H-pyridine
[0136] LC/MS (m/z) 298 (MH + ); RT=2.00; purity (UV, ELSD): 97%, 100%; yield: 0.28 g (30%).
Example 5
5a, 4-[2-(4-Methylphenylsulfanyl)phenyl]piperidine
[0137] Methyl Chloro-oxo-acetate (1.37 g, 11.25 mmol) was added to a stirred solution of 1-tert-butoxycarbonyl-4-[2-(4-methylphenylsulfanyl)phenyl]piperidin-4-ol (3.00 g, 7.5 mmol) and 4-(dimethylamino)pyridine (1.65 g, 13.5 mmol) in a mixture of dry CH 3 CN (24 ml) and CHCl 3 (12 mL) at 0° C. under argon. The reaction mixture was allowed to reach room temperature and then stirred 2 h. Ethyl acetate (140 mL) was added and some salts were removed by filtration through celite. The organic phase was washed with sat. NaHCO 3 (140 ml), brine (140 mL) and dried (MgSO 4 ). The solvents were evaporated in vacuo and the crude material was dried in vacuo. This material was dissolved in dry toluen (48 mL) under argon. Bu 3 SnH (3.27 g, 11.25 mmol) and AIBN (0.31 g, 1.88 mmol) were added. The solution was stirred under argon at 90° C. for 2.5 h. The solvent was evaporated in vacuo, and the crude material was purified by flash chromatography on silicagel (eluent: a stepwise gradient of ethylacetat in heptane from 10:90 to 20:80) to produce 44244-methylphenylsulfanyl)phenyl)-piperidine-1-carboxylic acid tert-butyl ester as a clear oil (1.94 g, 67%). This oil was dissolved in MeOH (9.2 mL) and HCl in diethylether (2.0 M) was added at 0° C. The reaction mixture was allowed to warm to room temperature and stirred overnight. The target compound was collected as its hydrochloride. M.p 229-231° C. Calculated for C 18 H 21 NS.HCl: C, 67.58; H, 6.63; N, 4.38. Found: C, 67.33; H, 6.97; N, 4.31. LC/MS (m/z) 284 (MH + ); RT=2.12; purity (UV, ELSD): 96%, 100%; yield: 0.26 g (46%).
[0000] Inhibition of the Uptake of [ 3 H]Serotonin into Whole Rat Brain Synaptosomes
[0138] The compounds were tested with respect to their 5-HT reuptake inhibiting effect by measuring their ability to inhibit the uptake of [ 3 H]serotonin into whole rat brain synaptosomes in vitro. The assay was performed as described by Hyttel Psychopharmacology 1978, 60, 13.
5-HT 2C Receptor Efficacy as Determined by Fluorometry
[0139] The compounds were tested with respect to their efficacy on 5-HT 2C receptor-expressing CHO cells (Euroscreen) as determined by fluorometric imaging plate reader (FLIPR) analysis. This assay was carried out according to Molecular Devices Inc. instructions for their FLIPR Calcium Assay Kit and as modified from Porter et al. British Journal of Pharmacology 1999, 128, 13.
[0140] Preferred compounds of the present invention exhibit serotonin reuptake inhibition below 200 nM (IC 50 ) in the assay above. More preferred are the compounds which exhibit inhibition below 100 nM and most preferably below 50 nM. Compounds of particular interest exhibit serotonin reuptake inhibition below 10 nM; | The invention provides compounds represented by the general formula I
wherein the substituents are defined in the application. The compounds are useful in the treatment of an affective disorder, including depression, anxiety disorders including general anxiety disorder and panic disorder and obsessive compulsive disorder. | 2 |
TECHNICAL FIELD
In accordance with the disclosed principles, a decorative roof profile and a method for attaching same to thermoplastic roofing membranes, more particularly welding a thermoplastic decorative profile to a thermoplastic single ply membrane is disclosed.
BACKGROUND
Thermoplastic roofing membranes, such as polyvinyl chloride (PVC) and thermoplastic polyolefin (TPO), are rapidly growing in market acceptance. However, even though they can be made in a wide variety of colors, they do not impart a good aesthetic appearance to a roof surface. In contrast, metal roofing has regular, parallel standing seams that join each sheet of metal. These seams, together with colored metal coatings, provide for an attractive roofing surface. In fact, metal roofing is frequently used as a decorative and functional roof surface for small commercial and public building roof sections that are visible from the street. Some plastic profile systems are available for attachment to thermoplastic roofing membranes, such that a metal roof-like appearance can be obtained. These profile systems are sometimes described as standing seam profiles (SSP).
To duplicate this appearance, thermoplastic strips have been secured to the thermoplastic membranes, sometimes by adhesive, and sometimes by the application of heat, all of which is done manually. An example of an adhesive system is a butyl peel and stick tape. Adhesive systems may require the roof membrane be primed prior to attachment, with difficulty being priming the exact area of attachment. Primer that extends onto the roofing membrane may be visible and discolor the membrane. Another disadvantage of adhesively attached profiles is that adhesive systems may not be as robust for the 20 to 30 year life expectancy of the roof system as compared to a permanent attachment method.
Applying heat to permanently attach the profiles may require a welder that is large and cumbersome. For a steep sloped roof, this is especially challenging. Also, the roofer will be required to guide the system in a straight line to achieve a good appearance, while keeping the profile in place, and maintaining a balance on a sloped roof.
Unfortunately, manual application of the strips is a time consuming and labor intensive process, increasing the cost of the roofing and decreasing the cost advantage gained by selecting thermoplastic roofing over metal roofing. Manual application also increases opportunity for error and is not conducive to creating straight and/or parallel and/or equidistant lines. What is needed in the art is a quick and inexpensive apparatus and method of attaching thermoplastic strips to thermoplastic roofing membranes.
SUMMARY
Embodiments of the invention provide a thermoplastic profile strip and a welding apparatus for permanently attaching the profile strip to a thermoplastic roofing material. In addition, methods for welding a thermoplastic profile strip to a thermoplastic membrane are also disclosed.
In one aspect, an improved thermoplastic profile strip is disclosed. In one embodiment of such a strip, the thermoplastic profile roofing strip may comprise a horizontal base extending longitudinally and having a notched profile. In addition, the thermoplastic profile strip may comprise a vertical central portion laterally connected at one edge and normal to the horizontal base. In such embodiments, the vertical central portion extends longitudinally along the horizontal base to provide the improved profile.
In another aspect, an apparatus for welding a thermoplastic profile strip to a thermoplastic membrane is provided. In one embodiment, such an apparatus may comprise a first nozzle capable of directing hot air onto an upper surface of a first edge of a thermoplastic profile strip, and a second nozzle capable of directing hot air onto an upper surface of a second edge of a thermoplastic profile strip. In addition, in such an embodiment, the apparatus may also comprise a tubular splitter capable of simultaneously supplying hot air to the first nozzle and the second nozzle. In more specific embodiments, the first and second nozzles each comprise a first portion for supplying hot air and a second portion configured to apply downward pressure on upper surfaces of the strip that have received hot air.
In yet another aspect, methods for welding a thermoplastic profile strip to a thermoplastic membrane are provided. In one embodiment, such a method may comprise placing a thermoplastic profile roofing strip onto a thermoplastic roofing membrane. Such a thermoplastic profile roofing strip may include a horizontal base extending longitudinally having a notched profile, and a vertical central portion laterally connected along one edge to the horizontal base, wherein the vertical central portion extends longitudinally along the horizontal base. In such an embodiment, the method may also include applying an apparatus for welding a thermoplastic profile strip to a thermoplastic roofing membrane. The method may then comprise splitting a supply of hot air to first and second nozzles, and simultaneously directing hot air onto upper surfaces of a first and second lips of the thermoplastic profile strip using the first and second nozzles. In addition, the method could then comprise advancing the apparatus along the length of the thermoplastic profile strip such that the first and second nozzles simultaneously supply the split hot air along the length of the thermoplastic profile strip.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of a thermoplastic profile strip to be welded to a thermoplastic roofing membrane.
FIG. 2 is a perspective view of an alternate embodiment of a thermoplastic profile strip.
FIG. 3A is a side view of a welder attachment for attaching a thermoplastic profile strip to a thermoplastic roofing membrane.
FIG. 3B is a front view of the welder attachment of FIG. 3A .
FIG. 3B is a detailed view of embodiments of the nozzle tips of FIG. 3A conjoined for use with the welding apparatus of FIG. 2 .
DETAILED DESCRIPTION
A thermoplastic profile strip 100 as shown in FIG. 1 . The profile strip 100 may be attached to a thermoplastic roofing membrane in accordance with the disclosed principles. The thermoplastic profile strip 100 is preferably produced as an integrally formed seamless thermoplastic object. Methods of production of the thermoplastic profile strip 100 may include extrusion, molding, etc. The thermoplastic profile strip 100 preferably includes an upstanding central portion 105 extending lengthwise along the strip and opposed flange portions 110 extending widthwise from the central portion 105 . In some embodiments, the opposed flange portions 110 extend from the central portion 105 in the range from about 0.5 inch to about 1 inch, and in a preferred embodiment may be about ⅝ inch. The opposed flange portions 110 length may depend on the height of the upstanding central portion 105 that needs to be supported.
In some embodiments, the upstanding central portion 105 height ranges from about 1 inch to about 3 inches, more preferably from about 2 inches to about 2.5 inches. In a preferred embodiment, the upstanding central portion 105 height is 1.25 inches. Opposite the upstanding central portion 105 and the opposed flange portions 110 is a bottom surface 115 . In a preferred embodiment, the bottom surface 115 is about ¾ inch. In alternate embodiments, the bottom surface 115 may range from about ⅛ inch to about 1 inch. In some embodiments, the bottom surface 115 may be coated with an adhesive. In some embodiments, the bottom surface 115 may be coated with a pressure sensitive adhesive and 125 a release liner 130 . In some embodiments, the adhesive 125 may be, but not limited to, butyl rubber adhesive and the release liner 130 may be, but not limited to, siliconized paper.
The upper portion of the upstanding central portion 105 includes an integral hook 135 . In a preferred embodiment, the hook 135 has a cross section similar to an upside down U. In an alternate embodiment, the hook 135 may also include a lip. In alternate embodiments, the hook 135 may be any cross sectional shape capable of being a guide or used with a lock as described below.
In an alternate embodiment, the thermoplastic profile strip 100 may have a triangular cross-sectional shape as seen in FIG. 2 . The opposed flange portions 110 may include a notched profile. The profile would extend along the length of both of the opposed flange portions 110 . The notched profile may be any shape, such as a square tooth (as shown) or saw toothed and the like. During continuous welding, the notched profile may enable the teeth to be heated along with sections of the thermoplastic roofing membrane. The welder foot may then “smear” the teeth out over the heated thermoplastic roofing membrane ensuring a good weld.
Embodiments of an apparatus 300 for welding the thermoplastic profile strip 100 to the thermoplastic roofing membrane are shown in FIGS. 3A-3B . Like numerals are used across the figures to describe similar parts of the apparatus 300 . In a preferred embodiment, the apparatus 300 includes a first nozzle 400 A, a second nozzle 400 B, a platform guiding device 500 , and a splitter 600 . In addition, other embodiments of a welding apparatus that may be employed with the profile strips of the present disclosure may be found in co-pending U.S. application Ser. No. 12/651,331, which was filed the same day as the present disclosure, and is commonly owned with the present disclosure and incorporated herein by reference in its entirety.
FIG. 3A is a side view of the apparatus 300 and FIG. 3B is a front view of the apparatus 300 connected to the first nozzle 400 A and the second nozzle 400 B. In a preferred embodiment, the first nozzle 400 A and the second nozzle 400 B are identical and only the first nozzle 400 A will be described. The splitter 600 supplies hot air to the first nozzle 400 A and the second nozzle 400 B. The splitter 600 includes an inlet 610 and a plurality of outlets 620 . In a preferred embodiment, the splitter 600 is fabricated from pipe components, i.e., fittings. In an alternate embodiment, the splitter 600 is an integrally fabricated piping component. The sizing of the splitter 600 including the inlet 610 and the plurality of outlets 620 will be dependent on the sizing of the first nozzle 400 A and the second nozzle 400 B, which will be sized dependent on the thermoplastic profile strip 100 . The splitter 600 will be connected to a hot air supply (not shown), preferably a hot air gun. In an alternate embodiment, the apparatus 300 may only include a first nozzle 400 A.
The first nozzle 400 A includes an inlet 405 and a tip 410 . The inlet 405 will be connected to one of the outlets 620 of the splitter 600 . The tip 410 includes an outlet for delivering a hot air stream to the edge of the opposed flange portions 110 . In an alternate embodiment, the tip 410 is shaped to be placed on the notched profile of the opposed flange portions 110 . The cross section of the first tip 410 is preferably shaped to provide an even flow of hot air across the notched profile. Moreover, the elongated pointed profile of the tip 410 allows heat to be applied from a back portion of the tip 410 , while the front end of the tip 410 continues to apply downward pressure to the welding area as the tip 410 is moved along the profile strip 100 .
As shown in FIG. 3B , the platform guiding device 500 is capable of moving the splitter 600 , first nozzle 400 A, second nozzle 400 B along the length of the upstanding central portion 105 of the thermoplastic profile strip 100 . In some embodiments, the platform guiding device 500 may be self-propelled while in other embodiments the platform guiding device 500 may be manually propelled by an operator. In a preferred embodiment, the platform guiding device 500 includes a platform 505 and a guide 510 . In a preferred embodiment, the platform 505 is capable of supporting the hot air supply and associated parts. The platform 505 may be shaped and sized by one of skill in the art to support the platform 505 , the guide 510 , and associated parts.
To ensure the hot air and pressure are applied to the welding area, the guide 510 travels along the upstanding central portion 105 of the thermoplastic profile strip 100 . In a preferred embodiment, the guide 510 is an upside down U in cross section sized to be placed over the thermoplastic profile strip 100 , preferably the hook 135 . The guide 510 may also include a guide roller. In some embodiments, the guide roller is sized to control the elevation of the platform guiding device 300 . In some embodiments, the guide roller is a silicon roller. In alternate embodiments, the guide roller may be made of any hard rubber with a smooth surface. In some embodiments, the guide 510 also includes a locking device. The locking device is shaped and sized to connect with the hook 135 of the thermoplastic profile strip 100 . In some embodiments, the locking device is a movable platform having a first position for providing access to place the guide 510 on the upstanding central portion 105 and a second position to place the movable platform in contact with the hook 135 of the thermoplastic profile strip 100 . In alternate embodiments, the guide 510 has a cross section for mounting on the cross sectional profile of the thermoplastic profile strip 100 .
Before the thermoplastic profile strip 100 is welded to the thermoplastic roofing membrane, the thermoplastic profile strip 100 may be temporarily attached to the thermoplastic roofing membrane in straight parallel lines using the adhesive 125 and release liner 130 . In operation, the first nozzle 400 A and the second nozzle 400 B are positioned as shown in FIG. 3B . The first nozzle 400 A and the second nozzle 400 B preferably drag over the teeth and are long enough that they cover several teeth simultaneously. As the platform guiding device 500 moves along the upstanding central portion 105 of the thermoplastic profile strip 100 , jets of hot air from the first nozzle 400 A and the second nozzle 400 B weld the notches to the thermoplastic roofing membrane 200 . The tip 410 may then “smear” the notched teeth out over the heated thermoplastic roofing membrane ensuring a good weld.
While a number of particular embodiments of the present invention have been described herein, it is understood that various changes, additions, modifications, and adaptations may be made without departing from the scope of the present invention, as set forth in the following claims.
Additionally, the section headings herein are provided for consistency with the suggestions under 37 C.F.R. 1.77 or otherwise to provide organizational cues. These headings shall not limit or characterize the invention(s) set out in any claims that may issue from this disclosure. Specifically and by way of example, although the headings refer to a “Technical Field,” such claims should not be limited by the language chosen under this heading to describe the so-called technical field. Further, a description of a technology in the “Background” is not to be construed as an admission that technology is prior art to any invention(s) in this disclosure. Neither is the “Summary” to be considered as a characterization of the invention(s) set forth in issued claims. Furthermore, any reference in this disclosure to “invention” in the singular should not be used to argue that there is only a single point of novelty in this disclosure. Multiple inventions may be set forth according to the limitations of the multiple claims issuing from this disclosure, and such claims accordingly define the invention(s), and their equivalents, that are protected thereby. In all instances, the scope of such claims shall be considered on their own merits in light of this disclosure, but should not be constrained by the headings set forth herein. | In accordance with the disclosed principles, a novel thermoplastic profile roofing strip and an apparatus for welding the thermoplastic profile roofing strip to a thermoplastic roofing membrane is disclosed. In one embodiment, the thermoplastic profile roofing strip may comprise a horizontal base extending longitudinally and having a notched profile. In addition, the thermoplastic profile strip may comprise a vertical central portion laterally connected at one edge and normal to the horizontal base. In such embodiments, the vertical central portion extends longitudinally along the horizontal base to provide the improved profile. Related methods of welding a thermoplastic strip to a thermoplastic membrane are also disclosed. | 4 |
[0001] This application claims the benefit under 35 USC §119(e) of U.S. Provisional Application No. 61/153,919, filed on Feb. 19, 2009; the disclosure of which is hereby expressly incorporated by reference in its entirety and is hereby expressly made a portion of this application.
FIELD OF THE INVENTION
[0002] Methods for separation of chemicals in the liquid and gaseous state are provided, which can be applied to the processing of biofuels.
BACKGROUND OF THE INVENTION
[0003] In the evolving biofuels industry much of the conventional process and refining equipment and many of the techniques are being applied to new feedstock for producing renewable fuels. Unlike the petroleum industry where economies of scale drove refineries to larger and larger facilities, the typical lower energy density of biofuels and dispersed agriculture nature of the feedstock result in bio-refineries that are typically smaller, more compact facilities appropriately scaled to the nearby feedstock. Corn ethanol facilities and biodiesel refineries are finding economic implementations in facilities from 10 million gallons to 100 million gallons of biofuels per year. As a result, the economics of byproduct processing, such as glycerin refining in a biodiesel facility or refining crude corn oil extracted from an ethanol facility, requires the application of advanced technologies which are economical at low capacities using small-scale equipment.
SUMMARY OF THE INVENTION
[0004] The increasing concern with global climate change and the increasing concentration of carbon dioxide in the atmosphere are driving biorefineries to greater energy efficiencies to reduce the carbon footprint of the refining processes.
[0005] What is needed are high efficiency bio-refinery and co-product extraction and purification processes that provide improved economics and lower energy consumption in small-scale equipment with broad application to the evolving bio-refinery industry.
[0006] Systems and methods of separating mixtures of compounds, where at least one compound is heat sensitive or where there is a tendency to form solids capable of forming a precipitate or scale that interferes with the operation of the separation system are desirable.
[0007] Accordingly, in a first aspect, a process is provided for separation and purification of compounds in a liquid mixture with low energy input comprising passing a feed mixture comprising a first compound and a second compound into a simulated moving bed chromatography apparatus; the first compound acting as a solvent for the second compound which forms a precipitate at concentrations above a solubility limit; passing an eluent solvent into the simulated moving bed chromatography apparatus to separate the feed into a first stream and a second stream, and optionally additional streams, wherein the first stream has an elevated concentration of the first compound in eluent and the second stream has an elevated concentration of the second compound, as compared to the feed; passing the first stream to a vapor compression distillation unit to generate a high purity stream of the first compound; vaporizing at least a portion of the eluent from the first stream at a first temperature to form a vapor, compressing the vapor to form an eluent condensate at a second temperature, such that the second temperature is greater than the first temperature, and the eluent condensate has a thermal energy content; and transferring at least a portion of the thermal energy content of the eluent condensate into the first stream to be used in vaporizing the eluent in the first stream.
[0008] In one embodiment of the first aspect, the first compound is present in the high purity stream of the first compound at a concentration of about 85% (wt.) or greater.
[0009] In one embodiment of the first aspect, the first compound is present in the high purity stream of the first compound at a concentration of about 90% (wt.) or greater.
[0010] In one embodiment of the first aspect, the first compound is present in the high purity stream of the first compound at a concentration of about 95% (wt.) or greater.
[0011] In one embodiment of the first aspect, the first compound is present in the high purity stream of the first compound at a concentration of about 98% (wt.) or greater.
[0012] In one embodiment of the first aspect, the first compound is present in the high purity stream of the first compound at a concentration of about 99% (wt.) or greater.
[0013] In one embodiment of the first aspect, less thermal energy is added to the process than would be needed to vaporize the high purity stream of the first compound.
[0014] In one embodiment of the first aspect, the process further comprises passing the second stream to a vapor compression distillation unit to recover additional eluent and to generate a concentrated second stream with less eluent.
[0015] In one embodiment of the first aspect, the process further comprises passing the second stream to a vapor compression distillation unit to recover additional eluent and to generate a concentrated second stream with less eluent, wherein the concentrated second stream has a concentration of eluent that is less than about one half an eluent concentration of the second stream.
[0016] In one embodiment of the first aspect, the process further comprises passing the second stream to a vapor compression distillation unit to recover additional eluent and to generate a concentrated second stream with less eluent, wherein the concentrated second stream has a concentration of eluent that is less than about one quarter an eluent concentration of the second stream.
[0017] In one embodiment of the first aspect, the process further comprises passing the second stream to a vapor compression distillation unit to recover additional eluent and to generate a concentrated second stream with less eluent, wherein the concentrated second stream has a concentration of eluent that is less than about one tenth of an eluent concentration of the second stream.
[0018] In one embodiment of the first aspect, the process further comprises passing the second stream to a vapor compression distillation unit to recover additional eluent and to generate a concentrated second stream with less eluent, wherein the concentrated second stream has a concentration of eluent that is less than about one twentieth of an eluent concentration of the second stream.
[0019] In a second aspect, a process is provided for separation and purification of compounds in a liquid mixture with low energy input comprising passing a feed mixture comprising a third compound and a fourth compound into a simulated moving bed chromatograph apparatus at a process temperature; the third compound and the fourth compound being liquids at the process temperature, at least one of the third and fourth compound being chemically or physically changed at a third temperature, the third temperature being greater than the process temperature and lower than a fourth temperature, the fourth temperature being the boiling point of the lower boiling of the third compound and the fourth compound; passing an eluent solvent into the simulated moving bed chromatography apparatus to facilitate separation of the compounds into a third stream and a fourth stream, such that the third stream has an elevated concentration of the third compound in eluent and the fourth stream has an elevated concentration of the fourth compound; passing the third stream to a vapor compression distillation unit to generate a high purity stream of the third compound; vaporizing the eluent from the third stream at a first temperature, compressing the vapor to form an eluent condensate at a second temperature such that the second temperature is greater than the first temperature, and the eluent condensate has a thermal energy content; and transferring at least a portion of the thermal energy content of the eluent condensate into the third stream to be used in vaporizing the eluent in the third stream.
[0020] In one embodiment of the second aspect, the third compound is present in the high purity stream of the first compound at a concentration of about 85% (wt.) or greater.
[0021] In one embodiment of the second aspect, the third compound is present in the high purity stream of the first compound at a concentration of about 90% (wt.) or greater.
[0022] In one embodiment of the second aspect, the third compound is present in the high purity stream of the first compound at a concentration of about 95% (wt.) or greater.
[0023] In one embodiment of the second aspect, the third compound is present in the high purity stream of the first compound at a concentration of about 98% (wt.) or greater.
[0024] In one embodiment of the second aspect, the third compound is present in the high purity stream of the first compound at a concentration of about 99% (wt.) or greater.
[0025] In one embodiment of the second aspect, a process is provided for separation and purification of compounds in a liquid mixture with low energy input comprising passing a feed mixture comprising a third compound and a fourth compound into a simulated moving bed chromatograph apparatus at a process temperature; the third compound and the fourth compound being liquids at the process temperature, at least one of the third and fourth compound being chemically or physically changed at a third temperature, the third temperature being greater than the process temperature and lower than a fourth temperature, the fourth temperature being the boiling point of the lower boiling of the third compound and the fourth compound; passing an eluent solvent into the simulated moving bed chromatography apparatus to facilitate separation of the compounds into a third stream and a fourth stream, such that the third stream has an elevated concentration of the third compound in eluent and the fourth stream has an elevated concentration of the fourth compound; passing the third stream to a vapor compression distillation unit to generate a high purity stream of the third compound; vaporizing the eluent from the third stream at a first temperature, compressing the vapor to form an eluent condensate at a second temperature such that the second temperature is greater than the first temperature; and transferring at least a portion of the thermal energy of the eluent condensate into the third stream to provide at least a portion of the energy needed to vaporize the eluent in the third stream, and less thermal energy is added to the process than would be needed to vaporize the high purity stream of the third compound.
[0026] In one embodiment of the second aspect, a process is provided for separation and purification of compounds in a liquid mixture with low energy input comprising passing a feed mixture comprising a third compound and a fourth compound into a simulated moving bed chromatograph apparatus at a process temperature; the third compound and the fourth compound being liquids at the process temperature, at least one of the third and fourth compound being chemically or physically changed at a third temperature, the third temperature being greater than the process temperature and lower than a fourth temperature, the fourth temperature being the boiling point of the lower boiling of the third compound and the fourth compound; passing an eluent solvent into the simulated moving bed chromatography apparatus to facilitate separation of the compounds into a third stream and a fourth stream, such that the third stream has an elevated concentration of the third compound in eluent and the fourth stream has an elevated concentration of the fourth compound; passing the third stream to a vapor compression distillation unit to generate a high purity stream of the third compound; vaporizing the eluent from the third stream at a first temperature, compressing the vapor to form an eluent condensate at a second temperature such that the second temperature is greater than the first temperature; transferring at least a portion of the thermal energy of the eluent condensate into the third stream to provide at least a portion of the energy needed to vaporize the eluent in the third stream; and passing the fourth stream to a vapor compression distillation unit to recover additional eluent and to generate a concentrated fourth stream.
[0027] In an embodiment of the second aspect, a process is provided for separation and purification of compounds in a liquid mixture with low energy input comprising passing a feed mixture comprising a third compound and a fourth compound into a simulated moving bed chromatograph apparatus at a process temperature; the third compound and the fourth compound being liquids at the process temperature, at least one of the third and fourth compound being chemically or physically changed at a third temperature, the third temperature being greater than the process temperature and lower than a fourth temperature, the fourth temperature being the boiling point of the lower boiling of the third compound and the fourth compound; passing an eluent solvent into the simulated moving bed chromatography apparatus to facilitate separation of the compounds into a third stream and a fourth stream, such that the third stream has an elevated concentration of the third compound in eluent and the fourth stream has an elevated concentration of the fourth compound; passing the third stream to a vapor compression distillation unit to generate a high purity stream of the third compound; vaporizing the eluent from the third stream at a first temperature, compressing the vapor to form an eluent condensate at a second temperature such that the second temperature is greater than the first temperature; transferring at least a portion of the thermal energy of the eluent condensate into the third stream to provide at least a portion of the energy needed to vaporize the eluent in the third stream; and passing the fourth stream to a vapor compression distillation unit to recover additional eluent and to generate a concentrated fourth stream, wherein the concentrated fourth stream has a concentration of eluent that is less than about one half an eluent concentration of the fourth stream.
[0028] In an embodiment of the second aspect, a process is provided for separation and purification of compounds in a liquid mixture with low energy input comprising passing a feed mixture comprising a third compound and a fourth compound into a simulated moving bed chromatograph apparatus at a process temperature; the third compound and the fourth compound being liquids at the process temperature, at least one of the third and fourth compound being chemically or physically changed at a third temperature, the third temperature being greater than the process temperature and lower than a fourth temperature, the fourth temperature being the boiling point of the lower boiling of the third compound and the fourth compound; passing an eluent solvent into the simulated moving bed chromatography apparatus to facilitate separation of the compounds into a third stream and a fourth stream, such that the third stream has an elevated concentration of the third compound in eluent and the fourth stream has an elevated concentration of the fourth compound; passing the third stream to a vapor compression distillation unit to generate a high purity stream of the third compound; vaporizing the eluent from the third stream at a first temperature, compressing the vapor to form an eluent condensate at a second temperature such that the second temperature is greater than the first temperature; transferring at least a portion of the thermal energy of the eluent condensate into the third stream to provide at least a portion of the energy needed to vaporize the eluent in the third stream; and passing the fourth stream to a vapor compression distillation unit to recover additional eluent and to generate a concentrated fourth stream, wherein the concentrated fourth stream has a concentration of eluent that is less than about one fourth an eluent concentration of the fourth stream.
[0029] In an embodiment of the second aspect, a process is provided for separation and purification of compounds in a liquid mixture with low energy input comprising passing a feed mixture comprising a third compound and a fourth compound into a simulated moving bed chromatograph apparatus at a process temperature; the third compound and the fourth compound being liquids at the process temperature, at least one of the third and fourth compound being chemically or physically changed at a third temperature, the third temperature being greater than the process temperature and lower than a fourth temperature, the fourth temperature being the boiling point of the lower boiling of the third compound and the fourth compound; passing an eluent solvent into the simulated moving bed chromatography apparatus to facilitate separation of the compounds into a third stream and a fourth stream, such that the third stream has an elevated concentration of the third compound in eluent and the fourth stream has an elevated concentration of the fourth compound; passing the third stream to a vapor compression distillation unit to generate a high purity stream of the third compound; vaporizing the eluent from the third stream at a first temperature, compressing the vapor to form an eluent condensate at a second temperature such that the second temperature is greater than the first temperature; transferring at least a portion of the thermal energy of the eluent condensate into the third stream to provide at least a portion of the energy needed to vaporize the eluent in the third stream; and passing the fourth stream to a vapor compression distillation unit to recover additional eluent and to generate a concentrated fourth stream, wherein the concentrated fourth stream has a concentration of eluent that is less than about one tenth an eluent concentration of the fourth stream.
[0030] In an embodiment of the second aspect, a process is provided for separation and purification of compounds in a liquid mixture with low energy input comprising passing a feed mixture comprising a third compound and a fourth compound into a simulated moving bed chromatograph apparatus at a process temperature; the third compound and the fourth compound being liquids at the process temperature, at least one of the third and fourth compound being chemically or physically changed at a third temperature, the third temperature being greater than the process temperature and lower than a fourth temperature, the fourth temperature being the boiling point of the lower boiling of the third compound and the fourth compound; passing an eluent solvent into the simulated moving bed chromatography apparatus to facilitate separation of the compounds into a third stream and a fourth stream, such that the third stream has an elevated concentration of the third compound in eluent and the fourth stream has an elevated concentration of the fourth compound; passing the third stream to a vapor compression distillation unit to generate a high purity stream of the third compound; vaporizing the eluent from the third stream at a first temperature, compressing the vapor to form an eluent condensate at a second temperature such that the second temperature is greater than the first temperature; transferring at least a portion of the thermal energy of the eluent condensate into the third stream to provide at least a portion of the energy needed to vaporize the eluent in the third stream; and passing the fourth stream to a vapor compression distillation unit to recover additional eluent and to generate a concentrated fourth stream, wherein the concentrated fourth stream has a concentration of eluent that is less than about one twentieth an eluent concentration of the fourth stream.
[0031] In a third aspect, a system is provided for separating two or more components from a process stream, the system comprising a simulated moving bed (SMB) subsystem with a mobile phase, the SMB subsystem configured to convert a feed stream comprising a first component and a second component, wherein the first component and the second component are present in the feed stream at a first ratio defined by the weight percent of the second component divided by the weight percent of the first component, and the first component is a solvent for the second component, and the second component forms a precipitate at a concentrations higher than a concentration present in the feed, into a first stream comprising at least a portion of the first component and at least a portion of the mobile phase, and a second stream comprising at least a portion of the second component and at least a portion of the mobile phase, wherein the first component and the second component are present in the first stream at a second ratio defined by the weight percent of the second component divided by the weight percent of the first component, wherein the first ratio is greater than the second ratio; and a vapor compression distillation subsystem, operating on a distillation feed stream comprising at least a portion of the first stream to separate an amount of the first component from at least a portion of the mobile phase that is present in the first stream with evaporation, the evaporation requiring a thermal energy input, and the system for separating two or more components from a process stream having a total thermal energy input, wherein the distillation feed stream is subjected to a maximum bulk temperature and a maximum surface temperature during processing in the vapor compression distillation subsystem, the total thermal energy input to the system being less than the thermal energy required to evaporate the amount of first component separated in the vapor compression distillation subsystem, and the second component does not form a precipitate in the distillation feed stream at a bulk temperature experienced by the portion of the first stream within the vapor compression distillation subsystem.
[0032] In an embodiment of the third aspect, the temperature experienced by the portion of the first stream is a bulk temperature.
[0033] In an embodiment of the third aspect, the temperature experienced by the portion of the first stream is the maximum bulk temperature.
[0034] In an embodiment of the third aspect, the temperature experienced by the portion of the first stream is the maximum bulk temperature, and the maximum bulk temperature is about 230° F. to about 260° F., or about 250° F. to about 280° F., or about 270° F. to about 300° F., or about 290° F. to about 320° F., or about 310° F. to about 340° F., or about 330° F. to about 360° F., or about 350° F. to about 400° F.
[0035] In an embodiment of the third aspect, the temperature experienced by the portion of the first stream is a surface temperature.
[0036] In an embodiment of the third aspect, the temperature experienced by the portion of the first stream is the maximum surface temperature.
[0037] In an embodiment of the third aspect, the temperature experienced by the portion of the first stream is the maximum surface temperature, and the maximum surface temperature is about 230° F. to about 260° F., or about 250° F. to about 280° F., or about 270° F. to about 300° F., or about 290° F. to about 320° F., or about 310° F. to about 340° F., or about 330° F. to about 360° F., or about 350° F. to about 400° F.
[0038] In a fourth aspect, a system is provided for separating two or more components from a process stream, the system comprising an SMB subsystem with a mobile phase, the SMB subsystem configured to convert a feed stream comprising a first component and a second component, wherein the first component and the second component are present in the feed stream at a first ratio defined by the weight percent of the second component divided by the weight percent of the first component, and at least one of the components is altered at a first temperature, the first temperature being lower than a temperature at which the other component is altered, and the alteration is not reversed completely upon cooling, into a first stream comprising at least a portion of the first component and at least a portion of the mobile phase, and a second stream comprising at least a portion of the second component and at least a portion of the mobile phase, wherein the first component and the second component are present in the first stream at a second ratio defined by the weight percent of the second component divided by the weight percent of the first component, wherein the first ratio is greater than the second ratio; and a vapor compression distillation subsystem, the vapor compression distillation subsystem operating on a distillation feed stream comprising at least a portion of the first stream to separate an amount of the first component from at least a portion of the mobile phase that is present in the first stream, the first component having a boiling point in its purified form at a second temperature at a pressure present within the vapor compression distillation subsystem, the second component having a boiling point in its purified form at a third temperature at a pressure present within the distillation subsystem, a portion of the mobile phase present in the distillation feed stream having a boiling point at a fourth temperature at a pressure present within the distillation subsystem, the fourth temperature being lower than the first temperature and the first temperature being lower than both the second and third temperatures, the vapor compression distillation subsystem having a first thermal energy requirement to be supplied to produce a mass of the first component, the first thermal energy requirement being less than an amount of thermal energy necessary to evaporate the mass of first component.
BRIEF DESCRIPTION OF THE DRAWINGS
[0039] FIG. 1 illustrates the integration of the SMB, polishing bed, and vapor compression distillation (VCD) for removing the eluent from the extract or product stream.
[0040] FIG. 2 illustrates the integration of the SMB, polishing bed, and two VCD units for removing the eluent from the extract or product stream and from the raffinate stream.
[0041] FIG. 3 illustrates the configuration of FIG. 1 further illustrating the thermal integration and recuperative heat exchangers.
[0042] FIG. 4 illustrates the configuration of FIG. 2 further illustrating the thermal integration and recuperative heat exchangers.
[0043] FIG. 5 illustrates a typical SMB system illustrating the inlet valve manifold assembly, the resin beds, and the outlet valve manifold assembly.
[0044] FIG. 6 is a graph of the solubility of sodium sulfate in glycerin-water showing representative operating points of an SMB separation.
[0045] FIG. 7 is a graph of glycerin purity versus glycerin loss from operation of an SMB system.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0046] The following description and examples illustrate some exemplary embodiments of the disclosed invention in detail. Those skilled in the art will recognize that there are numerous variations and modifications of this invention that are encompassed by its scope. Accordingly, the description of a certain exemplary embodiment should not be deemed to limit the scope of the present invention.
[0047] A family of methods and apparatus known as “distillation” can provide approaches for separating components with differing boiling points or vapor pressures. Some forms of distillation and distillation columns have been in common use for many years. A family of methods and apparatus known as “chromatography” provide approaches for separating liquid and gaseous materials which sometimes can be difficult to separate by distillation. Chromatographic separations can be used in laboratory investigations and in some industrial applications.
[0048] A more specialized family of distillation is vapor compression distillation (VCD), which is a specific class of distillation in which the vaporized component is compressed to effect the condensation of the vaporized component at a temperature greater than the temperature of vaporization. The positive temperature differential between the condensing and vaporizing fluids facilitates increased recycling of the heat in the vaporized phase back to the vaporizing liquid. VCD systems can be effective, especially in applications where there is a large difference between the boiling points of the components to be separated. VCD systems can be used in high capacity applications such as desalination, but accumulation of solids on the heat exchange surfaces can be problematic and can limit effective utilization of these techniques. Various approaches for avoiding the problems of scale formation have been attempted.
[0049] In U.S. Pat. No. 4,260,461, the feed material is acidified and degassed prior to processing to prevent carbonate deposits. In U.S. Pat. No. 4,539,076, problems of scaling are ignored and left for others to resolve for making a practical system. Use of each of these is limited to very specialized applications, such as where only carbonates present problems and where the conditions of pH, degassing, and processing time can be tolerated, without undue degradation of desirable compounds.
[0050] Other difficulties that can arise in a distillation operation relate to the potential for degradation or decomposition of desirable compounds due to the high temperatures present during processing. Operation at lower pressures can in some cases result in improvements, but frequently requires greater equipment size or multiple stages, adding expense and complexity with only a small change in the degree of degradation observed.
[0051] A more specialized family of chromatography is simulated moving bed (SMB) chromatography, which consists of two or more separation zones connected by a complex valve array. Each zone includes a bed or fraction of a bed containing a solid adsorbent phase (stationary phase) which is contained between a supply and withdrawal point. In many cases, zones of four, five, six, and more are used. Typically, one feed (F) stream of components to be isolated and at least one eluent (E) stream of solvent are passed into the SMB system, while at least one raffinate (R) stream and at least one extract (X) stream are withdrawn. In some cases a recycle loop is used, consisting of E or extract-rich eluent (EX). An SMB can operate by passing a feed stream comprising, for example, components A and B over a solid adsorbent phase which shows a higher affinity for component A than component B. The eluent stream is passed over the feed stream, pushing component B forward at a rate faster than component A and effecting separation of components A and B. By switching the zones in counter-flow direction to the eluent flow, component B can be removed downstream and component A can be removed upstream of the feed point.
[0052] SMB equipment can be used in many applications including specialty and high value, low volume applications. Other uses include separation of glucose and fructose in the food industry, and potentially the separation of glucose and xylose from biomass hydrolysate as an element of the evolving cellulosic ethanol industry.
Description of Vapor Compression Distillation
[0053] Vapor compression distillation can be used on various process streams to separate components. In some cases, use of vapor compression distillation can lead to reduced energy consumption when compared to various other forms of distillation.
[0054] Vapor compression distillation includes distillation systems that compress a vapor stream from a distillation column, such as a distillation overhead stream, and then exchange the heat from the compressed stream to another stream, such as a feed stream to the distillation system or to a stream within the distillation system, such as in a reboiler. The vapor can be compressed to the point where it forms a condensate, or not. In some embodiments, the compression can result in a portion of the vapor condensing and a portion not condensing. The amount of compression that is applied can vary based on the composition of the streams present and the results desired. In some embodiments, the degree of compression can be selected to result in the condensation temperature of the compressed stream being higher than the desired temperature of the stream that the heat is transferred to. In some embodiments, only a portion of the heat that is needed for the particular stream that is being heated is supplied from the compressed stream. In some embodiments, all or nearly all of the heat is supplied by the compressed stream. In some embodiments, the compressed stream can exchange heat with more than one other stream, such as in a reboiler and with a process feed to the distillation system. When the compressed stream is exchanged with more than one other stream, the compressed stream can exchange heat with both other streams simultaneously (such as by dividing the flow of compressed vapor to the two different streams), sequentially (such as by having the compressed stream exchange heat with one stream and then another), or some combination of simultaneously and sequentially. In some embodiments, additional heat can be added from steam, combustion, electricity, or some other source of heat to the stream receiving heat from the compressed stream.
[0055] The distillation portion of a VCD system can include a plate column, a packed column, a flash tank, centrifugal distillation unit, thin film distillation unit, molecular distillation unit, vacuum distillation unit (operating under any appropriate level of vacuum), pressure distillation units, or some other unit for separation of a gas and liquid phase, or combination of these units. The distillation can operate with one theoretical plate, more than one theoretical plate, or less than one theoretical plate. In some embodiments, the distillation portion of the system can be divided into several parts, such as where several columns, flash tanks, or other distillation units are connected in series or in parallel.
[0056] Additional information on design and implementation of vapor compression distillation in particular situations, such as with nonscale-forming processes and high carbonate sea water can be found in U.S. Pat. No. 4,539,076 and U.S. Pat. No. 4,260,461, respectively, incorporated herein by reference in their entireties.
[0057] Difficulties in implementing vapor compression to distillation can arise, especially in achieving significant energy savings, when a process stream with a tendency to form scale, precipitates, or other solids (collectively “scale”) is used. When the solids precipitate, they can deposit on heat exchange services and reduce the ability to transfer heat between a stream exiting the still (such as distillate, raffinate, or still bottoms) and another stream such as a feed to the still.
[0058] Scale or precipitate formation in a vapor compression distillation system might be avoided in some cases by removing only a portion of the solubilizing component from the feedstream, with the resulting increased losses from such an approach. Addition of a solvent to the scaling-prone stream to prevent scale formation can decrease the thermal efficiency by adding another material which must be heated or, in the alternative by cooling the hot stream prior to heat transfer.
[0059] Propensity for precipitate formation and scale formation of a distillation feedstream can be determined by heating a filtered (for example, filtered through filter paper or other suitable medium) sample of distillation feedstream with stirring (under pressure if necessary) and at a heating rate of about 0.2-15° C. per minute. When the bulk temperature of the distillation feedstream reaches the temperature for which precipitate formation is being evaluated, a sample is withdrawn, cooled, and examined visually or otherwise for precipitate formation or other changes associated with scale/precipitate formation.
Description of Simulated Moving Bed Chromatography
[0060] In some embodiments, problems associated with scale formation and the resulting inefficiencies in vapor compression distillation can be addressed by pre-treating the feed material in an SMB operation to modify the scaling tendency of the feed material. In some embodiments, at least a portion of one or more of the scaling substances can be removed. In some embodiments, at least a portion of one or more of the scaling substances can be replaced with a substance that is volatile. In some embodiments, the volatile substance can have a lower boiling point or higher vapor pressure than the non-scaling material in the feed. In some embodiments, a mobile phase of an SMB system can comprise the volatile substance. In some embodiments, a mobile phase of an SMB system can be primarily composed of the volatile material.
General Principles
[0061] Simulated moving bed chromatography (SMB) is a continuous form of chromatography which includes forms of chromatographic separation or other adsorptive processes where, for example, through a valving arrangement, movement of solid phase in a direction opposite of a mobile phase is simulated or accomplished during processing. Frequently, such systems allow for continuous feed streams to be used with resulting continuous outlet streams. General information on the design and operation of simulated moving bed chromatography systems can be found in U.S. Pat. No. 7,141,172, incorporated herein by reference in its entirety.
[0062] Separation generally occurs through some species in a feed having greater affinity for a stationary phase than other species in the environment within the columns or beds of the system. The environment can refer to such things as the concentration of various species present, mobile phase/solvent composition, temperature, pressure, etc. In a conventional (non-SMB) chromatography system, species with lower affinity for the stationary phase tend to move more quickly through the system. Species with a stronger affinity for the stationary phase tend to move more slowly through the system. In a SMB chromatography system, the slower species will tend to move in one direction (the direction of stationary phase flow), and the faster species will tend to move in the other direction (the direction of mobile phase flow).
[0063] The adsorption that takes place in this form of chromatography can include forms of adsorption related to hydrogen bonding, ionic bonding, chemical bonding, Van der Waal's binding, etc. Additional phenomena that can influence a separation include such things as diffusion of species into the stationary phase. Diffusion can be affected by such things as pore size, chemical composition of the stationary phase and liquid environment, temperature, pressure, flow rate, size of stationary phase particles, size of the diffusing species, and other factors that affect mass transport.
[0064] Frequently, an SMB system is described pictorially as a series of beds with the outlet of one connected to the inlet of the next in the direction of flow of the mobile phase. Frequently, the mobile phase flows from left to right and the simulated movement of the beds is from right to left. During a valve switch to simulate the movement of the beds, the leftmost bed is moved into the rightmost position. Eventually, each bed moves through the region where the more poorly adsorbed species is removed from the system. As a result, it is possible for the species more strongly absorbed to the stationary phase to be desorbed at the wrong time, and being unduly present in the stream intended to be depleted of the more strongly adsorbed species.
[0065] Selection of a mobile phase with appropriate solvation power or affinity for the particular species being separated can be an important aspect of the design of an SMB system, as can be the selection of appropriate stationary phase and flow rates and timing of bed movement. Less than ideal selection of one or more of these parameters can lead to undue fouling of the stationary phase, inadequate separation, high product losses, etc.
[0066] In some embodiments, the mobile phase can be utilized as a stream that passes from one bed to the next through the series of beds, and is recycled back to the first bed after exiting the last in the line. A portion of the mobile phase can be removed with each product, with makeup material added with the feed, or as a separate point in the process. In some embodiments, mobile phase can be added at more than one point.
[0067] In some embodiments, the mobile phase can be recycled to a point different from the first bed, with a second mobile phase used in the beds to the left of the bed where first mobile phase is recycled to. In some embodiments, where two or more mobile phases are used, the composition of each mobile phase can be the same or different. In some embodiments with two or more mobile phases, the material for the first mobile phase can be the same as the second mobile phase. In some embodiments where two mobile phases are present, the second mobile phase can act as a bridge step for the beds which it contacts, with the mobile phase flowing into the bed that the first mobile phase is recycled to. In some embodiments, the second mobile phase can flow into the bed receiving the recycled first mobile phase. In some embodiments, only a portion of the second mobile phase flows into the bed receiving the recycled first mobile phase. In some embodiments, one product is recovered from a first mobile phase, and another product is recovered from the second mobile phase. In some embodiments, the bed or beds treated with the second mobile phase are drained or purged prior to moving the bed to its next position.
[0068] In some embodiments, it is desirable to select a mobile phase having a lower boiling point than a temperature that can lead to precipitation of components in the feedstream to a distillation or vapor compression distillation system downstream of the SMB. In some embodiments it is desirable to select a mobile phase having a lower boiling point than the temperature where a component of the feed is altered physically or chemically. Physical or chemical altering includes any change that affects the separation or products. Physical or chemical alteration can include decomposition, polymerization, depolymerization, side reactions, chemical rearrangement of bonds, isomerization, refolding of proteins, changes in conformation, rearrangement of hydrogen bonds, precipitation, etc., and can be reversed upon cooling, not reversed upon cooling, or only partially reversed upon cooling. In some embodiments, the temperature where physical or chemical alteration occurs can be present in a distillation or vapor compression distillation system. In some embodiments, a mobile phase with a lower boiling point can allow for more favorable operation in a distillation (including vapor compression distillation) subsystem by modifying the separation that occurs in the distillation subsystem. For example, vaporization of the mobile phase present in the distillation feed can replace vaporization of a higher boiling component. This change can lead to lower scaling or precipitation tendencies within the equipment, resulting in improved heat transfer, especially over a sustained period, by operating at a lower temperature or by reducing the concentration of precipitating material in relation to the material being recovered from the feed. This change can also lead to reduced decomposition or chemical modification of components in the feed by allowing operation at a lower temperature than would normally occur. These changes can in turn facilitate additional improvements to a separation, such as allowing distillation under pressure rather than under vacuum and separation with a greater number of theoretical plates and/or higher throughputs.
Combined Vapor Compression Distillation and SMB Treatment
[0069] In FIG. 1 , a high efficiency separation method 1 is shown which includes a simulated moving bed (SMB) 10 unit, an optional ionic polishing unit 11 , and a vapor compression distillation (VCD) unit 12 . A stream 20 that consists of a mixture of feed components A and B, both of which are soluble in eluent solvent 30 , are fed to the SMB 10 to effect the separation of A from B by passing an eluent solvent 30 through the mixture in contact with the solid adsorbent in the columns of the SMB. The solid adsorbent in the columns can be selected from a variety of adsorbents which demonstrate an increased affinity for one compound over the other. For purposes of this discussion, we will assume that component A has a higher affinity for the solid adsorbent than component B. The discussion or selection of any specific solid adsorbent and the discussion or selection of any specific mixture of compounds A and B are not intended to limit the scope of this invention, but are provided as illustrative examples.
[0070] As the feed 20 passes over the solid adsorbent, component A demonstrates a greater affinity to the resin than compound B. The eluent solvent 30 passes through the feed mixture pushing both compounds downstream, but effectively component B has a greater eluting speed through the column than compound A because component B has a lower affinity for the solid adsorbent. The valve timing responsible for the simulated motion of the columns is adjusted with respect to mixture feed flow rates, the eluent flow rates, and the relative affinity of components A and B to the solid adsorbent. The result is a raffinate stream 31 primarily composed of eluent and component B with only reduced amounts of compound A and an extract stream 21 primarily composed of eluent and component A with only trace amounts of component B. In this embodiment, the extract stream is the primary product stream targeted for high purity, but in other embodiments either stream (or even both) could be the product stream, with one or both optionally treated to increase purity beyond that achieved with the SMB system alone, depending on the separation of interest. In some embodiments one of the components, such as a component B, can be a waste product.
[0071] The extract stream 21 is passed to an optional polishing bed 11 in which the amount of component B is further reduced to, for example, meet the final purity target. The outlet of the polishing unit 11 is dilute product stream 22 which is passed to a VCD unit 12 . The function of the VCD is to separate the eluent solvent from the product component A. The eluent is evaporated and condensed in the VCD to produce eluent stream 32 which is optionally recycled back into the SMB unit 10 . The high purity, high concentration product stream of component A is passed out of the VCD as product stream 23 .
[0072] In some embodiments, an optional separation system can be utilized to concentrate component B in the raffinate stream 31 . Various separation systems can be utilized including evaporators, filters, microfilters, ultrafilters, cross-flow filters, nanofilters, distillation, extraction, adsorption, absorption, vapor compression distillation, etc. In FIG. 2 , a system utilizing a second VCD system 13 is incorporated into the processes to enhance the eluent recovery and maximize the concentration of component B in the concentrated raffinate stream 34 . This VCD unit vaporizes and condenses the eluent from stream 31 to generate recycle stream 33 . The energy required for the vaporization of the eluent is recycled within the VCD unit to minimize energy consumption and maximize process efficiency. In some embodiments, the mass recovery of eluent from a raffinate stream 31 can be more than about 30%, or more than about 50%, or more than about 70%, or more than about 90% of the eluent in the raffinate stream 31 before the concentration of component B in the waste stream begins to reach its saturation point. In some embodiments, separation systems other than vapor compression distillation can be utilized which can facilitate recoveries beyond the point where saturation can occur.
[0073] In some embodiments, an energy recycling scheme can be implemented, such as is shown in FIG. 3 , which illustrates an embodiment of heat exchanger integration for a combined SMB-VCD system, which can optionally include heating the material fed to the SMB. FIG. 3 illustrates expanded details of a VCD unit 12 , consisting of a vapor compressor 41 , heat exchanger 43 , evaporation/distillation vessel 42 . The extract stream 21 passes through the polishing unit 11 and flows through recuperative heat exchanger 71 and enters the vapor compression unit 12 through connection 22 . A boost heater can be used to increase the temperature of stream 22 as it enters the vessel 42 where the lower boiling eluent fluid is vaporized and the higher boiling product compounds remain in liquid phase. The eluent vapor passes through connection 45 and enters compressor 41 where the pressure is increased to a level sufficient to cause the vapor to condense in heat exchangers 43 and 71 . The heat of condensation is transferred into the liquid mixture in vessel 42 and into incoming stream 22 at heat exchanger 71 , where the energy is balanced by the energy needed for vaporizing the eluent fluid. In some embodiments, the fluid in vessel 42 is recycled within the vapor compressor unit (pump not shown) to ensure high efficiency heat transfer and high degree of eluent removal. In this configuration of heat exchangers, the concentrated product stream 44 passes out of the vapor compression unit 12 through connection 44 where it enters heat exchanger 74 and helps to preheat feed mixture stream 20 , when desired; stream 44 then exits the system through connection 23 . The recovered eluent exits heat exchanger 71 , passes through connection 32 and into buffer tank 72 , where it is combined with feed eluent stream 30 . The eluent is then pumped by pump 73 through heat exchanger 75 and into the SMB unit 10 . Also illustrated in this embodiment is the option of having an eluent recycle loop 76 .
[0074] In some embodiments, an energy recycling scheme can be implemented, such as with evaporative concentration/distillation, on both the extract and raffinate streams from an SMB, as shown in FIG. 4 , which illustrates an embodiment of heat exchanger integration for a combined SMB-VCD system, where VCD is present on two outlet streams from an SMB. FIG. 4 illustrates a heat exchanger interface for the embodiment shown in FIG. 2 that incorporates a second VCD unit to support the recovery of eluent solvent from the raffinate stream 31 . In this embodiment a VCD unit 13 is shown indicating raffinate stream 31 flowing into the evaporative/distillation vessel 92 where some of the vaporized eluent flows through connection 95 to compressor 91 . The compressor increases the pressure of the vapor, causing condensation of the eluent and in heat exchanger 93 which transfers energy into the liquid in the vessel 92 or into the raffinate stream 31 by way of heat exchanger 98 . The condensed eluent solvent is collected in buffer tank 97 and pumped through heat exchanger 99 and back into the SMB 10 as a recycle eluent stream.
[0075] One embodiment of an SMB unit 50 is shown schematically in FIG. 5 , with four chromatography columns: 71 , 72 , 73 , and 74 , and two valve manifold blocks: inlet block 51 and outlet block 52 . Other configurations of the SMB unit 10 are viable with greater number of columns such as five, six, seven, eight, or more, and even with fewer columns depending on the SMB process used. Likewise, other valving or manifolding arrangements can be utilized, such as rotating valve assembles, multi-way valves, or other types of valves as well as shared or dedicated pipes/manifolds/headers/ducts. This illustration is provided only to describe a representative SMB and is not intended to limit the scope or definition of the method.
[0076] In one embodiment, an SMB system as in FIG. 5 can be divided into a three zone SMB, but in various other embodiments, other numbers of zones can be utilized. Three feed streams—eluent one 61 , eluent two 62 , and process feed 63 —and one recycle stream 64 are provided to the inlet manifold block 51 . Two product streams, extract 65 and raffinate 66 , the recycle stream 64 , and the column-to-column bypass streams are managed by the outlet manifold 52 . The following discussion is for a three zone SMB where column 71 represents the first zone, column 72 represents the second zone, and columns 73 & 74 represent the third zone. During operation, process feed 63 passes through manifold block 51 and enters column 73 , while eluent one 61 enters and passes to column 71 and eluent two 62 enters and passes to column 72 . Fluid from column 71 exits through outlet manifold block 52 and passes out through extract 65 . Fluid from column 72 exits through block 52 and is transferred to the inlet of column 73 along with process feed 63 . Fluid from column 73 exits through block 52 and is transferred to the inlet of column 74 , while the fluid passing through column 74 exits through block 52 and passes out through raffinate 66 . Once steady state is achieved, column 71 contains adsorbed component A and very little component B at the beginning of the switching cycle; columns 72 and 73 contain a mixture of components A & B; and column 74 contains eluent solvent. Eluent one 61 pushes the adsorbed component A out of column 71 and out through the extract 65 . Eluent two 62 pushes the mixture of components A and B in column 72 out and into column 73 , while mixing with process feed 63 at the inlet of column 73 . Eluent two 62 continues to push compound B downstream and eventually out of column 74 and into the raffinate 66 . After all of component A is removed from column 71 and before component A is pushed out column 74 with the raffinate 66 , the valves in manifolds 51 and 52 are switched, effectively moving the columns one position to the right, such that column 72 is moved into the first zone, column 73 is moved into the second zone, and columns 74 and 71 are moved into the first and second positions, respectively, of zone three. This switching effectively moves component A upstream while component B continues to move downstream, promoting the separation of the components.
[0077] In various other embodiments, other arrangements of an SMB system can be utilized and can be operated in different ways, such as by varying the number of columns; introducing the process feed at a different point; introducing eluent at a different point; removing extract and/or raffinate at a different point; and recycling, purifying, or otherwise modifying eluent utilized in the system.
[0000] Separation of Glycerin from Salt or Base
[0078] In one embodiment, a separation of glycerin from a salt or a base can be accomplished with vapor compression distillation with reduced tendency for scale formation and/or reduction in thermal efficiency over time by treating the contaminated glycerin stream in an SMB operation to replace the salt or base with a lower boiling component, such as water, prior to treatment in the vapor compression distillation unit.
Example 1
Desalting of Glycerin
[0079] A combination of VCD and SMB can be used to separate glycerin from a soluble salt. A laboratory prototype unit was designed and operated on glycerin contaminated with 2.5% sodium sulfate salt. The eluent solvent was de-ionized water. The unit consisted of four columns arranged as a three-zone SMB with inlet and exit solenoid valves assemblies. An ionic exclusion resin was selected because of its higher affinity to the glycerin than the ionic salt compounds. The columns were packed with 78 gm of the neutral form of a strong acid cation resin, LEWATIT® GF-404 resin (Lanxess, Leverkusen, Germany). Each column was 25 cm long with an inside diameter of 2.1 cm. Eluent solvent flow rates between 20 and 100 ml/minute were introduced at the inlet of zone 1 (1 column) to recover the purified glycerin, with all of the eluent collected after passing through the column. Eluent solvent flow rates between 20 and 100 ml/minute were introduced at the inlet of zone 2 (1 column) to flush the salt downstream. The material from zone 2 flowed to zone 3. Feed glycerin solution flow rates between 20 and 70 ml/minute were introduced at the inlet of zone 3 (2 columns). The switch time was varied between 30 and 60 seconds, depending on the various flow rates. Preliminary performance map of the glycerin SMB unit is illustrated in FIG. 7 . A typical operating point indicates the ability to achieve 99.8% glycerin purity with 83% recovery. The glycerin extract stream was recovered as a 25% (wt.) solution in water, and the salty raffinate stream was recovered as a stream having 0.7% (wt.) salt and 2% (wt.) glycerin in water. Since the boiling point of water is substantially lower than the boiling point of glycerin, the water can be evaporated at a higher pressure and could be used to evaporate glycerin without undue alteration of the glycerin to achieve a high concentration glycerin product stream. The energy required to convert a 25% (wt.) glycerin stream to a near 100% (wt.) glycerin stream by evaporating the water would require approximately 2,100 kilocalories/liter of glycerin. This amount of energy is approximately equivalent to 7 times the heat of vaporization of glycerin, which can be less efficient than a two-stage distillation unit.
[0000] Glycerin from Biodiesel Production
[0080] The production of biodiesel is frequently conducted in modular refineries, from micro-scale batch reactors (100 to 400 liters per batch) to small-scale continuous processes (1,000 to 4,000 liters per hour). Site-constructed facilities typically range from 4,000 liters per hour (10 M gallons/year) to 50,000 liters per hour (100 M gallons/year). With a typical continuous modular biodiesel production system (39 M liters per year or 10 M gallons per year) the unit consumes 4,113 kg/hr of vegetable oil, 588 kg/hr of methanol, 25 kg/hr of catalyst (NaOH), and produces 4,087 kg/hr of biodiesel, 632 kg/hr of g-phase (glycerin, catalyst, soaps, and methanol), and 7 kg/hr of waste. The glycerin-phase is treated to remove the methanol and soaps while neutralizing the catalyst with about 10% H 2 SO 4 solution to produce a crude glycerin solution consisting of 408 kg/hr of glycerin, 33 kg/hr of Na 2 SO 4 and 208 kg/hr of water or crude glycerin solution with a composition of about 63% glycerin, about 5% salt and other contaminants, and about 32% water. Principles related to the separation of glycerin and salt or base can be applied to the crude glycerin side stream associated with biodiesel production.
Example 2
Separation of Catalysts/Salt from Glycerin Byproduct of Biodiesel Production
[0081] One application of this method is the separation of the homogeneous catalyst from the co-product glycerin produced in biodiesel facilities. Frequently, in a biodiesel facility, triglycerides are mixed with alcohol and sodium hydroxide and are reacted at elevated temperatures to form an alkyl-ester (biodiesel) and glycerin. A majority of the catalyst exits the reactor in the glycerin-phase (g-phase), which can be neutralized with an acid such as sulfuric acid to facilitate separation and recycle of non-reacted triglycerides. Often, the excess alcohol in the g-phase is also removed before or after neutralization.
[0082] In operation, the g-phase can be further contaminated with other components of the vegetable oil or animal fat feed material used as the source of triacylglycerides, such as chromophores, partial glycerides, fatty acids, sterols, stanols, gums, waxes, proteins, carbohydrates, phospholipids, lysophospholipids, etc. as well as derivatives of these materials and side products of the reaction forming the biodiesel material, such as non glycerin organic matter. The presence of additional impurities such as these can add to the complexity of designing a suitable separation system, especially one which utilizes simulated moving bed technology. Issues that can arise include fouling of the stationary phase, reaction with the stationary phase, as well as the need to force the additional impurities to the exit point of the process desired. For example, selection of a stationary phase that adsorbed the impurities too strongly can result in the impurities remaining with the glycerin instead of the salts. Alternatively, if the impurities do not adhere strongly enough, they can move through the beds to quickly, and not be removed with the salts, but instead be recycled, potentially building up and fouling the system and/or contaminating the glycerin stream. In addition, each of these impurities can have different adsorption and solvation properties, resulting in the need to balance the stationary phase selection and the eluent composition.
[0083] In some embodiments, a system such as that described herein for the separation of salt from glycerin can be used with little modification. In some embodiments, an additional zone can be utilized for removal of organic contaminants with a suitable solvent as an eluent, such as an alcohol, an aldehyde, a ketone, a nitrile, a hydrocarbon, an aromatic, a halogenated compound, etc., in, for example, a step which isolates this eluent from the other eluent being used. In some embodiments, the conditions or composition of one of the eluents already incorporated into the system can be modified, such as by increasing or decreasing the polarity or dipole moment of the solvent. In some embodiments, increasing the salt concentration (such as by decreasing the amount of eluent, recycling raffinate, or adding salts) can result in shifting the adsorption and passage rate for various impurities, allowing them to be captured with the salts. In some embodiments, higher levels of eluent can be used to reduce the salt concentration, and shift the absorption characteristics of the impurities.
[0084] In some embodiments, the feed to the SMB can be further processed to remove particular impurities. Suitable methods of treatment include filtration, microfiltration, ultrafiltration, adsorption, extraction, absorption, etc. In some embodiments, highly nonpolar materials can be removed prior to treatment in the SMB operation.
Example 3
Purification of Glycerin Byproduct from Biodiesel Production by Distillation
[0085] A feedstream stream of glycerin and sodium sulfate can be separated in a two-stage vacuum distillation process. Glycerin (C 3 H 8 O 3 ) has a molecular weight of 92.1 g/mole, a boiling point of 290° C. (554 F), a heat capacity of 0.62 cal/g at 25° C., a heat of vaporization of 21,060 cal/mole at 55° C., a specific gravity of 1.262 at 25° C., and a vapor pressure of 0.195 mmHg at 100° C. Some industrial scale two-stage vacuum distillation systems (non-vapor compression distillation systems) can process approximately 7.6 million liters per year (about 2 million gallons per year or 2,234 lb/hr glycerin product), with approximately 80% recovery of the feed glycerin, and requiring about 1,266 kilocalories/liter (19,000 Btu/gallon) based on the glycerin product. This energy consumption is equivalent to approximately 4 times the heat of vaporization of glycerin.
[0086] Some industrial process uses a two-stage vacuum distillation method. A unit designed for approximately 7.6 million liters per year (2 million gallons per year or 2,234 lb/hr glycerin product), achieves approximately 80% recovery of the feed glycerin, and requires 1,266 kilocalories/liter (19,000 Btu/gallon) based on the glycerin product. This is equivalent to 4 times the heat of vaporization of glycerin. Vapor compression distillation is not used.
Example 4
Concentration of Purified Glycerin
[0087] By integrating an SMB unit with a VCD, unit a much higher efficiency and lower carbon footprint process can be achieved. In embodiments where the product from the SMB prototype unit is concentrated with a VCD unit, the estimated energy required can be about 160 kilocalories per liter of glycerin. This is equivalent to about 0.5 times the heat of vaporization of glycerin, which is about ⅛ the heat requirement for an industrial two-stage vacuum distillation process and about one 1/13 the heat requirement for an SMB process with conventional distillation of water eluent from the glycerin. As shown in FIG. 1 and FIG. 6 , the crude glycerin feed can be represented by composition 81 . During the SMB 10 processing step, two product streams are generated. The salt is concentrated into a raffinate stream 31 , which exits the SMB at a composition 84 , while the glycerin is concentrated into an extract stream 21 , which exits the SMB at a composition 82 . In one embodiment the extract stream is then concentrated by removal of water with a VCD 12 effectively reaching composition 83 without a significant reduction in the amount of heat in the distillation vapor stream being lost. Recovered water can be passed back to the SMB 10 through connection 32 . In some embodiments, an optional polishing bed 11 can be used if higher purity glycerin is the target product. Suitable polishing beds include activated carbon, the ionization resin, neutral adsorbents (polymeric, zeolites, silicas, etc.).
Example 5
Concentration of Salt Stream by Vapor Compression Distillation
[0088] In another embodiment, as shown in FIG. 2 and FIG. 6 , a portion of the water content of the raffinate stream can also be recovered with minimum energy input. A second VCD 13 is used to move the raffinate composition 84 to composition 85 , before the salt begins to reach its maximum concentration. At this point approximately 90% of the water in the raffinate stream has been recovered.
[0089] In FIG. 6 , the feed composition 81 is very close to the solubility curve for salt in the glycerin-water mixture. This characteristic indicates that if a VCD process were used in either the removal of water from the feed material or the direct distillation of glycerin, salt would precipitate out of solution because the composition would be above the solubility line 88 . This salt precipitate could coat the heat exchanger surface area and decrease the effectiveness of the VCD equipment by, for example, decreasing heat transfer efficiency, demonstrating a benefit of a combined SMB and VCD system.
Application to Temperature Sensitive Materials
[0090] The principles of combined vapor compression distillation and simulated moving bed processing, as described herein, can be applied to recovery of temperature sensitive products. In one embodiment, the use of water as a mobile phase in the recovery of glycerin from a stream comprising salt or base allows distillation of a stream comprising glycerin at a lower temperature without resorting to conditions of high vacuum or suffering undue product decomposition by evaporating lower boiling water instead of higher boiling glycerin. Other mobile phases can also be applied to this type of separation, such as alcohols, carbonyl compounds, hydrocarbons, etc. In other embodiments, the use of combined vapor compression distillation and simulated moving bed processing can be applied to other temperature-sensitive products, such as oils (including oils having highly unsaturated fatty acids) and other components of vegetable oils such as sterols, stanols, tocotrienols, etc.
Example 6
Separation of Free Fatty Acids from Crude Vegetable Oil
[0091] Another application of this method is the separation of free-fatty acids from triglycerides present in the mixture of off-specification crude corn oil extracted from the thin stillage of corn ethanol facility. Typically, this extracted oil is composed of 80-90% triglycerides, 10-20% free-fatty acids and 0-5% waxes or other compounds. A resin can be selected which has a stronger affinity to the free-fatty acids because of their polar nature or smaller molecular weight. In this example the free-fatty acids are compound A while the triglycerides are compound B. The eluent solvent can be selected from any of a series of organic solvents such as alcohols (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, pentanols, hexanols, etc.), carbonyl-containing compounds (aldehydes, ketones, acetone, 2-propanone, 2-butanone, etc.), nitriles, alkanes, aromatic solvents, halogenated organics, etc.,
[0092] All references cited herein, including but not limited to published and unpublished applications, patents, and literature references are incorporated herein by reference in their entirety and are hereby made a part of this specification. To the extent publications and patents or patent applications incorporated by reference contradict the disclosure contained in the specification, the specification is intended to supersede and/or take precedence over any such contradictory material.
[0093] The term “comprising” as used herein is synonymous with “including,” “containing,” or “characterized by,” and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps.
[0094] All numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification 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 herein are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of any claims in any application claiming priority to the present application, each numerical parameter should be construed in light of the number of significant digits and ordinary rounding approaches.
[0095] The above description discloses several methods and materials of the present invention. This invention is susceptible to modifications in the methods and materials, as well as alterations in the fabrication methods and equipment. Such modifications will become apparent to those skilled in the art from a consideration of this disclosure or practice of the invention disclosed herein. Consequently, it is not intended that this invention be limited to the specific embodiments disclosed herein, but that it cover all modifications and alternatives coming within the true scope and spirit of the invention. | The invention concerns separation methods and systems including those comprising a continuous chromatographic simulated moving bed integrated with vapor compression distillation to create a high efficiency separations platform applicable to a broad range of separation functions. | 2 |
BACKGROUND OF THE INVENTION
The present application is directed to an anaerobic upflow batch reactor for the removal of contaminants, especially organic contaminants, from waste water utilizing a processing method wherein the waste water being treated flows in a plug flow configuration from near the bottom of the reactor to near the top of the fluid within the reactor.
Historically, numerous systems have been developed by waste water engineers for the treatment of waste water to remove impurities therefrom. Such systems have included continuous flow type reactors as well as batch type reactors. Systems have also included aerobic, anaerobic and combinations of aerobic and anaerobic treatments of the waste water. The present invention is directed to a modification of anaerobic batch systems in order to produce special processing characteristics within the system.
In particular, upflow batch reactor systems have been produced in the past for treating the waste water and an example of such a system is shown in the Dague U.S. Pat. No. 5,185,079. Batch reactors have certain advantages over continuous flow reactors in that the material to be treated can be positively maintained within the batch reactor until the process is complete whereas in continuous flow reactors there is a possibility of incomplete reaction before the waste water exits the process.
The inventors of the present invention have found that careful control of certain parameters of a batch system substantially enhances the ability of the batch reactor to complete its task. In particular, they have discovered that, if the flow through the reactor can be maintained as a substantially true plug flow from near the bottom of the reactor to near the top of the liquid, a reaction gradient can be produced that has special advantages to the operation to the system. However, these advantages are mostly lost if flow in the reactor is not plug flow throughout. This is true even where the flow starts as plug flow, but does not raise substantially vertically through the reactor, such as where there is a side takeoff and a substantial amount of the flow is horizontal or diagonal relative to the reactor.
In particular, if the concentration of the biomass and food substrate which feeds the biomass within the waste water can be carefully controlled to move through the reactor in a movement that is designed to pass from the bottom of the reactor to near the top of the liquid in a mostly vertical direction (that is the individual molecules have a mainly vertical vector associated therewith and without substantial mixing, the advantageous growth of particular types of biomass in particular areas of the reactor can be enhanced and the biomass that might otherwise be entrained with the fully treated liquid, as the liquid leaves the reactor, can be substantially reduced.
The prior art upflow anaerobic batch reactors of the type shown in the above noted Dague patent have failed to take advantage of such a system and, in particular, have typically withdrawn fluid from the reactor from the side or otherwise unevenly such that movement through the reactor is not substantially up and down, but rather has a substantial sideways component. Withdrawal from the side, as in Dague and other prior art references, causes mixing which also defeats the goals of the process of the present application.
SUMMARY OF THE INVENTION
The present invention is directed to a method and apparatus for treatment of waste water to remove impurities, especially organic impurities, therefrom. In accordance with the invention waste water to be treated is flowed upwardly from near the bottom of a reactor to near the top of the fluid contained within the reactor while removing the fluid from the top in a generally uniform manner that requires the fluid to flow mostly upward rather than sideways, such that the waste water rises vertically throughout most of the process or in a plug flow fashion. That is, the waste water rises from near where it enters the reactor to near where it exits the reactor in a somewhat linear path rather than moving substantially sideways within the reactor and being withdrawn from the side of the reactor or being heavily mixed within the reactor. Obviously when speaking of fluid there is going to be a certain amount of mixing at any one time and there is normally a minimal amount of sideways flow especially near the withdrawal and input ports, since the ports require some spacing, but it is desirable to maintain mixing and sideways flow at a relatively low level and to maintain it on a local rather than regional basis within the reactor. Preferably, the waste water enters the reactor at numerous sites or ports spaced across the bottom of the reactor in somewhat of a uniform pattern and exits the reactor through similar locations or ports near the top of the fluid.
The reactor is operated as an upflow anaerobic reactor. As used herein the term anaerobic means that there is not a substantial amount of oxygen added to the fluid within the reactor, as is done in aerobic type reactors. It is possible that a certain amount of dissolved oxygen, which enters the anaerobic reactor with the waste water or otherwise, may be found within the reactor, but the major difference in comparison to aerobic processes is that substantial quantities of oxygen are not added to the fluid within the reactor. This enhances the growth of anaerobic type bacteria and other micro-organisms rather than aerobic type micro-organisms.
The purpose of operating the reactor in a plug flow mode and anaerobic state is to produce a gradient of biomass within the reactor that is preferential to the treatment of the waste water and so as to prevent a substantial portion of the biomass from leaving the reactor with the waste water that has been treated therein. The biomass within the reactor is made up of joined micro-organisms and it is preferable in accordance with this invention to encourage growth of heavier and larger biomass groups that have a tendency to remain near the bottom of the reactor or float in lower levels of fluid within the reactor, for example most floats and stays in the lower third of the fluid layer. Preferably light and highly floatable types of biomass, which are normally small clumps of micro-organisms as compared to the remaining biomass and which would likely float in the upper portion of the fluid layer, for example in the upper third of the fluid layer, are maintained at relatively low concentration throughout the reactor.
OBJECTS AND ADVANTAGES OF THE INVENTION
Therefore, the objects of the present invention are: to provide a waste water treatment process wherein waste water flows through a reactor in anaerobic conditions in a plug flow configuration; to provide such a process encouraging a biomass growth that decomposes contaminates within the waste water in such a pattern that the heaviest biomass concentration is near the bottom of the reactor and very little biomass concentration is near the top of the reactor; to provide a system wherein the process promotes the growth of heavier and larger biomass concentrations that remain near the bottom of the reactor and discourages the growth of lighter and smaller biomass concentrations that would tend to float higher in the reactor; to provide such a process wherein a gradient of decomposable food stuffs for the biomass or substrate is heaviest in the lower part of the reactor so as to encourage growth of suitable bacteria therein and lightest near the top of the fluid within the reactor so as to discourage growth of biomass in the upper portion of the reactor; to provide such a process wherein waste water is distributed at multiple locations spaced across the lower end of the reactor and withdrawn from similar multiple spaced locations across a withdrawal decanter located near the top of the fluid in the reactor so as to encourage waste water to rise relatively vertically through the reactor without substantial sideways movement and without substantial global mixing; to provide such a process for the recirculation of waste water from near the top of the fluid within the reactor to near the bottom thereof; to provide such an anaerobic process in combination with an aerobic waste water treatment process, especially an aerobic sequencing batch reactor, such that the anaerobic process functions to polish or further purify the waste water leaving the aerobic process; to provide an apparatus for use in conjunction with such a process; and to provide such a process an apparatus that are especially easy to operate, relatively inexpensive to produce and especially well suited for their intended usage. Other objects and advantages of this invention will become apparent from the following description taken in conjunction with the accompanying drawings wherein are set forth, by way of illustration and example, certain embodiments of this invention.
The drawings constitute a part of this specification and include exemplary embodiments of the present invention and illustrate various objects and features thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational and schematical view of a process in accordance with the present invention utilizing an anaerobic and upflow waste water treatment reactor.
FIG. 2 is a cross sectional view of the reactor, taken along line 2--2 of FIG. 1.
FIG. 3 is a cross sectional view of the reactor, taken along line 3--3 of FIG. 1.
FIG. 4 is a chart showing a typical substrate distribution profile in accordance with the present invention.
FIG. 5 is a chart showing a typical easily setteable biomass profile in accordance with the present invention.
FIG. 6 is a flow chart illustrating a modified process according to the present invention including both aerobic and anaerobic process apparatus.
DETAILED DESCRIPTION OF THE INVENTION
As required, detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which may be embodied in various forms. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed structure.
The reference numeral 1 generally designates an apparatus for treating waste water in accordance with the present invention. The apparatus 1 includes a vessel or tank 5, an influent system 6 and an effluent system 7.
The tank 5 has a cylindrical sidewall 10, a bottom 11 and a top 12 so as to form an inclosure 13 for receiving fluid 14 therein. The tank top 12 is raised in the center and the interior flow connects with a vent pipe 17 for transferring gas away from the tank 5.
The influent system 6 includes a conduit 20 joined at one end to a source of influent waste water and at the other end to a distribution manifold 21 within the tank 5. The distribution manifold 21 includes a series of spaced concentric and circularly shaped pipes 23 having spaced apertures 24 flow opening to the interior thereof and located along the top thereof. Each of the pipes 23 is flow connected interiorly and flow connected to liquid within the tank 5 through the apertures 24. The pipes 23 are also flow connected to a conduit 26 forming the remainder of the distribution manifold 21 which in turn flow connects with the conduit 20 such that influent can be distributed from the conduit 20 through the distribution manifold 21 and flow from the apertures 24 within the tank 5. Because of the spacing of the pipes 23 and the apertures 24, fluid is preferably dispersed in a generally uniform upward flowing pattern over the entire lower end of the tank 5. In particular, the pipes 23 are located close to the tank bottom 11 such that the influent flows into the tank 5 near the bottom 11 thereof.
The effluent system 7 includes a collection manifold 30 a pump 31 and a discharge conduit 32. The collection manifold 30 includes a series of pipes 34 which are essentially a mirror image of the pipes 23 of the distribution manifold 21. In particular, the pipes 34 are circular and arranged concentrically relative to one another with approximate equal spacing therebetween. Each of the pipes 34 include a series of evenly spaced apertures 35 thereabout. The apertures 35 face downward and toward the apertures 24 and are aligned so as to encourage the flow of water vertically between two opposed apertures 24 and 35 without substantial mixing within the tank 5. Although some mixing must occur in such a process, it is preferable to keep such mixing to a minimum in accordance with the invention.
The collection manifold 30 includes a series of floats 37 which are attached to the collection manifold 30 so as to allow it to freely float within liquid or fluid 14 within the tank 5. In particular, the floats 37 float at the surface 38 of the liquid 14 within the tank 5 and maintain the collection manifold 30 at a fixed spacing from the surface 38. Preferably the pipes 34 are spaced anywhere from several inches to eighteen inches from the surface 38 so as to discourage the entranement of scum floating on the surface 38 into the apertures 35. The collection manifold 30 also includes a joining conduit 39 that flow connects with each of the pipes 34 and in turn with each of the apertures 35 so that liquid within the tank 5 can flow into the conduit 39. Attached to the conduit 39 is a flexible conduit 41 which flow connects with a pivotable conduit 42. The pivotable conduit 42 is connected to the side of the tank 5 by a hinge 43 which allows the entire collection manifold 30 from the pivotable conduit 42 to the floats 37 to move vertically within the tank 5 so as to allow the pipes 34 to remain in a fixed position relative to the liquid surface 38 as the liquid surface 38 moves vertically within the tank 5. Centering struts or the like (not shown) may be utilized to keep the collection manifold 30 centered when needed.
The pivot conduit 42 is flow connected to a conduit 45 which in turn is connected to the pump 31. The pump 31 discharges through a valve 46 into the discharge conduit 32. In this manner fluid can be pumped from the interior of the tank 5 through the apertures 35, through the pump 31 and out the discharge conduit 32 when the valve 46 is open. The fluid pumped from the discharge conduit 32 is treated waste water and is transferred to storage, discharged to a stream or otherwise disposed of. The conduit 45 also connects with the influent conduit 20 through a valve 48. When the valve 48 is open, the valve 46 is closed and the pump 31 is operating, liquid within the tank 5 can be recirculated from near the top of the tank 5 through the apertures 35 to near the lower end of the tank 5 through apertures 24.
Connected to the tank bottom 11 is a sludge discharge conduit 50 which is flow connected to a storage location for receiving excess sludge (not shown) under control of a valve 51. In this manner excess sludge can be removed from the tank 5 and disposed to storage or other treatment.
Although the apparatus 1 may be utilized by itself in the treatment of waste water, it can also be utilized with other facilities. One such example would be to polish or further clean the water by destroying remaining organic materials contained within the waste water after the waste water has been treated by another type of waste water treatment facility. Shown in FIG. 6 is such an installation where waste water to be treated as represented by the block 55 is transferred to an anaerobic treatment apparatus, such as has been previously described, 1 and then to an aerobic apparatus represented by the block 56. Such an aerobic apparatus may be a sequencing batch reactor or another type of waste water treatment apparatus. The waste water after being treated in the aerobic treatment apparatus 56 is then transferred to disposal represented by the block 57. A suitable aerobic treatment apparatus of the type required for the present invention is known to those skilled in the art and has previously been described. For example, U.S. Pat. No. 5,021,161 to Calltharp et al discloses such an aerobic process which is incorporated herein by reference.
In use the apparatus 1 is essentially an upflow, anaerobic, plug flow type system or process wherein waste water flows from near the bottom of the tank 5 to near the top thereof in a generally vertical flow pattern. While distribution cannot be made on such a minute scale and although all possible disruptions of flow cannot be eliminated to such an extent that there is no mixing within the fluid being treated within the tank 5, it is preferable that as little horizontal mixing as possible occur while the waste water is flowing into or being treated in the tank 5.
Normally, the batch process utilizing the apparatus 1 will be initiated with a fill cycle at which time the collection manifold 30 is positioned at its lowest position within the tank 5. The lower most position of the collection manifold 30 will somewhat depend upon the interface level where clarified water occurs within the tank at the end of the previous batch process. In particular, the waste water is treated within the tank by reaction of substrate, which includes organic materials to be decomposed by the process, with biomass within the tank 5. Initially, the biomass forms a blanket near the bottom of the tank 5 and is composed of micro-organisms, especially anaerobic bacteria. As waste water flows into the tank 5 through the apertures 35, the waste water flows upwardly through a portion of this biomass such that the substrate within the waste water interacts with the biomass. The biomass is normally somewhat denser than the fluid within the tank and, therefore sinks to near the bottom of the tank. As the waste water entering the tank 5 flows through the biomass, a portion of the biomass rises with the fluid. This biomass that raises with the fluid has a tendency to rise to different levels within the tank 5 depending upon the type of biomass encountered.
In particular, relatively heavy and larger clumps of biomass are typically formed of certain types of bacteria and protein linkages which tend to stay nearer to the bottom of the tank then to the top. On the other hand there are relatively light micro-organism clumps which have a tendency to be easily floated and will be more likely to be found in the upper portion of the tank 5 during treatment. In accordance with the present invention it is preferable to encourage the growth of the heavier or denser micro-organism clumps that are more likely to be found near the bottom of the tank and which are more easily settled and to discourage the growth of the lighter and easily floatable micro-organism clumps of biomass that are likely to rise within the tank 5. Preferred substrate and biomass profiles are shown in FIGS. 4 and 5.
A major reason for preferring to have the larger portion of the biomass near the bottom of the tank 5 is that the biomass then settles quickly at the end of treatment during a settling cycle so that a substantial period of time is not required to settle the biomass. Furthermore, if there is little biomass within the upper region of the tank 5 at the time treatment is stopped, often decanting or removal of the treated waste water from near the top of the tank 5 can be initiated through the collection conduit 30 prior to complete settlement of the biomass in the lower regions of the tank 5. This substantially reduces the cycle time on each batch treatment by the apparatus 1.
Consequently, during a complete treatment cycle, the waste water coming in to the apparatus 1 is flowed through the apertures 24 into the tank 5 near the bottom 11 thereof and rises in substantially a plug flow pattern upwardly through the tank. Plug flow without substantial mixing is highly preferred in the present invention as this prevents short cutting or incomplete decomposition of impurities in the waste water within the system. That is, if certain portions of the fluid flow sideways or at an angle with respect to verticle, fluid with a high percentage of substrate may inappropriately mix with fluid having a low percentage of substrate so that there is not a uniform pattern of substrate within the fluid at different vertical levels within the fluid in the tank 5.
In accordance with the invention it is highly preferred that the largest concentrations of substrate or food for the biomass be located in the levels of fluid that are closest to the entry of the fluid into the tank, that is at the apertures 24. This is seen in FIG. 4 which is a chart showing a preferred concentration of substrate over the height of the liquid layer between the distribution manifold 21 and the collection manifold 30. The purpose of increasing the amount of substrate at the lower end of the liquid 14 within the tank 5 is to encourage the growth of biomass near the lower end of the fluid 14 and to discourage the growth of the light biomass near the upper end thereof. In this manner likewise the denser and more enlarged clumps of biomass are encouraged to grow and the lighter and smaller clumps of biomass are discouraged from growth. The chart shown in FIG. 5 illustrates the biomass profile over the height of the tank 5. Consequently, it is preferred to have the heaviest substrate and heaviest biomass near the lower end of the tank and the lightest biomass and lightest substrate concentration near the upper end of the liquid.
During treatment, liquid may be withdrawn from near the upper end of the flush level 14 through the collection manifold 30 and through the pump 31 so as to be distributed back into the distribution manifold with the valve 48 open and the valve 46 closed. In this manner fluid 14 that needs somewhat further treatment can be recycled in the same manner as discussed for incoming fluid so as to likewise encourage the biomass growth discussed above. In general fluid flow in, fluid flow out and combined fluid flow in and out to produce recycle are all plug flows.
It is possible to operate the process utilizing the apparatus 1 at psychrophilic temperatures, mesophilic temperatures, or thermophilic temperatures. If the system is operated in the mesophilic or thermophilic temperature ranges, normally some type of heating mechanism must be utilized to provide heat to the liquid within the reactor or tank 5. This can be accomplished by providing exchange of heat between influent and effluent in a heat exchanger and heating the recycling fluid by a heat exchanger (not shown) located external to the tank or by within the tank 5.
It is to be understood that while certain forms of the present invention have been illustrated and described herein, it is not to be limited to the specific forms or arrangement of parts described and shown. | A method for providing a uniform plug flow through an anaerobic wastewater treatment reactor includes distributing incoming wastewater generally evenly near the bottom of reactor and evenly collecting the wastewater near an upper level thereof so as to produce upward plug flow through the reactor during filling, recycle and decanting and minimize horizontal mixing. Such plug flow encourages growth of heavier biomass near the bottom of the reactor where substrate is greatest and discourages growth of light biomass near the top of the reactor where substrate is least. Wastewater is also preferably recycled from the top to the bottom of the reactor. Apparatus is provided to be used in conjunction with the method. The apparatus is also usable in conjunction with a subsequent aerobic sequencing batch reactor. | 2 |
BACKGROUND OF THE INVENTION
The invention is directed to a versatile, easily operated machine supported on wheels for movement along a row of tobacco plants to cut the plants and convey them without injury to a position on the machine where they may be loaded onto a lath shuttle assembly for drying. The cutting and conveying assembly prevents injury to the leaves of the plants and the bowed construction of the lath shuttle assembly and location of the rear wheels prevents injury to the leaves of the plants as they are conveyed rearwardly.
SUMMARY OF THE INVENTION
The invention is directed to a machine for harvesting tobacco which has a frame supported on wheels driven by a gasoline engine along a row of tobacco plants. The machine has a hydraulic system operated by the engine which actuates a hydraulic motor which drives the rear wheels of the machine. The engine also drives a second hydraulic motor which rotates a pair of cutters at the front of the machine located adjacent the seat for the driver of the harvester. A third hydraulic motor actuated by the engine drives a set of three conveyors which receives the cut tobacco plants and transports them rearwardly of the machine. To prevent injury to the plants, the conveyors are in the form of a trough with a generally large central conveyor and smaller side conveyors located on an upward slant relative to the central conveyor and which are driven at a faster speed than the central conveyor.
The rear portion of the machine is provided with a lath shuttle assembly consisting of a pulley and bracket arrangement in which a lath is manually loaded with the tobacco plants, is placed in the bracket and then pushed rearwardly for unloading. This simultaneously moves another lath forwardly to receive freshly cut tobacco plants. The supporting members of the shuttle are bowed so that the laths can pass without injurying the leaves of the tobacco loaded onto one of the laths.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational view of the tobacco harvesting machine with parts in section;
FIG. 2 is a top plan view of the machine of FIG. 1 with parts in section;
FIG. 3 is a detail view illustrating the drive of the cutters at the forward end of the machine;
FIG. 4 is a schematic view illustrating the universal joint for the drive of the rollers of the side conveyors and the hydraulic motor for driving the conveyors with the side rollers projected outwardly of their normal position to better illustrate the universal joints;
FIG. 5 is a detail enlarged side view illustrating the lath loading bracket of the assembly;
FIG. 6 is a detail view illustrating the drive of the central conveyor; and
FIG. 7 is a diagrammatic view of the network of the hydraulic system.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the drawings, there is shown in FIGS. 1 and 2 a machine for harvesting tobacco which has the frame 1 supported on the front wheels 2 and rear wheels 3 for movement along a row of tobacco plants.
The rear wheels 3 are located laterally inwardly of the front wheels and driven from a hydraulic system actuated by a gasoline engine 4 located above the rear wheels 2. A seat 5 is secured to the forward end of the frame 1 upon which the driver of the machine sits and controls the direction of travel of the front wheels 2 by the steering wheel 6. Frame 1 also supports a central platform 7 for workers who receive the cut tobacco plants and load them to the rear of the central platform, and a platform 8 at the rear of frame 1 also supports another worker for unloading the plants from the machine.
The machine has a self-contained hydraulic system which as illustrated in FIG. 6 consists of a pump 9 driven by engine 4, control valves 10 and 11, a hydraulic oil reservoir 12, flow control valves 13 and 14, a first hydraulic motor 15 to drive rear wheels 3 from engine 4, a second hydraulic motor 16 to drive the cutters 17 at the front of the machine, hydraulic motor 18 to drive a wide central conveyor 19 and side conveyors 20 located at the forward end of the machine and the requisite tubing for carrying the hydraulic fluid to the various components of the system.
The hydraulic system is actuated by the operator through control valves 10 and 11 which open and close passages in the piping system to control the flow of hydraulic fluid through the system. The right-hand control valve 10 controls flow of fluid to hydraulic motor 15 to drive rear wheels 3. The left-hand control valve 11 controls the flow of fluid to hydraulic motor 15 to rotate cutters 17 and to hydraulic motor 18 to drive the central conveyor 19 and side conveyors 20. The fluid in the system is metered through the flow control valve 13 to control the ground speed of the machine and through control valve 14 to control the speed of cutters 17 and the respective conveyors 19 and 20.
The cutters 17 located at the forward end of the machine in a low horizontal plane just above ground level are offset from the center of the machine so that they will move into contact with the tobacco plants to be cut which are located to one side of the machine, in this case the right side.
FIG. 3 illustrates the drive of the cutters 17 which are of disc shape and provided with a plurality of sharp knifelike edges 21. As shown in FIGS. 2 and 3, cutters 17 overlap slightly at their inner portions as they rotate. Cutters 17 are independently driven from hydraulic motor 16 through a sprocket and chain train consisting of a drive chain 22 encircling a sprocket driven by motor 16 and engaging large sprocket 23 rotatably connected to frame 1 and secured to the small sprocket 23a to drive the latter and which is connected to the small sprocket 24 by chain 25 secured to one of the cutters 17 rotated from sprocket 23a through chain 25. Drive chain 22 also drives large sprocket 26 rotatably connected to frame 1 and secured to the small sprocket 26a to drive the latter and which is connected to the small sprocket 27 secured to the other cutter 17 by the chain 28 which then rotates that cutter 17 from sprocket 26a. The described sprocket and chain arrangement prevents clogging of the chains with plants, dirt and other foreign material. In addition wiper blades 29 are affixed to frame 1 and overlie cutters 17 to wipe off accumulation of dirt and foreign matter between cutters 17 and their respective drive gears 24 and 27 as cutters 17 rotate.
As the tobacco plants are cut they are conveyed upwardly by the conveyor assembly.
The conveyor assembly has a central conveyor 19 with a wide reach and two side conveyors 20 having reaches of considerably lesser width. Side conveyors 20 slant downwardly to the central conveyor 19 and slightly overlap the latter to form a trough-like conveyor assembly and at the lower end the reach of conveyors 20 extend a considerable distance forwardly of central conveyor 19 over cutters 17.
The side conveyors 20 at the lower ends of each reach encircle an angularly located idler roller 30 which rotates on a shaft affixed to bracket 31 which is secured to the forward end portion of frame 1. At the upper end the reach of one side conveyor 20 encircles the roller 32 from which the side conveyor is driven and the reach of the other side conveyor 20 encircles the roller 33 from which it is driven. Rollers 32 and 33 are supported on brackets 34 which are connected to frame 1.
An idler roller 35 as shown in FIG. 2 is rotatably connected to frame 1 at the lower end of central conveyor 19 and is encircled by the reach of conveyor 19.
At the upper end of the conveyors the reach of central conveyor 19 passes over roller 36 and encircles the elongated driving roll 37, both of which are located inside of conveyor frame 38 and longitudinally spaced from each other.
The rollers 36 and 37 are rotated from sprocket 39 which is driven by the hydraulic motor 18 through a chain 40. Sprocket 39 and motor 18 are located outside of conveyor frame 38 and are secured to frame 1 by the brace 41. The drive chain 40 initially extends around gear 42 for driving the shaft of roller 36 and then extends rearwardly to encircle sprocket 43 for driving the shaft of roller 37 and then returns to sprocket 39 on hydraulic motor 18. The reach of central conveyor 19 is driven by rollers 36 and 37 as it passes over them and is changed from an upward extent to a horizontal extent as it passes over the forward roller 36. Motor 18 and sprocket 39 which is supported from frame 1 by brace 41 thus rotates chain 40 and rollers 36 and 37 through their respective sprockets 42 and 43 as the latter are driven by chain 40.
The respective rollers 32 and 33 which side conveyors 20 encircle are located at an angle with respect to the reach of central conveyor 19 and are each connected to shafts 44 of rollers 32 and 33 by a universal joint 45 so that they can be driven from shafts 44.
It has been found that in order to properly orient and carry the leaves of the tobacco plants upwardly without injury by the respective conveyors for discharge rearwardly it is necessary to have the side conveyors 20 travel at a greater speed than central conveyor 19.
There are several ways this can be accomplished but the best mode contemplated by the inventor and carried out successfully is to construct the side rollers 32 and 33 of side conveyors 20 of a greater diameter than the rollers 36 and 37 of central conveyor 19. For example, satisfactory results have been obtained when the rollers 32 and 33 have been six inches in diameter and rollers 36 and 37 only four inches in diameter.
The tobacco plants are discharged off the rear end of middle conveyor 19 as that conveyor extends a greater distance rearwardly than side conveyor 20. Normally they are caught by workmen as they come off the conveyors.
Above the location of the engine 4 and to the rear of the machine thereof is located a shuttle drying assembly. This assembly is supported from frame 1 of the machine by the horizontally spaced posts 46 and the cross bar 47. A cradle 48 is supported above posts 46 and cross bar 47 in which are located the sticks or lath 49 upon which tobacco plants 50 are assembled as can be seen in FIG. 1.
Two sets of the drying shuttle assembly units are shown in the drawings so that two workmen can load tobacco plants 50 for drying as they come off the conveyors. Only one set will be described as both operate in the same manner.
The shuttle employed on the machine has two angular shaped tracks 51 which extend rearwardly from posts 46 and cross bar 47 and are supported therefrom. The two tracks 51 are laterally spaced from each other and both are outwardly bowed as illustrated in FIG. 2 to increase the space between them.
A bracket 52 is hung from each track 51 and rides on tracks 51 on upper and lower rollers 53. In addition a central roller 54 engages the wall of each track 51 to prevent the brackets from swinging sidewise.
A pulley 55 is located at the rear of the tracks 51 and a smaller pulley 56 at the forward end of tracks 51 and the pulleys are encircled by the cable 57. As illustrated in FIG. 2, the bracket 52 there shown at the rear of the shuttle is connected to cable 57 as at 58. At the forward end of the shuttle the forward bracket 52 as seen in FIG. 2 is connected to cable 57 as at 59. The connection 59 is illustrated in phantom in FIG. 5. A stop 60 is provided at the forward end of the shuttle for engagement with one of the brackets 52 in a forward position and similarly a stop 61 is provided at the rear end of the shuttle for engagement with one of the brackets 52 when in the rearward position.
The tobacco plants 50 are hung on the laths 49 to be supported for drying which are flat and a removable steel spear is placed on the forward end of each lath by a workman for insertion through the stalk of plant 50 when the latter is loaded onto the lath 49 as illustrated in FIG. 1 which shows a number of plants 50 assembled on a lath.
A lath 49 is manually loaded onto the bracket 52 at the rear of the machine by sliding one end of lath 49 between the offset ears 62 which are secured to the side of each bracket 52 until the lath engages stop 63 also secured to each bracket 52 at the rear. When the lath 62 is loaded into the rearmost bracket 52, the foremost bracket 52 supports a lath 49 which protrudes forwardly while being loaded by the workman with tobacco plants 50. This is accomplished by piercing the end of the stalk of the plant with the spear at the forward end of the lath and then forcing plant 50 rearwardly over lath 62. When the forward lath 49 is loaded with plants 50, the workman pushes it rearwardly and this automatically brings the rear bracket 52 attached to cable 57 forwardly with an unloaded lath 49 to the loading position. Thus when the lath 49 is being loaded with plants 50 at the forward position a workman standing on rear platform 8 is loading a lath 49 into the ears 62 of bracket 52 at the rear of the machine.
The bowed construction of the tracks 51 of the shuttle eliminates any contact by the leaves of plant 50 with the adjacent lath 49 and bracket 52 being moved forwardly on the other side of the shuttle. This also positions the point of each lath 49 at substantially the same forward position for loading of plants 50.
In addition, by locating the rear wheels 3 inwardly of the front wheels 2 as previously described, the rear wheels 3 are removed from beneath the tobacco plants 50 and the plants can then ride to the rear of the machine free of wheels 3.
The process is repeated with the brackets 52 carrying laths 49 shuttling back and forth on tracks 51.
The tobacco harvester of the invention is readily operated and is efficient in cutting tobacco plants and loading to the rear of the machine without injury to the leaves of the plant where they are hung to be removed for drying.
Various modes of carrying out the invention are contemplated as being within the scope of the following claims particularly pointing out and distinctly claiming the subject matter which is regarded as the invention. | A tobacco harvester consisting of a mobile machine having a frame on wheels and which at the forward end supports rotary overlapping cutters adjacent the ground for cutting tobacco plants which are then deposited in a trough-like conveyor system consisting of a central conveyor and slanted side conveyors which are driven at a faster speed than the central conveyor to eliminate injury to the plants. The machine, cutters and conveyors are hydraulic driven from separate hydraulic motors actuated by a gasoline engine. The cut tobacco plants are carried rearwardly by the conveyor and manually hung individually on a lath which is located in a supporting shuttle assembly of bowed construction and then pushed rearwardly which brings forward another lath ready to be loaded with newly cut tobacco plants. Because of the bowed construction of the shuttle the laths pass without injuring the tobacco leaves. | 0 |
PRIORITY
[0001] The present application claims priority from a U.S. provisional application filed on Nov. 3, 2008 titled “Efficient Energy and Sulfur Recovery With Novel Isothermal Thermal Flame Reactor” and assigned U.S. Provisional Application Ser. No. 61/110,709; the entire contents of which are incorporated herein by reference.
PUBLISHED WORKS
[0002] The present application is directed to subject matter described in Sassi, M. and Gupta, A. K.: Sulfur Recovery from Acid Gases using the Claus Process and High Temperature Air Combustion (HiTAC) Technology, American Journal of Environmental Sciences, vol. 4, no. 5, 2008, pp. 502-511; the entire contents of which are incorporated herein by reference.
[0003] The present application is also directed to subject matter described in Selim, H., Gupta, A. K., and Sassi, M.: Acid Gas Composition Effects on the Optimum Temperature in Claus Reactor, 6 th International Energy Conversion Engineering Conference (IECEC), Jul. 28-30, 2008, Cleveland, Ohio, published by the American Institute of Aeronautics and Astronautics, Inc.; the entire contents of which are incorporated herein by reference.
TECHNICAL FIELD
[0004] The present disclosure relates to a method and system for enhanced recovery of sulfur in a thermal stage process with simultaneous energy recovery and elimination of unwanted pollutants, such as sulfur dioxide. The controlled thermal stage causes the hydrogen sulfide to break up into sulfur dioxide which further reacts with hydrogen sulfide to form molten sulfur. The method and system result in much higher sulfur recovery in the thermal stage of the reactor than that possible in the thermal stage of currently used Claus process. The process can be used for the removal and clean conversion of any compound that decomposes in thermal environment and requires controlled thermo-chemical parameters for enhanced recovery and performance.
BACKGROUND
[0005] Sulfur-bearing compounds are very detrimental to the environment and to to industrial process equipment. They are often obtained or formed as a by-product of separation and thermal processing of fuels containing sulfur, such as coal, crude oil and natural gas. The two sulfur compounds, which need special attention, are: hydrogen sulfide (H 2 S) and sulfur dioxide (SO 2 ). H 2 S is a highly corrosive gas with a foul smell.
[0006] Hydrogen sulfide is present in numerous gaseous waste streams from natural gas plants, oil refineries, wastewater treatment, among other processes. These streams usually also contain carbon dioxide, water-vapor, trace quantities of hydrocarbons, sulfur and ammonia. Waste gases with ammonia are called sour gases, while those without ammonia are called acid gases. Sulfur must be recovered from these waste streams before flaring them.
[0007] SO 2 is a toxic gas responsible for acid rain formation and equipment corrosion. Various methods of reducing pollutants containing sulfur are described herein below, with a focus on the Claus process. The Claus process has been known and used in the industry for over 100 years. It involves thermal oxidation of hydrogen sulfide and its reaction with sulfur dioxide to form elemental sulfur and water vapor. The Claus process is equilibrium-limited and usually achieves efficiencies in the range of 94-97%, which have been regarded as acceptable in the past years. Nowadays strict air pollution regulations regarding hydrogen sulfide and sulfur dioxide emissions call for nearly 100% efficiency, which can only be achieved with process modifications.
[0008] Sulfur recovery from sour or acid gas typically involves application of the Claus process using the reaction between hydrogen sulfide and sulfur dioxide (produced in the Claus process furnace from the combustion of H 2 S with air and/or oxygen) yielding elemental sulfur and water vapor:
[0000] 2H 2 S(g)+SO 2 (g)->(3 /n )S n (g)+2H 2 O(g)
[0000] with
[0000] ΔH r =−108 kJ moL −1
[0009] Therefore, higher conversions for this exothermic, equilibrium-limited reaction call for low temperatures which lead to low reaction rates, imposing the use of a catalyst. The catalytic conversion is usually carried out in a multi-stage fixed-bed adsorptive reactors process, to counteract the severe equilibrium limitations at high conversions. This technology process can possibly provide about 96-97% conversion of the influent sulfur in H 2 S to S. However, higher removal requires critical examination of the process and use of near isothermal reactor since the conversion is critically dependent upon exothermic and endothermic conditions of the reactions. Flameless combustion has been shown to provide uniform thermal field in the reactor so that the reactor temperature is near uniform. In addition it has been shown to result in compact size of the reactor, reduce combustion generated pollutants emission up to 50% and increase energy efficiency up to 30%. The application of this technology appears to offer great advantages for the process under consideration.
[0010] The adoption and further development of flameless combustion technology for sulfur recovery among other commercial and industrial heating processes is expected to be very crucial and beneficial, both economically and environmentally.
[0011] The conventional sulfur recovery process is based upon the withdrawal of sulfur by in-situ condensation within the reactor. The selective removal of water should, however, be a far more effective technique as its effect on the equilibrium composition in the mass action equation is much greater. The in-situ combination of the heterogeneously catalyzed Claus reaction and an adsorptive water separation seems especially promising, as both reaction and adsorption exhibit similar kinetics and pressure can be adapted to the needs of the adsorptive separation. Such an adsorptive reactor will lead to almost complete conversion as long as the adsorption capacity is not exhausted. There are numerous possibilities for implementing these two functionalities, ranging from fixed-beds with homogeneous catalyst/adsorbent mixtures to spatially structured distributions or even fluidized beds.
[0012] For the sulfur recovery process most of the previous studies have concentrated on the Claus catalytic conversion reactors and the Tail Gas Treatment Unit (TGTU). However, some previous studies have identified the Claus furnace as one of the most important yet least understood parts of the modified Claus process. The furnace is where the combustion reaction occurs with major initial sulfur conversion (through an endothermic gaseous reaction) takes place. Any SO 2 remaining is converted in the downstream catalytic stages. The contaminants (such as ammonia and BTX (benzene, toluene, xylene) are supposedly destroyed. The main two reactions in the Claus furnace are:
[0000] H 2 S+ 3/2O 2 →SO 2 +H 2 O (1)
[0000] with
[0000] ΔH r =−518 kJ moL −1
[0000] 2H 2 S+SO 2 → 3/2S 2 +2H 2 O (2)
[0000] with
[0000] ΔH r =+47 kJ moL −1
[0013] This last endothermic reaction is responsible for up to about 67% conversion of the sulfur at about 1200° C. Moreover, many side reactions take place in the furnace, which reduce sulfur recovery and/or produce unwanted components that end up as ambient pollutant emissions. Therefore, it would be useful to combine the endothermic and exothermic process using an isothermal reactor offered by the colorless (or flameless) oxidation combustion according to the present disclosure as described in the Detailed Description below.
[0014] A vast majority (about 92%) of the 8 million metric tons of sulfur produced in the United States in 2005 was recovered from industrial by-products using the Claus process. However, the traditional Claus process does face limitations and various process improvements have been investigated in order to satisfy the increasingly stringent emission regulations and the need to process gas streams and fuels with higher sulfur content. New technologies have to be developed in order to achieve near 100% removal of sulfur compounds from industrial flue gases.
[0015] A discussion follows regarding traditional sulfur recovery processes for understanding the Claus process.
[0016] The three main steps of sulfur recovery from sour gas are the following:
[0017] 1. Amine Extraction: Gas containing H 2 S is passed through an absorber containing an amine solution (Monoethanolamine (MEA), Diethanolamine (DEA), Methyldiethanolamine (MDEA), Diisopropylamine (DIPA), or Diglycolamine (DGA)), where the hydrogen sulfide is absorbed along with carbon dioxide. A typical amine gas treating process includes an absorber unit and a regenerator unit as well as accessory equipment. In the absorber, the down-flowing amine solution absorbs H 2 S and CO 2 (referred to as acid gases) from the up-flowing sour gas to produce a sweetened gas stream (i.e., an H 2 S-free gas) as a product and an amine solution rich in the absorbed acid gases. The resultant “rich” amine is then routed into the regenerator (a stripper with a re-boiler) to produce regenerated or lean amine that is recycled for reuse in the absorber. The stripped overhead gas from the regenerator is concentrated H 2 S and CO 2 . The extracted mixture of H 2 S and CO 2 , referred to as an acid gas, is passed into the Claus unit for sulfur recovery. The process is also known as Gas sweetening and Acid gas removal. Amines are also used in many oil refineries to remove acid gases from liquid hydrocarbons such as Liquefied Petroleum Gas (LPG).
[0018] 2. Claus Thermal Stage: H 2 S is partially oxidized with air (one-third of H 2 S is converted into SO 2 ) in the Claus furnace. The acid gas/air mixture is passed into a furnace operating at temperatures from 1300-1700 K, where the reactions are allowed sufficient time to reach equilibrium. The products from this step are: sulfur dioxide, water and unreacted hydrogen sulfide. Additionally some of the sulfur dioxide produced here reacts with hydrogen sulfide inside the furnace to produce sulfur according to reactions (1) and (2) shown above. The furnace products flow then into a waste heat boiler to condense the sulfur and produce high pressure steam for the Claus catalytic stages (see FIG. 6 ).
[0019] Depending on the calorific value of the acid gas, various methods of stable burning are achieved. If very lean acid gases are involved (low calorific value) then auxiliary fuel, oxygen enrichment or a by-pass stream has to be used. The H 2 S-content and the concentration of other combustible components (hydrocarbons or ammonia) determine the location where the feed gas is burned. Claus gases (acid gas) with no further combustible contents apart from H 2 S are burned in lances surrounding a central muffle. Gases containing ammonia, such as the gas from the refinery's Sour Water Stripper (SWS) or hydrocarbons are converted in the burner muffle.
[0020] 3. Claus Catalytic Stage: The remaining H 2 S, from the Claus furnace, is reacted with the SO 2 at lower temperatures (about 470-620 K) over an alumina- or titanium dioxide-based catalyst to make more sulfur:
[0000] 2H 2 S+SO 2 →⅜S 8 +2H 2 O (3)
[0000] ΔH r =−108 kJ moL −1
[0021] On average, about 70% of H 2 S and SO 2 will react via reaction (3). Note that in the catalytic stage mostly S 8 is produced, which is an exothermic reaction whereas in the thermal stage S 2 is the major product and the reaction is endothermic. Other allotropes of sulfur may also be present in smaller quantities.
[0022] The overall reaction for the entire process is:
[0000] 3H 2 S+1.50 2 →3 /n S n +3H 2 O (4)
[0000] ΔH r =−6268 kJ moL −1
[0023] Reactions (1) and (3) are exothermic and a cooling stage is needed following these steps in order to condense the sulfur produced. The condensed phase is then separated from the gas stream by draining it into a container. An interesting property of liquid sulfur is its increase in viscosity with temperature. This is due to polymerization of sulfur at around 430 K. Therefore, the temperature of condensed sulfur should be closely monitored to prevent polymerization and clogging of pipes used in the process. Care must also be taken in order not to pass condensed sulfur through the catalyst, which would become fouled and inefficient. Liquid sulfur adsorbs to the pores and deactivates the catalytic surface. Therefore, reheat stages using the previously generated steam are needed in order to keep the sulfur in gas phase while in the catalytic stage. Several methods of reheating used in industry are:
[0024] 1. Hot-Gas Bypass: involves mixing the two process gas streams from the process gas cooler (cold gas) and the bypass (hot gas) from the first pass of the waste heat boiler.
[0025] 2. Indirect Steam Reheaters: the gas can also be heated with high pressure steam in a heat exchanger.
[0026] 3. Gas/Gas Exchangers: whereby the cooled gas from the process gas cooler is indirectly heated from the hot gas coming out of an upstream catalytic reactor in a gas-to-gas exchanger.
[0027] 4. Direct-fired Heaters: fired reheaters utilizing acid gas or fuel gas, which is burned sub-stoichiometrically to avoid oxygen breakthrough and damage to Claus catalyst.
[0028] A typical Claus process involves one thermal stage followed by multiple catalytic stages in series to maximize efficiency. The need for multiple catalytic stages increases complexity and cost. Therefore, various methods of minimizing these steps in the process have been proposed.
[0029] A schematic of the process flow diagram along with approximate gas temperatures is shown in FIG. 1 . The flow diagram includes a burner 10 , furnace 12 , boiler 14 , condensers 16 a , 16 b , re-heater 18 , and catalytic stage 20 . During operation, high-pressure steam (40 atm) is generated in the boiler 14 and low-pressure steam (3-4 atm) is produced in the condensers 16 a and 16 b . A total of two to four catalytic stages 20 are typically used in order to maximize efficiency. The tail gas 22 is either routed to a clean-up unit or to a thermal oxidizer to incinerate the remaining sulfur compounds into SO 2 . Where an incineration or tail-gas treatment unit (TGTU) is added downstream of the Claus plant, only two catalytic stages are usually installed. Before storage and downstream processing, liquid sulfur streams from the process gas cooler, the sulfur condensers and from the final sulfur separator are routed to the degassing unit, where the gases (primarily H 2 S) dissolved in the sulfur are removed. Over 2.6 tons of steam will be generated for each ton of sulfur yield.
[0030] The Claus process is equilibrium-limited. In the furnace stage the SO 2 produced from the combustion process (reaction 1) recombines with H 2 S in an endothermic reaction to form S 2 (reaction 2). Adequate residence time has to be provided in order to allow this reaction, responsible for 60-74% of sulfur conversion, to reach equilibrium. Since the main Claus reaction 3 is exothermic, this stage calls for the use of low temperatures in order to shift the equilibrium constant towards higher product yields. The low temperatures, however, lead to decreased reaction rates, hence the need for a catalyst. The law of mass action for the Claus reaction is as follows:
[0000]
K
p
(
T
)
=
p
H
2
O
2
p
s
8
3
/
8
p
H
2
S
2
p
SO
2
(
5
)
[0031] Where, K P (T) is the chemical equilibrium constant and P H20 , P S8 are partial pressures of the products and P H2S >P SO2 and partial pressures of the reactants.
[0032] This equation illustrates the nature of equilibrium limitations involved in the Claus process; decreasing the process temperature can increase the equilibrium constant and thus increase conversion, but the lower limit of this temperature and hence the upper is limit of equilibrium conversion is set by the condensation temperature of sulfur. A typical arrangement for the Claus sulfur recovery process is shown in FIG. 2 .
[0033] Improvements on Claus Process: The traditional Claus process has been a reliable and relatively efficient way of removing hydrogen sulfide from the flue gas and converting it into elemental sulfur. It has, however, faced some shortcomings and limitations. Increasingly stringent air pollution regulations from oil, gas and chemical processing facilities combined with the fact that lower-grade, higher sulfur-content fuels will have to be used in the near future, call for improved efficiency of the process.
[0034] Eisner, et al. (M. P. Elsner, M. Menge, C. and Müller, D. W. Agar “The Claus Process: Teaching an Old Dog New Tricks” Catalysis Today 79-80 (2003) pp. 487-494) proposed an adsorptive water separation process applied in the catalytic reactor stage. Taking advantage of Le Chatelier's principle, this process removes H 2 O (one of the products) from the reaction, shifting equilibrium towards higher conversion (Equation (5)). An adsorptive reactor of this type could produce complete conversion in a single catalytic stage.
[0035] The Zeolite adsorbent beads saturate with water after a certain time and therefore need to be regenerated. This calls for a cyclic process where the flow of gas is reversed and hot gas is used to vaporize the adsorbed water off of the surface of Zeolite spheres and remove them from the reactor. The process can then be reversed again to regenerate the second adsorptive reactor ( FIG. 3 ).
[0036] FIG. 3 shows that 100% conversion can be achieved in the reactor for a longer time than in a conventional Claus reactor with no water adsorption. The decline in conversion efficiency after a period of about 1.3 hrs is due to the fact that the Zeolite spheres are saturated with steam and they need to be regenerated. It was also found that as a side effect of the water adsorption, the chemisorption of S0 2 on the surface of the alumina catalyst occurs.
[0037] A Cold Bed Adsorption (CBA) process, also known as the sub-dew point process developed by the Amoco Corporation has been shown to produce efficiencies in the range of 97.5-99.5%. In the CBA process the heterogeneous catalytic reaction is allowed to take place at low temperatures (below sulfur dew point), thus increasing equilibrium conversion. Additionally since the Claus reaction occurs in the gas phase, this liquid sulfur does not inhibit the reaction like sulfur vapor does, effectively removing one of the reaction products to result in a favorable shift in the reaction equilibrium and higher sulfur conversion. The condensed phase is then periodically desorbed from the catalytic surface by flowing hot gas through the unit to vaporize the condensate, thus regenerating the reactor. Therefore, this process is inherently a cyclic one.
[0038] There are normally two or more CBA reactors in series so that at least one can be operating sub-dew point while the other is being regenerated. Due to the cyclic nature of the CBA process, the CBA switching valves are subjected to very demanding sulfur vapor service that has caused significant operation and maintenance problems in many of the CBA plants.
[0039] Sulfur recoveries in excess of 99.5% have been achieved with the Modified Claus process with tail gas cleanup developed by Ortloff (“Modified Claus Process With Tail Gas Cleanup” http://www.ortloff.com/sulfur/claus-tailgas.htm). In this process the sulfur-bearing compounds (COS, CS 2 , SO 2 , SO 2 , S n ) in the tail gas are converted to H 2 S using hydrolysis and hydrogenation and recycled back into the Claus unit. Amine-based tail-gas cleanup is also used to recover the remaining hydrogen sulfide in the tail gas.
[0040] The Modified Claus Process with Tail Gas Cleanup Unit (TGCU) is used when very high sulfur recovery is necessary, such as for sulfur plants in petroleum refineries in the U.S. The U.S. EPA regulations normally require that the incinerated effluent from refinery sulfur plants contain no more than 250 ppmv SO 2 on a dry, oxygen-free basis. This usually corresponds to an overall sulfur recovery of 99.8-99.9%. The problem with any TGCU is that it usually costs as much as the whole Claus plant while it adds only about 2% in the total sulfur recovery. Lagas, et al. (J. A. Lagas, J. Borsboom, and G. Heijkoop “Claus Process Gets Extra Boost” Hydrocarbon Processing, April 1989: pp. 40-42) describe a selective oxidation process, in which the tail gas is selectively oxidized in the presence of active metal oxides to produce sulfur and small quantities of SO 2 . Total sulfur recovery of 99% has been achieved this way (99.4% with an additional hydrogenation step).
[0041] Oxygen enrichment technologies have been proposed to increase sulfur recovery, throughput of the system and decrease the size of the unit by reducing the amount of inert nitrogen from the process. The resultant high flame temperatures have to be dealt with using techniques such as staged combustion and water spraying because of material limitations. The increased complexity of the system is offset by the fact that better mixing, higher reaction rates, conversion and throughput for a given size of the unit are achieved.
[0042] FIG. 4 suggests that it is desirable to remove water from the reaction furnace during the process. As water is one of the products of the reaction, its removal will lead to the shift in equilibrium towards the product side and hence more conversion is achieved.
[0043] The removal of nitrogen and introduction of oxygen into the process has many effects. First, removal of the diluent nitrogen results in the increased partial pressure of each of the reacting species; second, the reduced volume of reacting gases is easier to mix; and, third, higher temperatures can be obtained. All three resulting in increases in the process rate ( FIG. 5 ).
[0044] The use of a gas recycling process has been proposed by the CNG group. The effluent gas from the first condenser was recycled back into the burner to attain overall sulfur recovery of 100%. However, intermediate stages had to be used to remove water vapor and nitrogen from the recycled gas to achieve efficient conversion and stable flame regime. A separator membrane can typically be used to separate nitrogen out of the stream. However, if pure oxygen is used in the combustion process, the membrane is not necessary and only water condensation is needed before the tail gas can be recycled back into the unit.
[0045] The heat recovery for this process is increased, since the water condensation heat can also be extracted out of the stream. In a recent work, El-Bishtawi, et al. (R. El-Bishtawi, and N. Haimour “Claus Recycle with Double Combustion Process” Fuel Processing Technology 86, pp. 245-260, 2004) describes a Claus recycle with double combustion process. The acid gas was partially combusted in the first furnace and the hot exhaust was passed into the second furnace where the remainder of oxygen was added to complete the reaction. The second furnace operated at a high temperature air combustion regime, since the inlet gas was above its auto-ignition temperature.
[0046] One sulfur condenser was used following the two furnaces. Part of the effluent gas was recycled back into the first furnace. It was reported that 100% conversion could be achieved without the use of catalytic reactors and with only one condenser. Such an arrangement should reduce the cost and complexity of the system by removing the catalytic stages. It was also found that the oxygen content should not exceed 78% in order not to exceed the maximum temperature limitations of the equipment materials.
SUMMARY
[0047] The present disclosure provides a method and system for recovering sulfur in a thermal stage process. In particular, the present disclosure relates to a method and system for enhanced recovery of sulfur in a thermal stage process with simultaneous energy recovery and elimination of unwanted pollutants, such as sulfur dioxide. The controlled thermal stage causes the hydrogen sulfide to break up into sulfur dioxide which further reacts with hydrogen sulfide to form molten sulfur. The method and system result in much higher sulfur recovery in the thermal stage of the reactor than that possible in the thermal stage of currently used Claus process. The process can be used for the removal and clean conversion of any compound that decomposes in thermal environment and requires controlled thermo-chemical parameters for enhanced recovery and performance.
[0048] The improved Claus process according to the present disclosure involves using high temperature air combustion technology (HiTAC) or otherwise called colorless (or flameless) combustion for application in Claus furnaces, especially those employing lean acid gas streams that contain large amounts of inert gas streams (such as nitrogen and CO 2 ) and which cannot be burned without the use of auxiliary fuel or oxygen enrichment under standard conditions. With the use of HiTAC, diluted H 2 S gas streams (less than 15% H 2 S), Low Calorific Value (LCV) fuels can be burned with very uniform thermal fields without the need for fuel enrichment or oxygen addition. The uniform temperature distribution favors clean and efficient burning with an additional advantage of significant reduction of NO x , CO and hydrocarbon emission.
[0049] The present disclosure further describes many different embodiments for a Claus reactor configured and designed for performing the improved Claus process according to the present disclosure.
[0050] These and other advantages and inventive concepts are described herein with reference to the drawings and the detailed description which follows.
BRIEF DESCRIPTION OF THE DRAWINGS
[0051] FIG. 1 illustrates a flow diagram of a prior art Claus process;
[0052] FIG. 2 illustrates a prior art arrangement of a Claus unit;
[0053] FIG. 3 illustrates a graph of hydrogen sulfide conversion as a function of time;
[0054] FIG. 4 illustrates a graph of calculated hydrogen sulfide conversion as a function of reactor temperature for different oxygen concentrations;
[0055] FIG. 5 illustrates a graph of calculated concentrations of sulfur species as a function of temperature;
[0056] FIG. 6 illustrates a diagram of a Claus system with high temperature air combustion according to the present disclosure;
[0057] FIG. 7 illustrates a flameless Claus reactor having a flame zone that covers almost the entire area of the combustion chamber;
[0058] FIG. 8 illustrates a prior art Claus reactor having a flame zone that covers only a reduced area of the combustion chamber;
[0059] FIG. 9 illustrates an embodiment or configuration of a Claus reactor using HiTAC technology in accordance with the present disclosure;
[0060] FIGS. 10 a - 10 c illustrate three different geometries for an interior of an input port of the Claus reactor taken along line A-A shown by FIG. 9 ; and
[0061] FIGS. 11-23 illustrate additional embodiments or configurations of a Claus reactor using HiTAC technology in accordance with the present disclosure.
DETAILED DESCRIPTION
[0062] Improvements on the Claus process in accordance with the present disclosure will now be described. In particular, a description is provided in Section I below directed to the use of HiTAC technology as a reliable and cost-effective alternative for improvement of concentrated or diluted acid gas treatment in the Claus process according to the present disclosure. The colorless or flameless (super-adiabatic) combustion according to the present disclosure is also described for processing acid-rich gas. Conclusions are presented in Section II.
I. Claus Process with HiTAC
[0063] In the case of diluted acid gas feeds (<15% H 2 S) (or concentrated H 2 S gas streams) special considerations have to be taken in order to maintain a stable flame in the burner and achieve good combustion efficiency. Common approaches include: oxygen enrichment, a split-flow process and use of auxiliary fuel. In the case of oxygen enrichment the flame temperature is increased by removing part or all of inert nitrogen from air, thus decreasing the thermal loading of the system. In the split-flow process part of the acid gas is allowed to bypass the burner, which leaves adequate fuel/air proportions in the burner and higher flame temperature. The by-pass flow is then reintroduced into the furnace at a later stage in order to keep the H 2 S:SO 2 ratio 2:1 (Eq. 2 and 3) to maintain an overall equivalence ratio of 3. Change in the distribution of equivalence ratio in the combustion chamber can significantly reduce the efficiency. For example, at an equivalence ratio of 2, the sulfur capture efficiency is reduced to about 55%. With the use of auxiliary fuel the calorific value of the gas is increased. Stable flame of a higher temperature is therefore possible.
[0064] Paskall (Paskall H. G., 1979, Capability of the modified Claus process. Western Research, Alberta, Canada) collected a substantial amount of field data and reviewed the literature data on sulfur conversion in Claus furnaces and recommended that sulfur conversions are greater in furnaces that are designed for greater gas mixing and turbulence and equipped with burners that provide for good mixing of the feed gas and oxidizer and in furnaces of smaller volume. HiTAC or flameless or colorless combustion furnaces can achieve all of these recommendations and beyond, providing the highest sulfur recovery. Furthermore, Khudenko et al. (B. M. Khudenko, G. M. Gitman, and T. E. P. Wechsler “Oxygen Based Claus Process for Recovery of Sulfur from H 2 S Gases” Journal of Environmental Engineering, November/December 1993, pp. 1233-1251) through several thermodynamic and process simulation scenarios showed that a dual thermal stage system with cold products recycle (very similar to flameless concept) provides the greatest capacity reserve. They claimed that, with the dual stage system, no changes in the existing process train are required, even when the throughput capacity of the existing conventional system is more than doubled.
[0065] Economically this is very wise and attractive for increasing sour gas production in the oil and gas industry due to the exploitation of aging reservoirs. A reciprocal flow filtration combustor with embedded heat exchangers for super-adiabatic combustion has been proposed and studied by the Gas Technology Institute (GTI) and the University of Illinois at Chicago (Fabiano Contarin, William M. Barcellos, Alexi V. Saveliev, and A. Lawrence Kennedy, “Energy Extraction from a Porous Media Reciprocal Flow Burner With Embedded Heat Exchangers”, Journal of Heat Transfer, February 2005, Volume 127, Issue 2, pp. 123-130). The motion of the flame zone to the downstream of the reactant gas mixture results in positive enthalpy flux to the cold gas and thus increasing the reactant temperature prior to combustion. This is similar to the principles of HiTAC.
[0066] A prototype was build and tested for sulfur recovery at GTI. The results showed that the super-adiabatic combustion (which is very similar to flameless or colorless combustion in principle, but taking place in a non-catalytic porous medium) significantly extends conventional flammability limits to the region of the ultra-low heat content mixtures (such as lean acid gas) and features ultra low emissions for NO x and CO.
[0067] Therefore, High Temperature Air Combustion (HiTAC) technology according to the present disclosure is an alternative treatment of lean to very diluted (<15% H 2 S) Low Calorific Value (LCV) acid gases at very high sulfur recovery (about 74% in the thermal stage). This will reduce the number of expensive catalytic stages. While a stable conventional flame is usually not achievable in this regime, HiTAC provides very lean homogeneous thermal field uniformity flames. Moreover, uniform thermal characteristics with high and uniform heat flux distribution in the combustion chamber are achievable for high yield of sulfur with no release of sulfur dioxide to the environment. This results in high overall yield of sulfur (about 74% in the thermal stage) during the thermal stage conversion, low emissions of sulfur dioxide gas and other pollutants (such as oxides of nitrogen, carbon monoxide and black carbon) from the thermal process.
[0068] The process also reduces mechanical stresses associated with the more conventional high temperature combustion process that results in high temperature fluctuations and hot spot zones with maximum and minimum temperatures. Uniform thermal field in the process is especially useful to reduce NOx emissions by avoiding the “hot spots” zones in the flames that are responsible for thermal NOx formation and cause excessive noise. With the improved process the need for by-pass feed stream, oxygen enrichment and multiple furnaces can be eliminated as the lean acid gas could be oxidized in a single furnace operating above the auto-ignition temperature of the mixture, with good conversion efficiency.
[0069] In fact, it has been reported that HiTAC technology has shown significant reduction in pollutants emissions (about 50%), reduction in the size of the combustion chamber (about 25%), reduced thermal losses to the environment and significant energy savings (about 30%). High temperature air combustion is especially useful for reducing NO x emissions due to its uniform thermal field and overall lower operating temperature and no adiabatic flame with hot spots that are responsible for thermal NO x formation. With the use of HiTAC the need for by-pass feed stream, oxygen enrichment and multiple furnaces could be eliminated as the lean acid gas could be oxidized in a single furnace operating above the auto-ignition temperature, with good conversion.
[0070] As far as practical considerations are concerned, the Claus process is well suited for the use of HiTAC technology. A novel flameless Claus reactor using HiTAC technology in accordance with the present disclosure is shown by FIG. 6 and designated generally by reference numeral 60 . As high pressure (HP) steam 62 is generated in a waste heat boiler 64 as well as in the condensers 66 a , 66 b , 66 c , it is readily available to preheat the incoming air stream 68 in a heat exchanger 70 . The incoming air stream 68 is heated in the heat exchanger 70 by the incoming high pressure steam 62 to generate hot air 72 . The hot air 72 is introduced, along with the acid gas 74 , to an efficient burner 76 . The burner 76 provides for good mixing of the feed gas 74 and oxidizer (hot air) 72 . Water 65 is used to cool the waste heat boiler 64 .
[0071] The byproducts of the burner 76 are then directed to a furnace 78 where the colorless (or flameless) oxidation combustion reaction and the initial sulfur conversion (through an endothermic gaseous reaction) take place and also where the SO 2 required by the downstream catalytic stages 80 is produced. The catalytic stages 80 produce low pressure steam 82 and tail gas 84 , as well as provide for the recovery of sulfur 86 . This Claus reactor is characterized as a flameless thermal Claus reactor since this controlled HiTAC condition provides an invisible flame in the thermal reactor.
[0072] As shown by the illustration of FIG. 7 , the flameless Claus reactor 60 has a flame zone 40 that covers almost the entire area of the combustion chamber 42 . As a result, approximately all the sulfur-containing compounds 44 (i.e., H 2 S) entering the combustion chamber 42 via input port 46 are incinerated, thereby having a greater elemental sulfur and sulfur dioxide recovery yield than prior art Claus reactors. These substances exit or exhaust from the combustion chamber 42 via an exhaust/heat exchanger unit 48 . Unit 48 eliminates unwanted gases and also preheats the oxidizer before it is routed to input port 46 .
[0073] In contrast, in a prior art non-flameless Claus reactor (see FIG. 8 ), the flame zone 50 covers only a reduced area of the combustion chamber 52 . As a result, not all of the sulfur-containing compounds 54 (i.e., H 2 S) which entered the reactor via input port 45 are incinerated. This is depicted by the H 2 S sulfur-containing compound 54 being outside the flame zone 50 in FIG. 8 . This sulfur-containing compound 54 exits the reactor through an exhaust pipe 56 .
[0074] In High Temperature Air Combustion, the air is brought to above the auto-ignition temperature of the fuel to obtain uniform ignition and combustion characteristics across the reactor. The reported auto-ignition temperature of hydrogen sulfide (563 K or 290° C.) is lower than a typical auto-ignition temperature for hydrocarbon fuels (400-600° C.) and therefore requires less energy extraction from the high-pressure steam to achieve ignition and sustained combustion. During the transient start-up period, preheating with an electrical heater or auxiliary fuel can be used after which self-sustained operation at steady-state conditions can be maintained. Issues of air/fuel mixing, flame characteristics, such as temperature, size and flammability limits, that are relevant for the Claus process, must first be investigated. The resultant uniform thermal field in the flameless combustor plus gas recycling is expected to produce close to 100% conversion.
[0075] For rich acid gas oxidation, flammability limits and flame stability are not an issue due to the high calorific value of the gas. However, thermal field uniformity offered by flameless or colorless combustion would always promote better conversion and lower pollutant emissions, among other benefits as mentioned above. Furthermore the super-adiabatic flame studies, discussed earlier, featured that fuel rich (much more than stoichiometric H 2 S to oxygen ratio) conditions promote H 2 S conversion to H 2 and S 2 rather than H 2 O and SO 2 . Their numerical results showed that at a super-adiabatic temperature of about 1650K and an equivalence ratio of about 10, an overall H 2 S conversion of 50% resulted with an H 2 /H 2 O selectivity of 57/43 and an S 2 /SO 2 selectivity of 99/1. These conditions, with even higher temperature, would be easily attained under flameless combustion with H 2 S recycling and pre-heating. This flameless combustion assisted-thermal decomposition of H 2 S would then eliminate any catalytic stage use and produce hydrogen which is highly needed in fuel processing and power production.
[0076] The thermal decomposition of H 2 S is a well researched route for the production of hydrogen and Cox et al. (Cox B. G., Clarke P. F. and Pruden B. B., 1998, Economics of thermal dissociations of H 2 S to produce hydrogen, Int. J. Hydrogen Energy, Vol. 23, No. 7, pp. 531-544) presented a study on the economics of thermal dissociation of H 2 S to produce hydrogen and some studies are even at the pilot plant stage. However, none of the early studies address the problem of heat transfer. Due to the endothermic heat of reaction, heat transfer limits the overall rate of reaction resulting in low conversions. However, with flameless or colorless combustion the H 2 S rich mixture reacts in a very hot homogeneous medium with no heat transfer limitations and therefore will present much higher conversions.
[0077] A description will now be provided with reference to FIGS. 9 and 11 - 23 which illustrate different embodiments or configurations of a flameless Claus reactor using HiTAC technology in accordance with the present disclosure. It is contemplated that these embodiments can be used for other chemical reactions besides performing the chemical reactions (1) and (2) associated with a Claus reactor. In each embodiment, the exhaust port also includes a heat exchanger for pre-heating the oxidizer before it is routed to one or more input ports.
[0078] FIG. 9 illustrates an embodiment of a Claus reactor 90 having four input ports 92 a - d for introducing a mixture of hydrogen sulfide and a preheated oxidizer 94 within a combustion chamber 96 of the reactor 90 . The oxidizer is heated by directing it in close proximity to a heat exchanger 98 which absorbs heat exiting from the exhaust 100 . The preheated oxidizer 94 and the hydrogen sulfide gas chemically react forming an H 2 S/oxidizer flamelet 102 for each input port 92 . The flamelets 102 incinerate the hydrogen sulfide gas within a uniform thermal (flameless) combustion zone 104 .
[0079] The Claus reactor 90 enables the combustion of hydrogen sulfide while simultaneously recovering sulfur and thermal energy at higher efficiency than prior art Claus reactors.
[0080] FIGS. 10 a - 10 c illustrate three different geometries for an interior 106 of the input ports 92 a - d of the Claus reactor 90 taken along line shown by FIG. 9 . The geometry of the input port 92 determines the direction(s) of the internal flow pattern 106 as shown by FIGS. 10 a - 10 c . Other factors that can be used to affect the direction(s) of the internal flow pattern is the location of an input port(s) for introducing an oxidizer fluid with respect to the location of an input port(s) for introducing hydrogen sulfide (see, e.g., FIGS. 11-18 ); velocity of the fluids introduced into the combustion chamber 96 ; the combustibility of the fluids; temperature within the combustion chamber 96 ; premixing the hydrogen sulfide with other fluids, such as nitrogen and/or carbon dioxide; and by controlling the amount of oxidizer introduced into the combustion chamber 96 via an air introduction system.
[0081] The reactor 90 and the other novel reactors described herein with respect to FIGS. 6 , 7 and 11 - 23 include one or more control modules 97 for controlling one or more of these factors which in turn controls the internal flow pattern, mixing and thermal field uniformity, and hence the amount of sulfur recovered and the amount of thermal energy. For example, it is desired for the temperature within the combustion chamber 96 to be less than 25K for optimum sulfur recovery.
[0082] FIG. 10 a illustrates the input port 92 having two side ports 110 a and 110 b for directing hydrogen sulfide gas to the combustion chamber 96 , and one, unobstructed main port 110 c for directing a preheated oxidizer to the combustion chamber 96 for mixing with and reacting with the hydrogen sulfide gas. The hydrogen sulfide gas and the preheated oxidizer are injected perpendicular to each other forming an internal flow pattern 106 in one direction.
[0083] The internal flow pattern 106 in the configurations shown by FIGS. 10-10 c , as well as FIGS. 11-18 , operates as an induced jet pump which causes significant recirculation of the oxidizer prior to chemical reaction of the reactants. This recirculation of the reactants maximizes the amount of sulfur recovered. The internal flow pattern can include swirl motion 108 ( FIGS. 10 b and 10 c ) by obstructing the main port 100 c with a divergent conical body 112 ( FIG. 10 b ) or a convergent conical body 114 ( FIG. 10 c ). The swirl motion 108 produces desired thermal characteristics within the reactor 90 , such as a uniform and defined thermal set point, and an increase in the amount of thermal energy generated. The internal flow pattern can also include other types of motion, including spiral motion as shown by FIGS. 11-18 .
[0084] FIG. 11 illustrates an embodiment of a Claus reactor 200 having two separate input ports 202 , 204 on the same side of the reactor 200 . One input port 202 is used for introducing an oxidizer into a combustion chamber 206 . The other input port 204 is used for introducing hydrogen sulfide into the Claus reactor 200 . The two reactant fluids intermix at an opposite end 208 of the reactor 200 forming a uniform thermal distribution flow pattern 210 . The pattern 210 is formed in a central area of the combustion chamber 206 as shown by FIG. 11 . An output port 212 is provided for the exhaust fluids to exit or exhaust from the combustion chamber 206 .
[0085] FIG. 12 illustrates an embodiment of a Claus reactor 300 similar to the embodiment shown by FIG. 11 . The Claus reactor 300 has two separate input ports 302 , 304 on the same side of the reactor 300 . One input port 302 is used for introducing a hydrogen sulfide-oxidizer mixture into a combustion chamber 306 . The other input port 304 is used for also introducing a hydrogen sulfide-oxidizer mixture into the Claus reactor 300 . The hydrogen sulfide and the oxidizer are premixed. The two reactant fluids intermix at an opposite end 308 of the reactor 300 forming a uniform thermal distribution flow pattern 310 . The pattern 310 occupies almost entirely the interior area of the combustion chamber 306 as shown by FIG. 12 . An output port 312 is provided for the exhaust fluids to exit the combustion chamber 306 .
[0086] FIG. 13 illustrates an embodiment of a Claus reactor 300 designated by reference numeral 400 . The Claus reactor 400 has a plurality of input ports 402 located on three sides of the reactor 400 . Each input port 402 is used for introducing a hydrogen sulfide-oxidizer mixture into a combustion chamber 406 . The hydrogen sulfide and the oxidizer are premixed. The two reactant fluids intermix within the combustion chamber 406 forming a uniform thermal distribution flow pattern 410 . The pattern 410 occupies almost entirely the interior area of the combustion chamber 406 as shown by FIG. 13 . An output port 412 is provided for the exhaust fluids to exit the combustion chamber 406 .
[0087] FIG. 14 illustrates an embodiment of a Claus reactor 500 similar to the embodiments shown by FIGS. 11 and 12 . The Claus reactor 500 has two separate input ports 502 , 504 on the same side of the reactor 500 . One input port 502 is used for introducing an oxidizer into a combustion chamber 506 . The other input port 504 is used for introducing hydrogen sulfide into the Claus reactor 500 . The two reactant fluids intermix in a central area of the reactor 500 forming a uniform thermal distribution flow pattern 510 . The pattern 510 occupies a central area of the combustion chamber 506 as shown by FIG. 14 . An output port 512 is provided for the exhaust fluids to exit the combustion chamber 506 . The flow pattern 510 is facilitated by the positioning of two triangular bodies 514 in proximity to the output port 512 . A side of each triangular body 514 elongates the length of the output port 512 to an area within the combustion chamber 506 so that the H 2 S gas stream is not directed with the exhaust fluids to the output port 512 .
[0088] FIG. 15 illustrates an embodiment of a Claus reactor 600 having two separate input ports 602 , 604 on the same side of the reactor 600 for introducing hydrogen sulfide into a combustion chamber 606 . The reactor 600 also includes two separate input ports 614 , 616 on an opposite side from the input ports 602 , 604 for introducing an oxidizer into the combustion chamber 606 . The reactant fluids intermix throughout a central area of the reactor 600 forming a uniform thermal distribution flow pattern 610 . The pattern 610 is formed in the central area of the combustion chamber 606 as shown by FIG. 15 . Two output ports 612 are provided on opposite ends of the reactor 600 for the exhaust fluids to exit the combustion chamber 606 .
[0089] FIG. 16 illustrates an embodiment of a Claus reactor 700 having two separate input ports 702 , 704 on the same side of the reactor 700 and positioned at an angle of approximately 45 degrees from a horizontal axis of the reactor 700 . One input port 702 is used for introducing an oxidizer into a combustion chamber 706 . The other input port 704 is used for introducing hydrogen sulfide into the Claus reactor 700 . The two reactant fluids intermix at a central area of the combustion chamber 706 forming a uniform thermal distribution flow pattern 710 . The pattern 710 is formed in a central area of the combustion chamber 706 as shown by FIG. 16 . An output port 712 is provided for the exhaust fluids to exit the combustion chamber 706 at an end opposite the end where the input ports 702 , 704 are located.
[0090] FIG. 17 illustrates an embodiment of a Claus reactor 800 having three separate input ports 802 , 804 , 808 . Two of the input ports 802 , 804 are located on two different sides opposite from each other, and one input port 808 is located at a third side. The input port 808 is used for introducing an oxidizer into a combustion chamber 806 . The other input ports 802 , 804 are used for introducing hydrogen sulfide into the Claus reactor 800 . The two reactant fluids intermix towards the right region of the reactor 800 forming a uniform thermal distribution flow pattern 810 as shown by FIG. 17 . An output port 812 is provided for the exhaust fluids to exit the combustion chamber 806 . It is contemplated that obstructing bodies are placed in proximity to the input ports 802 , 804 within the combustion chamber 806 for obstructing the flow of the incoming fluids and force them to be directed towards a desired direction and/or create an incoming flow pattern.
[0091] FIG. 18 illustrates an embodiment of a Claus reactor 900 having two separate input ports 902 , 904 on opposite sides of the reactor 900 . One input port 902 is used for introducing an oxidizer into a combustion chamber 906 from a top-left area of the combustion chamber 906 . The other input port 904 is used for introducing hydrogen sulfide into the Claus reactor 900 from a bottom-right area of the combustion chamber 906 . The two reactant fluids intermix forming a uniform thermal distribution flow pattern 910 . The pattern 910 is formed in a central to high region of the combustion chamber 906 as shown by FIG. 18 . An output port 912 is provided for the exhaust fluids to exit the combustion chamber 906 . A separating wall 914 is also included to separate the area of the combustion chamber 906 where intermixing between the reactants occurs and an area of the combustion chamber 906 where no intermixing occurs. Obstructing bodies 916 are placed within the combustion chamber 906 so that the H 2 S gas stream is not directed with the exhaust fluids to the output port 912 .
[0092] FIG. 19 illustrates an embodiment of a Claus reactor 1000 similar to the embodiment shown by FIG. 14 . The Claus reactor 1000 includes two separate input ports 1002 , 1004 located on the same side of the Claus reactor 1000 . One input port 1002 is used for introducing an oxidizer into a combustion chamber 1006 . The other input port 1004 is used for introducing hydrogen sulfide into the combustion chamber 1006 . The two reactant fluids intermix in a central area of the reactor 1000 forming a uniform thermal distribution flow pattern 1010 . The pattern 1010 occupies a central area of the combustion chamber 1006 as shown by FIG. 19 . An output port 1012 is provided for the exhaust fluids to exit the combustion chamber 1006 . The flow pattern 1010 is facilitated by the positioning of two concave bodies 1014 in proximity to the output port 1012 . A side of each concave body 1014 elongates the length of the output port 1012 to an area within the combustion chamber 1006 and also causes the oxidizer and the hydrogen sulfide to be directed towards the input ports 1002 , 1004 .
[0093] FIG. 20 illustrates an embodiment of a Claus reactor 1100 having seven separate input ports 1002 a - d , 1004 a - c located on two different sides of the Claus reactor 1100 . Input ports 1002 a - d are used for introducing an oxidizer into a combustion chamber 1106 . The other input ports 1004 a - c are used for introducing hydrogen sulfide into the combustion chamber 1106 . The two reactant fluids intermix in a central area of the reactor 1100 forming a uniform thermal distribution flow pattern 1110 . The pattern 1110 occupies a central area of the combustion chamber 1106 as shown by FIG. 20 . Two output ports 1012 a - b are provided for the exhaust fluids to exit the combustion chamber 1106 .
[0094] FIG. 21 illustrates an embodiment of a Claus reactor 1200 having four separate input ports 1202 a - d located on one side of the Claus reactor 1200 for introducing an oxidizer into a combustion chamber 1206 . There is also one other input port 1204 located on an opposite side of the Claus reactor 1200 for introducing hydrogen sulfide into the combustion chamber 1206 via six sub-input ports 1206 . The two reactant fluids intermix in a central area of the reactor 1200 forming two uniform thermal distribution flow patterns 1210 a - b . The patterns 1210 a - b occupy a top and bottom central area of the combustion chamber 1206 as shown by FIG. 21 . Two output ports 1212 a - b are provided for the exhaust fluids to exit the combustion chamber 1206 .
[0095] FIG. 22 illustrates an embodiment of a Claus reactor 1300 having three separate input ports 1302 a - c located on one side of the Claus reactor 1300 for introducing an oxidizer into a combustion chamber 1306 . There is also one other input port 1304 located on a side perpendicular to the one side of the Claus reactor 1300 for introducing hydrogen sulfide into the combustion chamber 1306 via six sub-input ports 1306 . The two reactant fluids intermix in a central area of the reactor 1300 forming a uniform thermal distribution flow pattern 1310 . The pattern 1300 occupies a central area of the combustion chamber 1306 as shown by FIG. 22 . Two output ports 1312 a - b are provided for the exhaust fluids to exit the combustion chamber 1306 .
[0096] FIG. 23 illustrates an embodiment of a Claus reactor 1400 having three separate input ports 1402 , 1404 a - b located on one side of the Claus reactor 1400 for introducing an oxidizer into a combustion chamber 1406 via input port 1402 and hydrogen sulfide via input ports 1404 a - b . There are twelve sub-input ports 1408 for input port 1402 and six sub-input ports 1409 for each of input port 1404 a - b . The two reactant fluids intermix in a central area of the reactor 1400 forming a uniform thermal distribution flow pattern 1410 . The pattern 1400 occupies a central area of the combustion chamber 1406 as shown by FIG. 23 . Two output ports 1412 a - b are provided on opposite sides from each other for the exhaust fluids to exit the combustion chamber 1406 .
[0097] It can be seen from the embodiments described above that the uniform thermal distribution flow patterns can be formed based on the number of input ports for the oxidizer and for the hydrogen sulfide, and/or the interior design of the combustion chamber. Accordingly, the uniform thermal distribution flow pattern(s) for a Claus reactor according to the present disclosure can be controlled based on the design of the flameless Claus reactor.
II. Conclusions
[0098] A new sulfur recovery process from acid gases is described above and claimed below that provides much higher efficiency than the more commonly used Claus flame thermal reactor. The conventional and modified Claus process and its derivatives have been presented and discussed, each with distinct advantages. It is shown that any improvements towards high sulfur recovery cause very high cost additions to an already economically deficient process.
[0099] The Claus reactor according to the present disclosure features greater yield of sulfur and chemical energy without any environmental impact. The lean acid gases provide complete sulfur recovery from more conventional stream while controlled well mixed advanced Claus reactor provides high yield of sulfur recovery under conditions of fuel-rich acid gas composition. Therefore, the technology according to the present disclosure features a new way for the efficient low cost removal of chemically bound sulfur in the gas to sulfur and chemical energy, thus reducing the complexity and the cost of the more traditional Claus sulfur recovery process.
[0100] The described embodiments of the present disclosure are intended to be illustrative rather than restrictive, and are not intended to represent every embodiment of the present disclosure. Various modifications and variations can be made without departing from the spirit or scope of the disclosure as set forth in the following claims both literally and in equivalents recognized in law. | A method and system are presented for the combustion of hydrogen sulfide mixed with other gases for simultaneous recovery of sulfur and energy from hydrogen sulfide at higher efficiency. The amounts and velocity of the hydrogen sulfide into the reactor is selected in such a way that it is not possible to burn the hydrogen sulfide in a normal thin reaction zone during its combustion that normally prevails in almost all flame combustion devices. The injected hydrogen sulfide gas is mixed in a thermal reactor with fresh air and hot active combustion gases in the reactor on account of internal jet pump effect and self-induced entrainment. The reaction is exothermic so that the chemical energy present in hydrogen sulfide is recovered together with the sulfur that is tapped off from he process. The reactor process can also be used for other gas and chemicals that require controlled reactor thermo-chemical environment. Various reactors are shown capable of controlling the formation of a thermal distribution flow pattern based on the position and position and direction (and other factors) regarding fluid introduction within a combustion chamber of the reactors. | 2 |
FIELD OF THE INVENTION
This invention relates to thermoplastic film bags, such as undershirt type grocery bags or the like. In particular, it provides a bag closure.
BACKGROUND OF THE INVENTION
Plastic bags are steadily gaining acceptance where consumer goods of all types must be bundled up for transport away from the point of sale. These bags are used in many different types of retail settings to include grocery stores, department stores of all types, building supply stores and any other setting where a lightweight, strong, easy to dispense bag, is required. The advantages of plastic bags over kraft paper bags are numerous. They are lighter in weight, take up less room when folded, resist water, and may be fabricated with integral handles that provide for easy transport of the loaded bag. They are reusable as trash can liners or can be reused to carry other items. Thermoplastic bags are also recyclable.
One disadvantage of plastic bags is their lack of inherent rigidity and ease of closure. The result of this disadvantage is seen in the grocery bag application where it is not unusual for a fully loaded bag to be placed on a consumer's vehicle seat just before leaving with the purchase. As the vehicle turns, the bags typically fall over spilling their contents. The consumer is then faced with the time-consuming and inconvenient task of packing the bag a second time before it can be removed from the vehicle.
There are several disclosures relating to providing a closure for plastic bags or flexible bags of some type. One group of such disclosures addresses the problem by providing a separate closure means or device to secure the bag. U.S. Pat. No. 3,820,200 to Myers discloses a bag closure comprising a flat disc of resilient material provided with an I-shaped slit therein. The end of the bag to be closed is drawn through the slit which grips the bag tightly, achieving closure.
A similar approach is shown in U.S. Pat. No. 4,174,554 to Flantua which discloses a closure having a base portion and a tongue portion. This device is wrapped around the bunched together bag sides which are trapped between the base and tongue portions. Closure is achieved by pulling the tongue portion through an opening in the base portion and lockingly engaging neck areas of the tongue portion in corresponding areas of the tongue portion. Both these devices suffer the disadvantage of requiring the user to bear the expense and keep track of a number of small, easily lost pieces. Further, it is possible that during use sharp edges on these items could damage the bag precluding reuse of the bag. An additional disadvantage is that once the fully loaded bag has been picked up, the closure device could become very tightly jammed into place and, thus, very difficult to remove.
Another approach for providing a bag closure is disclosed in U.S. Pat. No. 3,186,626 to Shvetz, the invention of which employs tie-strip portions created by perforations formed into the top of the bag. When the perforated areas are pulled two tie-straps are separated from the bag and can be tied together to provide closure. The major disadvantage of this method is that the resulting knot is extremely difficult to loosen. The forces generated when a knotted plastic bag is picked up close the knot so tightly that destruction of the bag may be required in order to gain access to the contents.
This disadvantage is shared by the closure of U.S. Pat. No. 5,044,775 to Rutledge which utilizes plastic film tie elements which are welded to the end portion and adjacent to the top of the bag. When engaged, the tie element of that invention creates a tightly bunched neck area held secure by the tie element. Again, once this closure is engaged on a fully loaded bag, it is extremely difficult to disengage the closure without possibly damaging the bag.
U.S. Pat. No. 3,865,303 to Korn also discloses a pair of tieing strips anchored at one end of the bag described therein. The free ends of the tieing strips are insertable through openings provided in the bag walls. After insertion through the openings the strips are pulled to effect a constriction of the mouth of the bag and the free ends of the strips are tied together. Once any fully loaded bag, particularly a plastic bag, has been closed using a knot in the bag material, the resulting knot can be difficult, if not impossible, to open without rendering the bag unusable. Thus the ability to reuse the bag is lost.
U.S. Pat. No. 4,273,174 to Potter discloses a handbag having two integral strap-loops. The strap-loops can be folded one atop the other to effect a loose closure to the bag. Such an approach is not acceptable for loaded plastic bags because when similarly constructed handles of those bags are so engaged, the contents of the bag will spill out when the bag is tipped over.
As can be seen, the many attempts to provide a bag closure have disadvantages that render the bag difficult to open after closure, may damage the bag during opening after closure, or may require the extra cost and effort of a separate closure device. The present invention represents a significant advance because it avoids those disadvantages, providing a closure that is easy to use, secure and easy to reopen after closure permitting reuse of the bag. Moreover, for bags suspended from a bag dispensing rack, the strap of the present invention provides a convenient means to pull the lead bag open for loading.
It is also possible to use the bag of the present invention in a bag dispensing system utilizing a pack of unitized bags. U.S. Pat. Nos. 5,183,158 to Boyd et al. and 4,989,732 to Smith, the contents of which are incorporated herein by reference in their entirety, describe a pack of unitized bags which are releasably connected such that when one bag is pulled from the dispensing rack after loading, the next bag in the pack is pulled open. That releasable connection can also be achieved using the easy-open bag pack, method of forming and system disclosed in U.S. Pat. No. 5,507,713, the contents of which are incorporated herein by reference in their entirety. That application discloses a bag pack made up of bags that have been subjected to a corona discharge treatment. The corona treatment is sufficient to cause adjacently facing treated surfaces of adjacent bags within the bag pack to releasably fuse to each other upon a localized application of force using a novel upper and lower anvil means. These and other advantages and features of the invention will be readily apparent to one of ordinary skill in the art upon an examination of the specification and drawings herein.
SUMMARY OF THE INVENTION
In accordance with the present invention, there is provided a closeable thermoplastic bag comprising a front wall, a rear wall, gussetted side walls connecting the front and rear walls; an open mouth defined by the front, rear, and side walls; handles, extending upwardly from either side of the open mouth, the handles being integral extensions of the walls and having an inside edge and an outside edge; a strap having a first end and a second end attached to the front wall at the ends, defining an opening between the strap and the front wall, whereby the handles can be grasped and pulled through the opening so as to close the open mouth securely thereby preventing articles contained within the bag from falling out when the bag is tipped over. The strap is positioned adjacent to the bag mouth so as to open the mouth when the strap is pulled. The ends of the strap form two attachment zones.
Additionally, according to this invention, there is provided a flexible undershirt bag having side walls and open top disposed between spaced handle portions, the handle portions having an inside edge, an outside edge and extending upward from the side walls and having an improved closure comprising a thin flexible closure member attached to the front bag wall and adjacent to the handles forming an opening between the member and the front wall adapted to accommodate a human hand during closure by grasping and pulling the handle portions through the closure member so as to close the open mouth securely, thereby preventing articles contained within the bag from falling out when the bag is tipped over. The strap is positioned adjacent to the mouth so as to open the mouth when the strap is pulled.
The advantages of this invention over other types of bag closures are numerous. The closure member is integral to the bag so that no separate device or piece need be bought or inventoried. The closure also acts as a handle providing an easy means for the bag to be pulled from a unitized bag pack. This bag can be closed with a quick, one-handed operation. The opening between the closure member and the bag wall can be sized to accommodate a large hand, yet still provide ease of operation and secure closure. This invention enables the consumer to reuse bags of all types because the closure can be reopened without damaging the bag. Thus the value of the bag to the consumer is greatly increased.
Therefore, it is an object of this invention to provide a thermoplastic bag which can be closed securely with one hand.
It is another object of this invention to provide a closeable thermoplastic bag which can be easily reopened after closure without damaging the bag.
It is still another object of this invention to provide a thermoplastic bag having a closure member positioned on the front wall of the bag just below the bag mouth.
It is yet another object of this invention to provide a bag that can be closed so that the articles contained therein will not spill out when the bag is tipped over.
Still another object of this invention is to provide a bag having a closure member that can be used as a handle to pull the bag open from a unitized pack of bags.
Other objects and the several advantages of the present invention will become apparent to those skilled in the art upon a reading of the specification and the claims appended thereto. The invention itself, together with further objects and attendant advantages, will best be understood by reference to the following detailed description, taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is an elevation of the bag showing the closure strap positioned just below the mouth of the bag.
FIG. 2. is a side view showing the closure strap being used to pull open a lead bag from a unitized pack of bags.
FIG. 3 is a top view of the bag showing the opening defined by the closure strap and the front wall of the bag.
FIG. 4. is a perspective view showing the user's hand inserted through the opening of FIG. 3 and grasping the bag handles.
FIG. 5 is a perspective view of the bag in the closed condition with the handles pulled through the opening of FIG. 3.
FIG. 6 is an elevation of the closure strap positioned on a very large bag.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a novel bag that can be closed in such a manner that the contents of the bag will not fall out when the bag is tipped over. The bag closure is simple to use requiring only one hand to operate. FIG. 1 is an elevation of the bag 1, also known as undershirt bag, showing the closure strap 2 attached to the front wall 1A of the bag. The closure strap 2 is centered on the front wall 1A of the bag from side to side and is positioned just below the mouth 3 of the bag. The importance of the distance between the top edge of the strap and the mouth of the bag is discussed further herein. Although a strap is shown and discussed herein, it to be understood that any thin, substantially flexible member of sufficient strength and configuration to perform as described herein may be used to carry out the present invention. The terms strap or member herein both refer to the same element of this invention.
The bag has two handles 4 which are integral extensions of the front, rear and side walls. Each of the handles has an inside edge 5 and an outside edge 6. The lower end of each inside edge 5 terminates in an arcuate area 7 that functions as a stress relief notch as shown in U.S. Pat. No. Re. 34,019 to Kuklies et al., the disclosure of which is incorporated herein by reference in its entirety. The stress relief notches reduce the tendency of some thermoplastic bags to tear during loading and carrying.
FIG. 1 also shows a triple gusset arrangement whereby the gussetted side walls of the bag are connected to the front bag wall and rear bag wall by two pleats 8. The pleats 9 are about a third of the depth of the gussets 9 in the side walls. This arrangement is used to increase the usable bag volume for a given bag face dimension. The face dimension is the width of the bag in the lay-flat condition. The present invention is also intended to be used with other undershirt bags not having the triple gusset arrangement.
Turning now to FIG. 2, it can be seen that the closure strap 2 can be used to pull open the lead bag 21 in a unitized pack 22 of bags suspended from substantially parallel support rods 23 of the type commonly known in the art. The lead bag 21 is releasably connected to the next bag 24 in the pack. As the loaded lead bag is pulled from the pack the releasable connection serves to open the mouth of the next bag. The positioning of the attachment zones 10 near the bag mouth 3 helps to open the lead bag 21 fully. The closure strap 2 provides a more convenient, easy to grasp means for the user to open the lead bag.
The closure strap 2 can be fabricated from any thin, flexible material. Preferably, it is constructed of polyethylene which is at least 0.0254 mm (1 mil) thick and still more preferably from about 0.0254 (1) to 0.13 mm (5 mils) thick. Though the thickness may vary, desirably it should be thicker than the bag wall material. The strap may be fabricated from any other suitable plastic material that does not stretch excessively when pulled to open a bag pack. Suitable materials include, but are not limited to, linear low density polyethylene, high density polyethylene, and low density polyethylene. The term polyethylene is intended to include both homopolymers of ethylene and also copolymers of ethylene. Generally, the lower the stretch modulus of the strap material the better the performance of the strap.
The physical size of the strap may vary proportionally with the size of the bag on which it is installed. To consider a non-limiting example, for a grocery bag of size about 55.9 cm (22 in) in overall height and about 30.5 cm (12 in) in width, a suitable strap size would be about 20.3 cm (8 in) in width and about 1.91 cm (3/4 in) to about 2.54 cm (1 in) in height. The attachment zones 10 on that size strap should preferably be about 2.03 (0.8) to about 03.05 (1.2) cm (in) wide. As the bag dimensions are changed to meet the needs of each particular use, the strap dimensions may also be varied to provide secure closure. In order to ensure adequate performance of the closure, the combined area of the attachment zones 10 should be about 18% to about 30% of the area of the closure strap 2.
The strap is attached to the bag via two attachment zones 10 located at the ends of the strap. These zones are spaced apart to create a large enough opening 11 as shown in FIG. 3 between the strap 2 and bag front wall 1A so that a user's hand can be inserted through that opening to grasp the handles as shown in FIG. 4. The opening 11 must be large enough to accommodate the user's hand but small enough to hold the bag closed as shown in FIG. 5. Turning now to FIG. 1, it can be seen that the inside edges of the attachment zones 11 are in approximate alignment with the inside edges 5 of the handles. The distance (D) between the inside edges of the attachment zones should be maintained slightly larger than the distance (d) between the inside edges 5 of the handles 4. The overall width of the closure strap 2 will preferably be greater than distance (d) such that the closure strap 2 extends beyond both inside edges 5. The relationship between strap width and bag width can be described by the ratio of the width of the strap to the width of the bag. That ratio should be about 2:3 to about 3:4. Although this closure may be installed on many different types of thermoplastic bags, it is contemplated that the strap will preferably have a width less than that of the bag on which it is installed.
As mentioned earlier the present invention is adaptable to a wide range of sizes of thermoplastic bags. When the bag size increases substantially from that in the embodiment described above, strap positioning criteria do not change but strap sizing criteria may be adjusted. FIG. 6 shows an elevation of a very large bag 12 with the closure strap 2 positioned thereon. By a very large bag it is meant a bag of about 38.1 cm (15 in) to about 45.7 cm (18 in) in width and about 71.1 cm (28 in) to about 81.2 cm (32 in) in overall height. Such a bag can have a distance (d) between handle inside edges 5 of about 25.4 cm (10 in) to about 35.6 cm (14 in). Referring again to FIG. 6 it can be seen that as used on a very large bag, the overall width of the closure strap can be reduced to about the distance (d) between inside handle edges 5. A savings on strap material costs may be achieved since satisfactory closure performance will take place with a less wide strap. In the very large bag application, the attachment zones 10 should comprise the same proportion of the overall strap area as described above.
Attachment of the closure strap 2 to the front wall of the bag is achieved using any method that will produce a bond that has at least as much strength as the bag wall. The bond should be sufficiently strong to prevent delamination of the closure member from the bag wall when the bag is fully loaded and being transported and also when the closure member is used to pull open a lead bag from a unitized pack. One method of attaching the strap to the bag wall is ultrasonic welding. This technique is well known in the art and will not be discussed in detail herein. More preferably the bond is accomplished by using in the attachment zones a pressure sensitive, double-sided adhesive tape. This type of tape is commonly known in the art and can be dispensed, stripped, cut and applied automatically. Still more preferred is the use of an adhesive coating. This adhesive material can be a glue that will produce a bond of the strength described above. The glue can be either acrylic or water-based. A further important characteristic of the glue is that it should not contaminate scrap bag material that is recycled for the manufacture of new bags. Typically scrap material is ground up and added to virgin material as it is fed into the manufacturing apparatus. An unsuitable glue would cause film break in the material used to construct the bag walls resulting in costly waste of material.
It is desirable to provide a means to prevent the closure member 2 from sagging when installed on the bag 1. Accordingly the present invention contemplates the installation of a tacky area 13 as shown on FIG. 1 centered on the surface of the closure member facing the front wall of the bag. A corresponding tacky area is provided on the bag front wall in alignment with the tacky area on the closure member. Mating the two bag components will lightly tack the closure member to the bag thereby preventing sag. This measure also holds the closure member in place until the bag is ready for use. The joining of the closure member to the bag wall is cohesive rather that an adhesive in that the resulting bond will be temporary. It is not intended that this bond have the high adhesive strength of the attachment zones 10. Rather the bond should be sufficient to prevent any sag in the closure member from the time the member is applied to the bag until the time the bag is pulled open for loading. The shape of the tacky areas can be circular, square or some other shape so long as a sufficient amount of cohesive material is applied.
As discussed above, the closure strap should be positioned on the bag wall just below the bag mouth. That positioning is important; because if the handle is positioned too far below the bag mouth, it will be difficult for the user to insert his hand through the opening 11 to grasp the handles 4 as shown in FIG. 4. Moreover, as the strap position is lowered on the bag wall, the forces generated in the attachment zones 10 while carrying a fully loaded bag will be greatly increased thereby raising the likelihood of attachment failure. Strap position has a significant effect on both ease of use and potential closure failure. It has been found that the distance from the top of the strap the to the bag mouth should not be more than about 2.54 cm (1 in).
The closure strap can be installed on any type of thermoplastic bag having handles 4 long enough to achieve closure using the strap and still provide an adequate grip to the user. Handles that are too short may not hold the bag closed securely when the bag is tipped over. The proper functioning of the present invention may require a handle length that is longer than that common in the art. Handle length as referred to herein means the length L, shown in FIG. 1. Preferably the handle length is about 15.2 cm (6 in) to about 20.3 cm (8 in). Particularly preferred is a handle length of about 17.8 cm (7 in). FIG. 4 shows the first of the two steps involved in using the closure of the present invention on a thermoplastic film bag. The user first inserts a hand through the opening 11 from below and grasps both handles 4 firmly. The handles are then pulled down through the opening with the user's hand passing through the opening a second time. The handles are then pulled straight up to a vertical final closure position as shown in FIG. 5. The bag is now ready for pickup and transport away from the point of loading. FIG. 5 further illustrates that the closure strap 2 tensions the handles when the bag is picked up to form a secure closure of the bag mouth 3. The strap is also tensioned when the bag is tipped over so as to prevent the articles contained therein from spilling out. An additional advantage of the present invention is the easy manner in which the closed bag may be reopened for unloading. When the bag is at rest the closure strap relaxes, allowing the handles to be pulled back through the strap with ease. Thus, the bag can be closed securely, reopened and reused without damage to the bag.
Although the present invention has been described with preferred embodiments, it is to be understood that modifications and variations may be utilized without departing from the spirit and scope of this invention, as those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the appended claims. | A grocery bag or the like having a closure member which securely closes the mouth of the bag so as to prevent items contained therein from falling out when the bag is tipped over. Closure is accomplished by a thin flexible strap attached to the front wall of the bag just below the bag mouth defining an opening between the strap and bag wall. The user may close the bag by inserting the hand through the opening defined by the strap and the bag front wall, grasping the bag handles and pulling the handles through the opening. | 1 |
CROSS REFERENCE TO RELATED APPLICATION(S)
[0001] The present application claims priority from U.S. patent application Ser. No. 60/557,768, filed Mar. 30, 2004, entitled “System, Method and Software Arrangement for bi-allele haplotype phasing,” the entire disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a system, method, and software arrangement for determining co-associations of allele types across consecutive genetic loci, permitting the haplotyping of genetic samples at one or more contiguous loci. The system, method, and software arrangement described herein can employ genotype data generated from a wide range of mapping methods to determine chromosomal haplotypes. As such, the system, method, and software arrangement of the present invention may be useful as an aid to the diagnosis and treatment of any disease which has a genetic component.
[0004] 2. Background Information
[0005] Diploid organisms are those whose somatic cells contain two copies of each chromosome. Each of these two copies of a particular chromosome may be distinguished by the presence, within the DNA which comprises the chromosome, of certain genetic variations, which may include restriction fragment length polymorphisms (RFLPs), single nucleotide polymorphisms (SNPs), sequence tag sites (STSs), microinsertions, microdeletions, or variable numbers of tandemly repeated elements (VNTRs). Based on the presence or absence of particular polymorphisms at specific loci, chromosomes may be assigned to one of two “haplotypes,” the name used to refer to the collection of identifiable genetic features present on one of the two haploid chromosomes that are contained within the diploid set. In certain situations, particular haplotypes may be associated with the presence or absence of a particular mutation or other functional variation in specific genetic loci. Because these genetic variations or genotypes may be associated with certain disease states or even with predisposition to disease, determination of relationships between haplotypes and genotypes are of intense interest in genetic research.
[0006] One of the most difficult problems in determining haplotypes in diploid organisms is establishing the proper assignment of multiple polymorphic markers to the same chromosome. Thus, distribution of two different variants (or alleles) at two different genetic loci, for example A/a and B/b, could generate haplotypes AB, Ab, aB or ab depending upon the distribution of the two alleles between the two chromosomes. The problems of inferring diploid haplotypes through the use of population data have been extensively investigated and widely acknowledged. See Clark, 1990, Mol. Biol. Evol. 7:111-122; Excoffier and Slatkin, 1995, Mol. Biol. Evol. 12:921-927; . Ma et al. 2000, Neural Computation 12:2881-2907; Gusfield, 2001, J. Computational Biology 8:305-323; Stephens et al., 2001, Am. J. Hum. Genet. 68:978-989; and Niu et al., 2002, Am. J. Hum. Genet. 70:156-169.
SUMMARY OF THE INVENTION
[0007] The present invention relates to a system, method, and software arrangement for determining co-associations of allele types across consecutive genetic loci, permitting the haplotyping of genetic samples at one or more contiguous loci. The system, method, and software arrangement described herein can employ genotype data generated from a wide range of mapping methods to determine chromosomal haplotypes. According to one exemplary embodiment of the present invention the system, method, and software arrangement for haplotype reconstruction of the instant invention detects polymorphic marker types at one or more contiguous genetic loci and then establishes the maximum likelihood that an arbitrary assignment of polymorphic markers to a particular haplotype adequately account for the particular genotypes observed at any given locus. The system, method, and software arrangement described herein may be useful as an aid to the diagnosis and treatment of any disease that has a genetic component associate therewith.
[0008] In contrast to these previous approaches, the present invention addresses the use of multiple independent mapping techniques (for example, those performed on a collection of large DNA fragments) as a source of the base data used to infer haplotypes. Such single molecule methods and technologies, which include optical mapping and “polony” (See Mitra et al., 1999, “In Situ Localized Amplification and Contact Replication of Many Individual DNA Molecules,” Nucleic Acids Research 27:e34-e34), may permit the application of high-throughput methodologies to the haplotyping of a diploid individual in a population. Moreover, unlike the previous haplotyping approaches described above, the present invention determines the haplotype of an individual without reliance upon the haplotype statistics of the population to which the individual belongs. A further advantage of the instant method is its potential to determine an individual's haplotype with accuracy and resolution far beyond methods based on population studies, both in the worst-case and in the average-case scenarios.
[0009] Thus, in accordance with an exemplary embodiment of the present invention, a system, process and software arrangement are provided for obtaining information associated with a haplotype of one or more genetic samples from genotype data. In particular, the genotype data is received, and polymorphic genetic markers are identified from the genotype data. Further, at least one association of the polymorphic genetic markers across genetic loci (which can be consecutive) may be determined to obtain the information.
[0010] In one further embodiment of the present invention, the genotype data can be obtained from the corresponding one or more genetic samples, the genotype data being contained in at least one dataset. The association can be determined at one or more contiguous loci. The determined association may constitute the haplotype of the one or more genetic samples. The polymorphic genetic markers may be restriction fragment length polymorphisms (“RFLPs”), single nucleotide polymorphisms (“SNPs”), sequence tag sites (“STSs”), insertions, microinsertions, deletions, microdeletions, variable numbers of tandemly repeated elements (“VNTRs”), microsatellites, expanded repeats of variable repeat number, or any combination thereof.
[0011] In still another exemplary embodiment of the present invention, the genotype data can be obtained from single DNA molecules with locations of polymorphic genetic markers. The polymorphic genetic markers are determined using at least one of a Maximum Likelihood Estimator (“MLE”) algorithm and an Expectation Maximization (“EM”) algorithm. The polymorphic genetic markers may be defined as events, and
X ( D ) = { 1 if Φ ^ ( D ) : μ ^ 1 - μ ^ 2 - δ > 0 0 o . w . ,
where {circumflex over (Φ)} (D) denotes the limit of the EM-algorithm with data set D at the loci j.
[0012] For example, the associations of the polymorphic genetic markers across consecutive genetic loci at one or more contiguous loci are determined through the formulation of a maximum likelihood problem. The likelihood function of the maximum likelihood problem can be given by:
L ( θ ) = P ( D | θ ) = Γ ( N ) ∏ ρ ∈ M Γ ( N α p ) ∏ ρ ∈ M θ ρ α p N ,
and the maximum likelihood estimation can include a finding
ρ ε A so that L (ρ)≧ L ω ) ∀ω ε A.
[0013] For a set of genetic loci {j 1 , j 2 , . . . ,j v }, a likelihood function L M[j 1 ,j 2 , . . . j v ] can be defined as that most likely to produce posterior α j 1 , j 2 . . . j v over the space M[j 1 , j 2 , . . . j v ]. The associations of the polymorphic genetic markers across the genetic loci at one or more contiguous loci are determined through maximizing
Π ρε{0,1} M-1 θ ρ α ρ N over θ ε
or minimizing
∑ j ∈ [ 1 … M ] ( α j - θ j ) 2 α j over θ ∈ A .
[0014] The associations of the polymorphic genetic markers at one or more loci, thereby producing a contig, can be determined through an application of a V ERIFY -P HASE function. The V ERIFY -P HASE FUNCTION may determine one or more selected phasing criteria. The phasing criteria may be a statistically-significant rejection of Hardy-Weinberg Equilibrium. The association of the polymorphic genetic markers over the contig can be computed through application of a MLE-C OLLAPSE function. Further, the association of polymorphic genetic markers at one or more contiguous loci, thereby producing a contig, can be determined through an application of a C OMPUTE -P HASE function or a JOIN function.
[0015] According to yet another exemplary embodiment of the present invention, a linear number of the polymorphic genetic markers can be examined. The information associated with the haplotype data may be determined without a need to obtain at least one of first data associated with a pedigree and second data associated with a sub-population of individuals. In addition, further information associated with a confidence level of accuracy of the information can be obtained. A resolution and the further information may be proportional to an amount of effort associated with the determination of the information.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 shows an exemplary collapse of the phase of two polymorphic loci into a single haplotype according to an exemplary embodiment of the present invention.
[0017] FIG. 2 shows an exemplary illustration of the phase of three polymorphic loci provided into two complementary haplotypes in accordance with the exemplary embodiment of the present invention.
[0018] FIG. 3 shows an illustration of exemplary haplotypes determined by application of the system, method and software arrangement according to the exemplary embodiment of the present invention to Dataset I.
[0019] FIG. 4 shows an illustration of exemplary haplotypes determined by application of the system, method and software arrangement according to the exemplary embodiment of the present invention to Dataset II.
[0020] FIG. 5 shows a block diagram of an exemplary embodiment of a system according to the present invention which is capable of storing thereon the storage arrangement of the present invention, and operable to execute thereon the method according to the present invention.
[0021] FIG. 6 shows a flow diagram of a top level of an exemplary embodiment of the method according to the present invention for establishing the haplotype of one or more genetic samples from genotype data obtained from the corresponding one or more genetic samples.
DETAILED DESCRIPTION OF THE INVENTION
[0022] The problem of reconstructing two haplotypes from genotype data generated by general mapping techniques can be considered according to the exemplary embodiment of the present invention, with a focus on single molecule methods. The genotype data is a set of observations D=<d i > iε[1 . . . N] . Each observation is derived from one of the two distinct but unknown haplotypes. Each observation di=<d ij > jε[1 . . . M] is a set of observations over the loci index j with d ij ε R r .
[0023] Mapping processes are subject to noise, for which a Gaussian model d ij ˜N(μ,σ) with parameter μ depending on the underlying haplotype of d i can be assumed. Mapping processes are designed to discriminate the polymorphic allele types in the data space for each locus. Hence, the set of observation points <d ij > iε[1 . . . N] can be derived from a mixed distribution, which may display bimodal characteristics in the presence of a polymorphic feature. By estimating the parameters of the distribution, a posteriori distribution that a particular point in R r may be derived from an allele type can be assigned.
[0024] Since the mapping errors for d ij and d ij , can be assumed to be independent, determining and computing the posteriori distribution for haplotypes with product allele types is likely straightforward, and is one of the advantages of utilizing single molecule methods in association studies.
[0025] One of the problems of phasing is to determine which haplotypes are most likely to account for the observed genotype data. It is preferable to establish the phase by inferring the most likely parameter correlations across the loci index accounting for the posteriori distribution.
[0000] Mapping Techniques
[0026] The system, method and software arrangement according to an exemplary embodiment of the present invention is applicable to datasets generated by a wide spectrum of mapping techniques. In this manner, a large number of polymorphic markers of different types (e.g. SNPs, RFLPs, micro-insertions and deletions, satellite copy numbers) can be used in an association procedure in accordance with the present invention. An exemplary embodiment of system, method and software arrangement presented herein can utilize mapping techniques capable of a) discriminating alleles at polymorphic loci, and b) providing haplotype data at multiple loci. Other known polymorphic genetic markers may be used by the system, method, and software arrangement according to the present invention.
[0027] A mapping technique designed for association studies should preferably be discriminating. In particular, for each polymorphic loci, data points in the data space R r which are derived from separate allele types should preferably form distinct clusters in the data. One of the exemplary techniques which allows an observation of a single haplotype over multiple loci may preferably be used for an efficient phasing procedure that can be used. For example, single molecule methods may be of exemplary interest. The models and analysis presented herein relates to and is effected by such methods' applicability to association studies.
[0028] As an example, the length between two restriction fragments may be considered. The observable x may be modeled as a random variable depending on the actual distance μ.
P ( x | μ ) = 1 2 π μ exp ( - ( x - μ ) 2 2 μ )
[0029] Then, it is possible to isolate a specific pair of restriction sites on one of the haplotypes H 1 , and let the distance between them be provided by μ 1 . The distance between the homologous pair on the second haplotype H 2 can be provided by μ 2 . An observation x from the genotype data can then be either derived from H 1 or H 2 , denoted x˜H 1 and x˜H 2 , respectively.
P ( x ) = P ( x | x ∼ H 1 ) P ( x ∼ H 1 ) + P ( x | x ∼ H 2 ) P ( x ∼ H 2 ) = 1 2 π μ 1 exp ( - ( x - μ 1 ) 2 2 μ 1 ) P ( x ∼ H 1 ) + 1 2 π μ 2 exp ( - ( x - μ 2 ) 2 2 μ 2 ) P ( x ∼ H 2 ) .
[0030] Using the RFLP sizing mapping technique, observable d ij , can have independent error sources depending on loci-specific parameters. The set {d ij, i ε [1 . . . N]} can provide points in R which may be discriminated using, e.g., a Gaussian Mixture model. Due to the uncertainty of mapping and underlying haplotypes, posteriori distribution α(x)=[P(x˜H 1 ),P(x˜H 2 )] can be selected to model the data rather than determined allele types.
[0031] The additional description of the exemplary embodiment of the present invention is organized into the following four sections: Section 1 describes the EM-Algorithm procedure used with the exemplary embodiment of the present invention, Section 2 discusses the phasing problem, addressed by the present invention, Section 3 describes a procedure implementation and examples thereof, and Section 4 describes results and applications of the present invention.
[0032] Section 1. EM-Algorithm for Detection of Bi-Allelic Polymorphisms of the Present Invention
[0033] The use of the EM-Algorithm for inferring parameters of a Gaussian mixture model is a well known technique (see Dempster et al., 1977, J. Roy. Stat. Soc. 39:1-38; and Roweis et al. 1999, Neural Computation 11:305-345), and, as described herein, also useful in the detection of biallelic polymorphisms.. In the presence of polymorphisms at loci j, informative mapping data can provide a bimodal distribution in the data space R r . Detailed exemplary computations for E-Step and M-Step of the EM-Algorithm are described herein in the Examples section. For each locus j, the EM-algorithm can be executed in accordance with the present invention until convergence occurs, the result being: <α k (x),{circumflex over (Φ)}=<{circumflex over (μ)} 1 ,μ 2 , . . . ,μ K ,σ>>. In this example, α is a posteriori probability that data point x is derived from allele type k ε [1,2, . . . , K].
[0034] Criteria for Polymorphisms. Let {circumflex over (Φ)} (D) denote the limit of the EM-algorithm with data set D at the loci j. The following issue may be raised: when will a locus exhibit two specific allele variations? In the setting when K=2, as in the remainder of this description (hence {circumflex over (Φ)}=<μ 1 ,μ 2 ,σ>), polymorphic loci are defined as events:
X ( D ) = { 1 if Φ ^ ( D ) : μ ^ 1 - μ ^ 2 - δ > 0 0 o . w .
[0035] Effectiveness of the EM-Algorithm. Mapping techniques may contain errors that are Gaussian across a diverse set of technologies. Genetic markers may be associated or linked to allele types in the population. The mixture model/technique treated with EM Algorithm can operate effectively, and possibly distinguishing fits beyond visual accuracy. The constraint for a single value of α can force the EM-Algorithm to result in one of two steady states, e.g., μ 1 ≠μ 2 or μ 1 =μ 2 (a single Gaussian). Although the EM-Algorithm estimates are slightly biased, the estimators are consistent, and the bias is known to diminish with larger data sets.
[0036] The individual experimental data {d ij :i ε[1 . .. N]} can be mapped to posteriori probability that measures over the allele classes. Thus, a probability function a (y) reflecting a confidence (in the presence of mapping error) that point y corresponds to one of our allele types can be produced. For polymorphism assignments, false positives are unlikely to disturb the phasing, while false negatives may affect the size of phased contigs.
[0037] Section 2. Phasing Genotype Data
[0038] “Phasing” is the problem of determining the association of alleles, due to a linkage on the same haplotype. Letting Λ j be the allele space at loci j, a haplotype may be considered an element of the set: Π j ε[1,2, . . . ,M] Λ j .
[0039] In phasing polymorphic alleles for an individual's genotype data (a mix of two haplotypes), it can be assumed that about half of the data can be derived from each of the underlying haplotypes H 1 and H 2 . In this context, haplotypes have a complementary structure in that the individual's genotype should be heterozygous at each polymorphic locus.
[0040] A haplotype space can be defined in accordance with the present invention, and methods for estimating the probability that an observation di is derived from a particular haplotype over a set of loci are described. The maximum likelihood problem for haplotype inference can then be formulated, and this formulation may be the proposed solution to the phasing problem.
[0041] Haplotype Space and Joint Distributions. The full space of haplotypes is the product over all allele spaces {1, 2, . . . ,M}. In general, haplotype space is in one-to-one correspondence with M={−1,l} M . The discrete-measure space (M,2 M ) can be used to denote the haplotypes, while M[j 1 , j 2 , . . . , j v ] denotes the haplotypes over the range of loci j 1 , j 2 , . . . , j v . The result of phasing genotype data may be a probability measure on the space (M, 2 M ). Noiseless data may result in a measure assigning ½ to each of the complementary haplotypes, and 0 to all others. This uniform measure over complements corresponds to perfect knowledge of what the haplotypes are. The procedure that can be used by an exemplary embodiment of the system, method and software arrangement of the present invention is consistent in that the correct result is achieved for suitably large data sets.
[0042] For example, let Λ j be the allele set for the polymorphic loci j. Two bi-allelic loci j and j′ can be used. For clarity, we will assume that Λ j ={A,a} while Λ j′ ={B,b}. A data observation d i may be derived from one of the four classes: AB, Ab, aB, ab. Because the mapping noise at loci j and j′ are independent, the probability (based on the loci a posteriori) that the observation can be derived from the following four classes:
P ( d i ˜AB )=α jA ( d ij )α j′B ( d ij′ )
P ( d i ˜Ab )=α jA ( d ij )α j′b ( d ij′)=α jA ( d ij )(1−α j′B ( d ij′ ))
P ( d i ˜aB )=α ja ( d ij )α j′B ( d ij′)=( 1−α jA ( d ij ))α j′B ( d ij′)
P ( d i ˜ab )=α ja ( d ij )α j′b ( d ij′ )=(1−α jA ( d ij ))(1−α j′B ( d ij′ ))
[0043] α jj′ (i) can be defined as the estimated probability distribution for observation i on haplotypes over the loci j, j′:
α jj′ (i) =[α jj′AB ( d i ),α jj′Ab ( d i ), α jj′aB ( d i ), α jj′ab ( d i )]
[0044] α jj′ is defined as the estimated probability distribution over the data set on haplotypes over the loci j, j′:
α j j ′ ( D ) = 1 N ∑ i = 1 N α j j ′ ( i )
[0045] For ρ ε M[j 1 , j 2 . . . , j M ] and α j w ρ w (d i )=Prob(d i ˜ρ w ) with ρ w ε Λ j w , the estimates can be extended to any set of indices producing:
α j 1 j 2 … j w ( i ) = [ ∏ w ∈ [ 1 … v ] α j w ρ w ( d i ) ] ρ ∈ M [ j 1 , j 2 , … , j v ] α j 1 j 2 … j v = 1 N ∑ i α j 1 j 2 … j v ( i )
[0046] Complementarity. In phasing the diploid genotype data into two haplotypes ρ 1 , ρ 2 ε M, there may be a special property present, e.g., haplotype ρ 2 can be complementary to haplotype ρ 1 , denoted {overscore (ρ)} 2 =ρ 1 . The complementary pair of haplotypes may be represented by a change of variables ω ε {−1,1} M-1 , and the transformation to the haplotypes may be given by the map:
ρ 1 ( b ) = { - 1 if b = 1 - 1 ∏ j = 1 : ( b - 1 ) w ( j ) for b ∈ [ 2 … M ] ρ 2 ( b ) = { 1 if b = 1 1 ∏ j = 1 : ( b - 1 ) w ( j ) for b ∈ [ 2 … M ]
In evaluating the data, there may be a possible 2 M-1 complementary pairs of allele types to search.
[0047] The confidence of a set of complementary haplotypes can be modeled as a probability distribution on the discrete measure space (M, 2 M ), which is the convex hull of the following set of extremal points which correspond to certain knowledge of complementary haplotypes.
A = { θ ρ : θ ρ ( δ ) = { 1 2 if δ = ρ 1 2 if δ = ρ _ 0 o . w . for δ ∈ M }
[0048] These values can represent the uniform distribution over complementary haplotypes and geometrically are vertices of a high dimensional hypercube. For example, let A[j 1 , j 2 , . . . , j v ] be the corresponding distribution over the haplotype space M[j 1 , j 2 , . . . , j v ].
[0049] Maximum Likelihood Problem. For every loci j, it can be assumed that the data {d ij :i ε [1 . . . N]} contains an equal distribution of data from the underlying haplotypes H 1 , H 2 that can be inferred. Using the estimated values α for the joint distribution over loci product spaces, the haplotypes most likely producing a can be computed. The corresponding maximum likelihood problem may be formulated as follows:
[0050] Let the likelihood function be given by:
L ( Θ ) = P ( D | Θ ) = Γ ( N ) ∏ ρ ∈ M Γ ( N α p ) ∏ ρ ∈ M Θ ρ α p N MLE 1 Find ρ ∈ A so that L ( ρ ) ≥ L ( ω ) ∀ ω ∈ A .
[0051] Similarly, for any specified set of loci {j 1 , j 2 , . . . , j v }, a likelihood function L M[j 1 ,j 2 , . . . j v ] maybe defined as the most likely to produce posterior α j 1 , j 2 . . . j v over the space M[j 1 , j 2 , . . . j v ].
Lemma 1 If d ( α , A ) < ∈ for some ∈ small enough , and d ( α , A ) = min θ ∈ A α - θ 2 . Maximizing ∏ ρ ∈ { 0 , 1 } M - 1 Θ ρ α p N over Θ ∈ A is equivatent to minimizing ∑ j ∈ 1 … M ( α j - Θ j ) 2 α j over Θ ∈ A .
[0052] The description provided below in the Examples section is derived from a Taylor-series expansion of the likelihood function. It demonstrates that the MLE result in set A is the vertex of a 2 M-1 hyper-cube closest to the estimated joint probability function α, measured by a modified L 2 norm.
[0053] With this result, the following function to be used in the algorithms presented later can be assumed:
Algorithm 1 MLE - COLLAPSE ( j 1 , j 2 … , j v ) Compute ρ ∈ A [ j 1 , j 2 … , j v ] minimizing ∑ j ∈ j 1 , j 2 … , j v ( α j - Θ j ) 2 α j over Θ ∈ A return ρ
[0054] Section 3. Exemplary Procedures
[0055] Exemplary procedures generally focus on growing disjoint-phased contiguous sets of loci called contigs. For example, all loci can be assigned an arbitrary phase and begin as a singleton phased contig. A J OIN operation checks if these phased contigs may be phased relative to one another using a function called V ERIFY -P HASE . V ERIFY -P HASE can be designed to check a phasing criteria, for example refuting a hypothesis of Hardy-Weinberg Equilibria is discussed below in the Examples section. Other examples of suitable phasing criteria are known to those of ordinary skill in the art. Such criteria may, for instance, be based on the statistical distribution of haplotypes in the ambient population, on the perfect phylogeny hypothesis, or on the relation to genotypes of parents, siblings and other closely-related family members.
[0056] If a pair of phased contigs can be joined by passing the test, implied by V ERIFY -P HASE function, then the disjoint sets are combined into a single phased contig and the joint distribution over the set is computed with the MLE-C OLLAPSE function. After completion of a successful join operation, the resulting distribution function may be regarded as the most likely one among all haplotypes that can generate the observed data over the specified loci. Because the growth of contigs is monotonic and depends on local information available at the time of the operation, an ADJUST operation is also considered that fractures and rejoins contigs using a larger locality of data than what was available during the J OIN.
[0057] The operations are described in detail, the results are analyzed, and methods for avoidance of incorrect operations are indicated.
[0058] Collapse. The collapse of the phase operation can be described as the MLE-C OLLAPSE function, the example of which is shown in FIG. 1 which provides a collapse of the phase of two polymorphic loci 30 into a single haplotype 40 . It may be used to update a joint probability distribution over a set of contigs, and has the effect of keeping the contig structures bound to haplotype states which simplifies the computing of a phase. FIG. 2 shows an exemplary illustration of the phase of three polymorphic loci 70 provided into two complementary haplotypes 80 in accordance with an exemplary embodiment of the present invention
[0059] Join: Let K be a parameter denoting neighborhood size. Let C 1 ={j 1 , j 2 , . . . , j v } and C 2 +{j′ 1 , j′ 2 , . . . j′ w }; then the join operation is as follows:
[0060] Given joint-probability functions α j 1 , α j 2 , . . . α j v , α j′ 1 , α j′ 2 , . . . α j′ w , compute the joint probability function α C 1 , C 2 with formula
α C B ,C 2 =α (j v )(j′ 1 j′ 2 . . . j′ ω ) =ω j v ,j′ 1 α (j ω )(j′ 1 j′ 2 . . . j′ ω ) +ω j v j′ α (j v )(j′ 1 j′ 2 . . . j′ w ) +. . . +ω j v ,j′ K α (j v )(j′ 1 j′ 2 . . . j′ K . . . j′ ω )
with
α ( j v ) ( ( j 1 ′ j 2 ′ … j κ ′ … j w ′ ) = ∑ i = 1 : N α j v j x ′ ( i ) = ∑ i = 1 : N α j u ( i ) ( d ij u ) α j x r ( i ) ( d ij x ′ )
ω j v , j x ′ = κ 1 d ( j v , j x ′ )
Here , κ = 1 1 d ( j v , j 1 ′ ) + 1 d ( j v , j 2 ′ ) + … + 1 d ( j v , j κ ′ ) and d ( j v , j x ′ )
is proportional to genomic distance between loci j v and j x ′ .
Algorithm 2
COMPUTE - PHASE
( C 1 = { j 1 , j 2 , … , j v } , C 2 = { j 1 ′ , j 2 ′ , … , j w ′ } , κ )
assume j v in C 1 is such that
d ( j v , C 2 ) ≤ d ( j 1 C 2 ) ∀ j ∈ C 1 ;
Compute α ( j v ) ( j 1 ′ , j 2 ′ , … , j w ′ ) using parameter κ .
return α ( j v ) ( j 1 ′ , j 2 ′ , … , j w ′ )
Algorithm 3
JOIN
( C 1 = { j 1 , j 2 , … , j v } , C 2 = { j 1 ′ , j 2 ′ , … , j w ′ } , κ )
COMPUTE - PHASE
( C 1 = { j 1 , j 2 , … , j v } , C 2 = { j 1 ′ , j 2 ′ , … , j w ′ } , κ )
if ( VERIFY - PHASE ( α j 1 j 2 … j v ) ) then
α j 1 j 2 … j v ← MLE - COLLAPSE ( j 1 j 2 … j v ) ;
[0061] The method, system and software arrangement of an exemplary embodiment according to the present invention can estimate the haplotypes by solving an ordered set of local MLE problems.
[0062] Implementation. Input. The input is a set of data points {d ij ε R r : i ε [1 . . . N], j ε [1 . . . M]}. The following assumptions are made about the input:
For each j the points d 1j ,d 2j , . . . d Nj are derived from the Gaussian mixture model corresponding to mapping data at polymorphic loci j. For each i points d i1 , d i2 , . . . , d iM are independent random variables with parameters associated to underlying haplotypes.
[0065] With the knowledge of the mapping order of polymorphic loci, the positions of the genome can be assumed to be χ 1 , χ 2 , . . . , χ M .
[0066] Implementation. Pre-Process. The EM-algorithm procedure can be executed for each locus: {d ij : i ε [1 . . . N] observable}→{{circumflex over (Φ)} j : α j }∀j ε [1, . . . , M].
[0067] The result is a set of estimates for bi-allelic loci, {{circumflex over (Φ)} 1 , {circumflex over (Φ)} 2 , . . . , {circumflex over (Φ)} M }, as well as a set of functions estimating the probability that any data point derives from the distinct alleles {α 1 , α 2 , . . . , α M }.
[0068] Next, a join schedule can be constructed. Letting β j =χ j+1 −χ j , the results are sorted into an index array giving an increasing sequence: j 1 , j 2 , . . . j v , . . . j m-1 .
[0069] Implementation. Main Algorithm and Data Structure. Contigs can be maintained in a modified union-find data structure designed to encode a collection of disjoint, unordered sets of loci, which may be merged at any time. Union-find supports two operations, UNION and FIND (see Taijan, 1983, Data Structures and Network Algorithms, CBMS 44, SIAM, Philadelphia). For example, UNION can merge two sets into one larger set, and FIND can identify the set containing a particular element. Loci j may be represented by the estimated distribution α J , and can reference its left and right neighbor. At any instant, a phased contig may be represented by:
An MLE distribution or haplotype assignment for the range of loci in the contig (if one can be evaluated). Boundary loci: Each contig has a reference to left- and right-most locus.
[0072] In the vth step of the procedure, consider the set of loci determined by β v , {j v , j v+1 }: If FIND (j v ) and FIND (j v+1 ) are in distinct contigs C p and C q , then (a) attempt to UNION C p and C q , by use of the JOIN operation, and (b) update the MLE distribution and boundary loci at the top level if the JOIN is successful.
[0073] Implementation. Output. Output can be a disjointed collection of sets, each of which is a phased contig. It represents the most likely haplotypes over that particular region.
[0074] Implementation. Time Complexity. The preprocess may involve using the EM-algorithm/procedure once for each locus. The convergence rate of the EM-algorithm procedure has been analyzed (see Ma et al., 2000, Neural Computation 12:2881-2907) and depends on the amount of overlap in the mixture of distributions. For moderate-sized data sets, no difficulties with convergence of the EM-algorithm procedure have been observed.
[0075] The time complexity of the main exemplary procedure can be estimated by implementing the K-neighbor version. For each β jv there may be two find operations. The number of union operations preferably does not exceed the cardinality of the set {β j: j ε [j 1 , j 2 , . . . j M-1 ]}, as contigs grow monotonically. The time-cost of a single “find” operation is preferably at most γ(M), where γ is the inverse of Ackermann's function. Therefore, the time cost of all union-find operations is preferably at most O(Mγ(M)). The join operation, on the other hand, uses the execution of the K-neighbor optimization routine, at a cost of O(K). Thus, the main exemplary procedure has a worst-case time complexity of
O ( M (γ( M )+ K ))= O ( Mγ ( M ))
and may be regarded as approximately linear in the number of markers, M for all practical purposes, since K is likely a small constant.
EXAMPLES
RFLP Examples
[0076] The method, system and software arrangement of the exemplary embodiment of the present invention can be demonstrated on two simulated data sets composed of ordered restriction fragment lengths subject to sizing error. FIG. 3 , which shows exemplary haplotypes, obtained using such exemplary embodiment is presented in the following bands:
The band 100 nearest the bottom in the layout is the simulated haplotype. The second band 110 from the bottom is the haplotype molecule map for a diploid organism. These molecules (which are sorted into two haplotype classes in the layout) can be mixed and made available to the procedure of the present invention as a single set of genotype data. The third band 120 from the bottom shows the results of the EM-algorithm and the set of markers that are determined to have polymorphic alleles. The fourth band 130 in the layout provides the history of contig operations. From this tree, it is possible to view: 1) the developing k-neighborhoods, and 2) the distinct phased contigs. The top band 140 in the layout provide the algorithmic output for this problem, including phased-in subsets that span the distance indicated by the bars above and below the loci markers. The areas where phase structure overlaps but cannot extend are regions that are of interest to target with more specific sequences, in order to extend the phasing.
[0082] Parameters of the simulations are summarized in Table 1.
TABLE 1 Parameters* employed in performing the simulations for Datasets 1 and 2. Parameter Symbol Data Set 1 Data Set 2 Number of molecules M 80 150 Number of fragments RFLP F 20 100 and non RFLP Size of the genome G 12000 50000 Expected molecule size EMS 2000 2000 Variance in molecule size VMS 50 500 Variance in fragment length size VFS 1 20 P-value that any given fragment P-BIMODE .5 .3 is an RFLP Expected separation of means ERFLPSEP 10 50 for RFLP Variance in the separation of VRFLPSEP .01 6 means for RFLP *Any parameter with both an expectation and variance can be generated with a normal distribution.
[0083] A simple VERIFY-PHASE function which checked that the posteriori distribution C a , C b is separated by a distance of C>0 from the point
[ 1 2 , 1 2 ]
may be used as an example. In practice, it was discovered that the parameter C should preferably depend on the local coverage.
[0084] For the first simulation on dataset I, shown in FIG. 3 , a relatively small set was chosen so that the potential limitations of the procedure may be revealed. Here the neighborhood size was set to k=5. False positive RFLP detections were not guarded against, yet phasings are computed. It is clear that mistakes provided therein were likely due to the low coverage library.
[0085] In the second simulation on dataset II, seen in FIG. 4 , the result 200 shows that good phasing results may be achieved even on large, sparse data sets.
MLE Estimate
If d ( α , A ) < ∈ for some ∈ small enough . Maximizing
∏ ρ ∈ { 0 , 1 } M - 1 Θ ρ α p N over Θ ∈ A is equivatent to minimizing
∑ j ∈ 1 … M ( α j - Θ j ) 2 α i over Θ ∈ A .
Proof . Let F { Θ } = n ! Π jw1 : k n j Π jw1 : k Θ j n j .
Computing the second variation :
F ″ ( θ ) = ( [ n 1 2 θ 1 2 n 1 n 2 θ 1 θ 2 ⋯ n 1 n k θ 1 θ κ n 2 n 1 θ 2 θ 1 n 2 2 θ 2 2 ⋯ n 2 n k θ 2 θ κ ⋮ ⋮ ⋯ ⋮ n k n 1 θ κ θ 1 n k n 2 θ κ θ 2 ⋯ n k 2 θ κ 2 ] - [ n 1 θ 1 2 0 ⋯ 0 0 n 2 θ 2 2 ⋯ 0 ⋮ ⋮ ⋯ ⋮ 0 0 ⋯ n k θ κ 2 ] ) F ( θ )
Since F ( θ ) is smooth in θ , Taylor ' s remainder theorem gives ,
F ( Θ ) = F ( α ) + ∇ F ( α ) · ( Θ - α ) + ( Θ - α ) T F ″ ( α ) ( Θ - α ) + o ( ( Θ - α ) 2 )
When α = n 1 n , … , n k n , ∇ F ( α ) = 0 , this is a standard MLE
result for a multi - nominal distribution .
Computing the quadratic function :
( Θ - α ) T F ″ ( α ) ( Θ - α ) = ( Θ - α ) T ( n 2 [ 1 1 ⋯ 1 1 1 ⋯ 1 ⋮ ⋮ ⋯ ⋮ 1 1 ⋯ 1 ] - n [ 1 α 1 0 ⋯ 0 0 1 α 2 ⋯ 0 ⋮ ⋮ ⋯ ⋮ 0 0 ⋯ 1 α κ ] ) F ( α ) · ( Θ - α ) = F ( α ) n 2 ( ∑ j ( Θ j - α j ) ) 2 - F ( α ) n ∑ j ( Θ j - α j ) 2 α j = - F ( α ) n ∑ j ( Θ j - α j ) 2 α j
Thus for an θ very near to α the level curves of F are
given by Θ δ = { θ : F ( θ ) = F ( α ) - δ } are approximately ellipsoids . F ( Θ ) = F ( α ) - F ( α ) n ∑ j ( Θ j - α j ) 2 α j + o ( ( Θ - α ) 2 )
= F ( α ) - F ( α ) n ∑ j ( Θ j - α j ) 2 α j + o ( ∑ j ( Θ j - α j ) 2 α j )
Let ( Θ - α ) α 2 = ∑ j ( Θ j - α j ) 2 α j . Letting L 1 = L ( α ) and
assuming there is a second local optima for the likelihood
function value at L 2 , let V ( α ) = { Θ : L ( Θ ) > L 1 - L 1 - L 2 2 } .
We must show that there is a δ so that
{ Θ : ( Θ - α ) α 2 < δ } ⋐ V ( α ) .
And this is clear from the inequality
L 1 - L 1 n Θ - α α 2 - o ( Θ - α α 2 ) < F ( Θ ) < L 1 - L 1 n Θ - α α 2 + o ( Θ - α α 2 )
by choosing a δ small enough that L 1 n δ + o ( δ ) < L 1 - L 2 2 . We conclude
that if there is a point of A ∈ { Θ : Θ - α α 2 < δ } then it must be the
unique maxima in A for our likelihood function .
Test for Hardy-Weinberg Equilibria at Different Loci
[0086] The Chi-squared statistical test for determining whether allelic data at loci j and j′ display linkage disequilibrium, and hence are not in Hardy-Weinberg Equilibrium (HWE) has been reviewed in great detail. See Weir, 1996, Genetic Data Analysis II, Sinauer Associates, Sunderland, Mass. for details and a complete statistical treatment. The Chi-squared statistical test for gametic disequilibrium at two loci has been modified by using additive disequilibrium coefficients to adjust to our population model. The end result is a Chi-squared statistical test that allows the rejection of HWE from observed frequencies alone. Since determination of linkage is a prerequisite to phasing, or at least in finding structure in the joint distribution over allele spaces of adjacent loci, this statistical test is important. The boundaries of haplotype blocks (or phased contigs) are an interesting and important issue in understanding population dynamics.
[0087] For example, let D ab denote the disequilibrium coefficient between alleles a at loci j and b at loci t :
D ab =p ab −p a p b
Where p ab , p a , p b are the population frequencies for allele type: ab, a, b respectively. In the presence of HWE D ab can be expected to be zero. Letting {circumflex over (D)} ab denote an estimate from estimate frequencies:
{circumflex over (D)} ab ={tilde over (p)} ab −{tilde over (p)} a {tilde over (p)} b
with:
{overscore (p)} a =1/ N Σ i=1:N α aj (d ij ), {overscore (p)} b =1/ N Σ i=1:N α bj′ ( d ij′ )
[0089] Computation of Expectation and Variance:
E ( D ^ ab ) = N - 1 N D ab
V ( D ^ ab ) ≈ 1 N [ p a q a p b q b + ( 1 - 2 p a ) ( 1 - 2 q a ) D ab - D ab 2 ]
[0090] The variance can be computed using Fisher's approximate variance formula. Under the assumption that loci j and j′ are in HWE, D ab =0 and:
E HWE ′ ( D ^ ab ) = 0
V HWE ( D ^ ab ) = 1 N p a q a p b q b
[0091] From this information, it is possible to construct a Chi-Squared test to evaluate the hypothesis that alleles a and b at loci j and j′ are acting as they would if they were in HWE.
χ ab 2 = z 2 = ND ab 2 p ~ a A q ~ a A p ~ b B q ~ b B
[0092] It is possible to reject the HWE hypothesis correctly 9 times in 10 by using a reference value of z 2 >2.71, or we may reject HWE correctly 99 times in 100 using reference values z 2 >6.63. If alleles are linked by a haplotype, this test may be used as the V ERIFY -P HASE function mentioned previously in this text.
[0093] EM-Algorithm Analytic Results
[0094] A. An Example Using RFLP Markers
[0095] The data at loci j can refer to the observed distances between restriction sites j and j+1, as they are derived from two haplotypes H 1 and H 2 with underlying genome distances μ 1 and μ 2 . The distribution of data points for loci j is given by:
f j ( x ) = 1 2 πμ j1 2 exp ( - ( x - μ j1 ) 2 2 μ j1 2 ) α j1 ( x ) + 1 2 πμ j2 2 exp ( - ( x - μ j2 ) 2 2 μ j2 2 ) α j2 ( x )
[0096] It is preferable to make a simplifying assumption that σ=½ (μj 1 +μj 2 ) so that f j may be closely approximated by:
F j ( x ) = 1 2 πσ 2 exp ( - ( x - μ j 1 ) 2 2 σ 2 ) α j 1 ( x ) + 1 2 πσ 2 exp ( - ( x - μ j 2 ) 2 2 σ 2 ) α j 2 ( x )
[0097] For loci j the set of points {d ij =i ε [1, 2, . . . N]} is data. It is preferable to infer the model parameters Φ={σ=μ 1 , μ 2 } and posteriori distribution or by use of the EM-algorithm. The subscript j can be dropped in the following equation, the objective being to iteratively optimize the function:
H ( α , Φ ) = ∑ i ∈ 1 : n ∑ k ∈ 1 : 2 ( α k ( d ji ) ln G k ( d ji ❘ Φ ) - σ k ( d ji ) ln ( α k ( d ji ) ) )
With G k ( x ❘ ϕ ) = 1 2 πσ 2 exp ( - ( x - μ k ) 2 2 σ 2 ) the k th Gaussian
kernel .
[0098] Optimization can be done in two steps:
1. E-STEP Holding Φ fixed, optimize H(α, Φ) over α, letting Φ be the previous estimate of parameters. The result for the argmax α is:
α k ( x ) ← G k ( x ❘ Φ ) ∑ i G l ( x ❘ Φ )
2. M-STEP Holding α fixed, optimize H(αΦ) over Φ (using the previous estimate of parameters on the hidden categories α (y), which depend on the previous estimate denoted {circumflex over (Φ)}=[{circumflex over (μ)} 1 , {circumflex over (μ)} 2 , ]). The result argmin H(&, Φ) is:
μ k ← ∑ i = 1 : n d k ( d ij ) d ij ∑ i = 1 : n d k ( d ij )
σ ← 1 2 ∑ j ≠ 1 : 2 1 N ∑ i = 1 : N α ^ j ( d ij ) ( d ij - μ ^ j ) 2
[0103] The EM-algorithm procedure can be executed until convergence in the parameter space occurs. Exemplary detailed computations for the E-Step and M-Step are provided in the appendix. Detailed proofs of each step are provided below.
[0104] E-Step
[0105] Proof. Consider the calculus problem of optimizing:
f ( ϕ ) = ϕ ( A 1 - log ( B ϕ ) ) + ( 1 - ϕ ) ( A 2 - log ( B ( 1 - ϕ ) ) )
f ′ ( ϕ ) = 0 ⇒ ϕ ′ = ( 1 ⅇ A 1 - A 2 + 1 )
[0106] Φε (0, 1). Apply this fact to the optimization problem of finding numbers Q=<α iv > 1:N,vw1:2, so that the following function is optimized.
∑ i = 1 : n ∑ ν = 1 : 2 ( α i ν ( A i ν - log ( B α ω ) ) ) = ∑ i = i : n α i ν ( A i 1 - log ( B α ω ) ) + ( 1 - α ω ) ( A i 2 - log ( B ( 1 - α ω ) ) )
[0107] Where
A 1 = ( dj - μ 1 ) 2 2 σ 2 and A 2 = ( dj - μ 2 ) 2 2 σ 2 and B = 2 πσ 2 .
It is shown that the answer is given by maximizing each summand and hence given by:
α 1 = ( 1 ⅇ ( ( d i - μ 1 ) 2 2 σ 2 - ( d i - μ 2 ) 2 2 σ 2 ) + 1 ) = G 1 ( d i ) G 1 ( d i ) + G 2 ( d i )
and similarly for σ 2 .
[0108] M-Step
[0109] Proof. Consider the calculus problem of optimizing:
f ( μ 1 , μ 2 , σ ) = ∑ i = 1 : N ∑ ν = 1 : 2 q ν i log ( 1 2 πσ 2 exp - ( α i - μ ν ) 2 2 σ 2 ) + H = ∑ i = 1 : N ∑ ν = 1 : 2 q ν i ( - ( α i - μ ν ) 2 2 σ 2 - log 2 πσ 2 ) + H
[0110] Where H is constant in (μ 1 , μ 2 , σ). Consider the partial derivative of f with respect o μ v :
∂ f ∂ μ ν = ∑ i = 1 : N ∂ ∂ μ ν ( q ν i 2 σ 2 ( - α i 2 + 2 α i μ ν - μ ν 2 - 2 σ 2 log 2 πσ 2 ) ) = 1 σ 2 ∑ i = 1 : N q ν i α i - μ ν q ν i
[0111] Thus, the following is obtained:
∂ f ∂ μ ν = 0 ⇐ μ ν = ∑ i = 1 : N q i ν α i ∑ i = 1 : N q i ν
[0112] Now consider the partial off with respect to σ:
∂ f ∂ σ = ∑ i = 1 : N ∑ ν = 1 : 2 q ν i ( ( α i - μ ν ) 2 2 σ 2 - 1 )
[0113] Section 4. Conclusions
[0114] The simulation results described herein demonstrate that locally the phasing may be highly accurate. When local coverage derived from one haplotype is low, the detection of polymorphisms can become difficult. In the first dataset, a false negative detection may be found on the 8th marker from the left. This false negative was due to zero coverage from one of the haplotypes at that point. The ninth marker can be a false positive detection, and may be attributed to zero coverage from one haplotype and low coverage (two molecules) from the alternative haplotype. The false positive does not cause errors in the phase information for correctly detected polymorphic loci in the phased-contig achieved over marker index in the set {7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19}. Designing a mapping experiment targeting a polymorphic marker in the set {6, 7, 8, 9, 10} can allow one to phase the two contigs into a single contig.
[0115] The results of the method for haplotype phasing of the present invention may be assessed in terms of two absolute quantities: resolution and accuracy. Not only does the method of the present invention provide conclusions, it also reports a confidence level associated with the conclusion. Since an individual's haplotype structure is singular and absolute, any method that makes conclusions about that structure should assess its own accuracy. The method according to the present invention provides this assessment in such a way that the resolution and accuracy of the conclusions drawn for an individual scale with the amount of effort (i.e. mapping experiments) expended on that individual. This feature of the method is important because (a) an accurate and high resolution determination of an individual's haplotype structure may be drawn in the absence of knowledge or information from her/his pedigree or sub-population, in contrast to population-based studies, which rely on mapping data from a set of closely related individuals, and (b) since resolution and accuracy scale with effort, the same scaling relationship is present for cost. In various applications of the method and system of the instant invention where different resolutions and accuracies are required, the present method provides a better estimate for the same cost when compared to currently available alternative methods.
[0116] FIG. 5 shows a block diagram of an exemplary embodiment of a system 300 according to the present invention which is capable of storing thereon the storage arrangement of the present invention, and operable to execute thereon the method according to the present invention. In particular, the system includes a processing arrangement 310 and a storage arrangement 320 . The storage arrangement 320 can be one or more hard drives, memory (read-only memory, random access memory—“RAM”, DRAM), CD-ROMs, floppy disks, etc. and/or combination thereof, and may store thereon a software arrangement (e.g., a software program). The software program can be accessed by the processing arrangement 310 (e.g., a processor such as Intel Pentium® processor), and the software arrangement can make the processing arrangement operable to execute the exemplary embodiment of the present described herein.
[0117] For example, the system 300 can receive genotype data associated with one or more genetic sample, either from external sources or from the storage arrangement 320 . The processing arrangement 310 (executing the software arrangement obtained from the storage arrangement 320 ) obtains the data, and performs the procedures in accordance with the exemplary embodiment of the present invention. After the processing is completed by the processing arrangement 310 , the processing arrangement can obtain and output haplotype data for respective genetic sample (in block 340 ). In addition or as an alternative, the processing arrangement 310 can obtain a confidence level of accuracy of the obtained haplotype data (block 350 ), and/or results of examination of a linear number of polymorphic genetic markers (block 360 ).
[0118] FIG. 6 shows a flow diagram of a top level of one exemplary embodiment of the method 400 according to the present invention for establishing the haplotype of one or more genetic samples from genotype data obtained from the corresponding one or more genetic samples. This method can be executed by the system 300 of FIG. 5 , or by any other arrangement or system that is capable of implementing the method. For example, in step 410 , the genotype data (associated with one or more genetic samples) is obtained. Then, in step 420 , the polymorphic genetic markers are identified from the genotype data. Further, one or more associations of the polymorphic genetic markers across genetic loci are determined to obtain the information associated with the haplotype data.
[0119] While the invention has been described in connecting with preferred embodiments, it will be understood by those of ordinary skill in the art that other variations and modifications of the preferred embodiments described above may be made without departing from the scope of the invention. Other embodiments will be apparent to those of ordinary skill in the art from a consideration of the specification or practice of the invention disclosed herein. For example, the exemplary embodiments of the present invention can also be applicable for polyploid organisms, as well as diploid organisms. It should be understood that the present invention is operable on one or more chromosome of an organism, and can be used even if certain marker information is ambiguous or missing altogether. It is intended that the specification and the described examples are considered as exemplary only, with the true scope and spirit of the invention indicated by the following claims. Additionally, all references cited herein are hereby incorporated by this reference as though set forth fully herein. | The present invention relates to a method, system and software arrangement for determining the co-associations of allele types across consecutive loci and hence for reconstructing two haplotypes of a diploid individual from genotype data generated by mapping experiments with single molecules, families or populations. The haplotype reconstruction system, method and software arrangement of the present invention can utilize a procedure that is nearly linear in the number of polymorphic markers examined, and is therefore quicker, more accurate, and more efficient than other population-based approaches. The system, method, and software arrangement of the present invention may be useful to assist with the diagnosis and treatment of any disease, which has a genetic component. | 6 |
FIELD OF THE INVENTION
The present invention relates generally to energy production devices, more specifically but not by way of limitation, an energy production device that captures the motion of ocean waves and converts that motion into a usable energy form.
BACKGROUND
Global demand for energy is increasing year after year. Despite recent economic stagnation in various parts of the world, energy consumption and the requirement for more alternative sources of energy has increased. The increased demand for conventional energy sources such as but not limited to oil, has placed an increased focus on generating energy from alternative sources. Alternative energy sources such as wind and solar have been developed but are struggling to be commercialized and achieve market penetration due to issues such as but not limited to high component cost.
Alternative energy sources such as wind and solar have additional shortcomings that have limited the use of these energy sources. Solar technology has yet to develop the needed capacity to operate anything but small devices without the need for a significant amount of photovoltaic cells, which create logistic, and many other issues for implementation. Wind power generation has garnered negative social feedback, as many residents do not want wind farms in their area due to noise levels and aesthetic concerns.
Hydro powered devices have been utilized for many years but with limited exposure. It is well known that river dams are equipped with hydroelectric equipment and have successfully generated power for decades. While river currents and the manipulation thereof have been utilized to generate power, there has been minimal attempt to harness the power of the ocean in order to create a sustainable source of power. Approximately 38% of the population lives within 100 km of a coast. The ocean consistently generates energy in the form of tides and waves as a result of gravity and other atmospheric conditions. The undulating motion of the waves and the virtual consistent presence thereof represents a significant opportunity to transform that energy into a usable energy source such as but not limited to electricity.
Accordingly, there is a need for an apparatus that can convert the undulating motion of ocean waves into a usable energy form that can be subsequently distributed to communities proximate the coastal regions and beyond.
SUMMARY OF THE INVENTION
It is the object of the present invention to provide a power generation device that converts the energy in ocean waves into a usable energy source.
Another object of the present invention is to provide a power generation device that converts the energy of ocean waves into a usable source that utilizes a network of buoyant objects operable to engage waves of various heights.
A further object of the present invention is to provide a device operable to convert the energy of ocean waves into a usable form of energy wherein the network of buoyant objects are operably coupled to a framework of support rods.
Still a further object of the present invention is to provide an apparatus that converts the motion of ocean waves into a usable energy source wherein the framework of support rods are configured in multiple levels.
An additional object of the present invention is to provide an apparatus that converts the undulating motion of ocean waves into a usable energy wherein the buoyant objects are operably coupled to air pumps having pistons that are disposed within cylinders that generate air pressure as the buoyant objects move in an upwards-downwards motion.
Yet a further object of the present invention is to provide an apparatus that converts ocean wave motion into a usable energy form that collects the air pressure generated by the air pumps into a central storage tank.
Another object of the present invention is to provide an apparatus that converts the undulating motion of ocean waves into a usable energy form that includes an additional air storage tank located onshore that is operably coupled to a pneumatic generator, air driven turbine or other device operable to convert air pressure into a energy source such as but not limited to electricity.
To the accomplishment of the above and related objects the present invention may be embodied in the form illustrated in the accompanying drawings. Attention is called to the fact that the drawings are illustrative only. Variations are contemplated as being a part of the present invention, limited only by the scope of the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
A more complete understanding of the present invention may be had by reference to the following Detailed Description and appended claims when taken in conjunction with the accompanying Drawings wherein:
FIG. 1 is a schematic top view of an embodiment of the present invention; and
FIG. 2 is a schematic of the pistons and air collection pipes of the present invention; and
FIG. 3 is a schematic of the air supply pipes of the present invention; and
FIG. 4 is a schematic side view of an embodiment of the present invention.
DETAILED DESCRIPTION
Referring now to the drawings submitted herewith, wherein various elements depicted therein are not necessarily drawn to scale and wherein through the views and figures like elements are referenced with identical reference numerals, there is illustrated a wave powered energy conversion system 100 constructed according to the principles of the present invention.
Referring in particular to FIG. 4 , the wave powered energy conversion system 100 further includes a tank 2 having at least one wall 4 , top 6 and a bottom 8 operable to form an interior volume. The tank 2 is manufactured from a suitable durable material such as but not limited to aluminum and functions to store pressurized air therein. Pressurized air is introduced into the tank 2 via a network of air collection pipes 12 as discussed herein. The tank 2 is equipped with conventional pneumatic valves and is constructed so as to maintain a pressure therein that is greater than that of atmospheric pressure. The tank 2 is operably coupled to support posts 10 which are driven into the sea floor utilizing suitable techniques to provide stability for the wave powered energy conversion system 100 . The support posts 10 are generally cylindrical in shape and constructed of a suitable durable material such as metal. It is contemplated within the scope of the present invention that any number of support posts 10 could be utilized to support the tank 2 . Superposed the tank 2 and integrally secured thereto is an air tower 14 that is generally modified cylindrical in shape having an opening 15 proximate the top 16 . The air tower 14 is secured to the tank 2 utilizing suitable techniques and functions to supply air to the network of air supply pipes 18 (discussed further herein). While not illustrated herein, the air tower 14 and thus the main air supply pipe 20 , are pneumatically isolated from the interior volume of the tank 2 proximate the top 6 of the tank 2 utilizing conventional isolation construction techniques and/or valves. The pneumatic isolation functions to allow the air supply pipes 18 to have introduced thereinto a constant supply of air while maintaining the tank 2 can be pressurized to a desired air pressure. Those skilled in the art will recognize that the air tower 14 could be pneumatically isolated utilizing numerous different techniques and/or valving. Proximate the top 16 of the air tower 14 is cover 22 . The cover 22 is suspendly mounted utilizing conventional techniques over the opening 15 so as to substantially inhibit rain or ocean water from entering the opening 15 . While no height for the air tower 14 is required it is contemplated within the scope of the present invention that the air tower 14 extends above the water level 1 so as to substantially avoid any water entry from wave splashes or the like. While the tank 2 and air tower 14 are illustrated as having a particular shape in the drawings submitted herewith, it is contemplated within the scope of the present invention that the tank 2 and air tower 14 could be manufactured in numerous different sizes and shapes.
As shown in particular in FIG. 2 , a support ring 24 is circumferentially mounted to the tank 2 . The support ring 24 is manufactured from a suitable durable material such as but not limited to aluminum and is mounted to the tank 2 utilizing conventional fasteners (not illustrated herein). The support ring 24 is mounted to the tank 2 such that a void 25 is present between the support ring 24 and the wall 4 of the tank 2 . The void 25 allows the main support rod 27 connected at joint 28 sufficient room for a pivotal connection. Extending outward from the support ring 24 are a plurality of main support rods 27 . The main support rods 27 are organized in parallel pairs 31 and are manufactured from a suitable durable material such as but not limited to corrosion resistant metal. The main support rods 27 are manufactured from a lightweight material and are generally hollow being sealed so as to increase their inherent buoyancy. The main support rods 27 are pivotally connected to the support ring 24 at joint 28 with fastener 29 . Fastener 29 is generally surroundably mounted to the support ring 24 and is movably coupled thereto so as to allow an upwards-downwards movement of the main support rods 27 . As discussed further herein, the main support rods 27 function to drive the third level air pumps 80 . The main support rods 27 function to provide a structural support framework and are operably coupled with the plurality of secondary support rods 30 . It is contemplated within the scope of the present invention that the main support rods 27 could be configured in numerous different lengths dependent upon the surface area of ocean that the wave powered energy conversion system 100 is configured to cover. In the preferred embodiment of the present invention, there are four parallel pairs 31 of the main support rods 27 . The four parallel pairs 31 define quadrant areas 201 . The drawings submitted herewith provide illustration of either one or a portion of the quandrant areas 201 .
Extending generally perpendicular to the main support rods 27 are a plurality of secondary support rods 30 . The secondary support rods 30 are movably coupled to the main support rods 27 at point 32 utilizing suitable durable techniques and are manufactured from a corrosion resistant material. Further the secondary rods 30 are lightweight, rigid and generally hollow being sealed in construction so as to increase their natural buoyancy. The secondary support rods 30 are manufactured to a desired length so as to provide sufficient length to allow a sufficient quantity of first level air pumps 90 to be operably coupled thereto in a particular quadrant area 201 . It is contemplated within the scope of the invention that numerous different quantities of secondary support rods 30 could be operably coupled to the main support rods 27 so as to be configured for distribution across a desired surface area of the ocean.
Operably connected to the secondary support rods 30 are a plurality of lever arms 35 . The lever arms 35 are movably mounted to the secondary support rods 30 and are generally perpendicular thereto. The lever arms 35 are manufactured from a suitable durable material and are movably coupled so as to allow an upwards-downwards movement thereof with respect to the secondary support rods 30 . The lever arms 35 include a first end 36 and second end 37 . Secured to the second end 37 of the lever arm 35 is a buoyant object 40 . The buoyant object 40 is manufactured from a suitable durable material such as but not limited to plastic and has a positive buoyancy so as to maintain a position at the surface of the water level 1 . The buoyant object 40 functions to move the lever arms 35 in an upwards-downwards motion as the water level undulates due to natural wave activity. As the lever arms 35 move in the aforementioned manner, the piston rod 42 is also moved in an upwards-downwards motion consistent with the lever arm 35 .
The piston rod 42 is operably coupled to the lever arm 35 and secured thereto utilizing suitable durable techniques. The piston rod 42 is secured in a manner such that it is extending generally upward from the lever arm 35 . The main support rods 27 , secondary support rods 30 and lever arms 35 are operably connected as described herein and function to move in an upwards-downwards motion being driven by the buoyant objects 40 as a result of the natural undulating motion of ocean waves. The piston rod 42 is manufactured from a suitable durable material such as aluminum and is operably coupled to the piston 44 that is disposed within the first level air pump 90 . FIG. 2 herein illustrates the lever arm 35 , piston rod 42 and piston 44 without the first level air pump 90 in order to provide views thereof. FIG. 4 submitted herewith illustrates the piston rod 42 and piston 44 wherein the piston 44 is disposed within the first level air pump 90 and further illustrates the air collection pipe 70 operably coupled therewith. The first level air pump 90 is manufactured from a suitable durable material and is generally cylindrical in shape have a wall 91 forming an interior volume 92 . The first level air pump 90 is a conventional air pump and operates such that the reciprocating movement of the piston 44 within the interior volume 92 pressurizes the interior volume 92 and the pressurized air is subsequently transferred to the passage 69 of the air collection pipe 70 for distribution to the tank 2 thus increasing the air pressure within the tank 2 .
Each of the buoyant objects 40 is independently movable with respect to the adjacent buoyant object 40 . As each buoyant object 40 moves on the surface of the water level 1 the lever arm 35 is reciprocated so as to further reciprocate the piston rod 42 driving the piston 44 disposed within the first level air pump 90 . As the first level air pump 90 is operated, pressurized air is delivered to the tank 2 via the air collection pipe 70 . The air collection pipe 70 is a conventional hollow pipe that delivers the pressurized air to the tank 2 . The air collection pipe 70 is flexibly coupled to the tank 2 so as to ensure consistent engagement therewith in the event of any movement of the air collection pipe 70 . The independently movable configuration of each lever arm 35 allows relatively small movements, i.e. smaller ocean waves that may or may not be present in all of the quadrant areas 201 , to be utilized to drive the first level pumps 90 so as to capture the energy of the smaller waves and operate the first level air pumps 90 to create pressurized air delivery to the tank 2 . Additionally, support braces 298 are secured intermediate the air collection pipe 70 and main support rod 27 . The support braces 298 function to provide structural rigidity and a resistive force that allows the buoyant object 40 to move the lever arm 35 in a manner that effectively moves the piston 44 within first level air pumps 90 . This configuration inhibits the air collection duct 70 from moving in sync with the main support rod 27 in an upward direction, which would negate the amount of travel of the piston 44 within the first level air pump 90 . The support braces 298 are manufactured from a suitable durable material such as but not limited to metal tubing and/or metal rod. This configuration allows the wave powered energy conversion system 100 to capture wave motion that may only be present in a small area proximate thereto or when the natural ocean waves are smaller in size. It is contemplated within the scope of the present invention that any number of first level air pumps 90 could be present. Furthermore, it should be noted that FIG. 2 , herein illustrates only an exemplary configuration of first level air pumps 90 and buoyant objects 40 and it is contemplated within the scope of the present invention that the first level air pumps 90 and buoyant objects could be configured such that they completely surround the tank 2 in the aforementioned quadrant areas 201 .
Still referring to FIGS. 2 and 4 , a plurality of second level air pumps 85 are present. The second level air pumps 85 have second level pistons 86 operably disposed therein that are moved in a reciprocating manner by the second level piston rod 87 . The second level piston rod 87 is operably coupled to support rod 50 . Support rod 50 is secured to adjacent secondary support rods 30 distal to the second level air pumps 85 and is generally perpendicular with respect to the adjacent secondary support rods 30 . The second level air pumps 85 are driven by wave sizes that are larger than wave sizes that are operable to drive the first level pumps 90 . By way of example but not limitation, as a wave engages the buoyant objects 40 attached to secondary support rods 110 , 111 such that all of the buoyant objects 40 are lifted to a maximum height as allowed by the lever arms 35 this results in the upward movement of the secondary support rods 110 , 111 thus providing operation of the second level air pump 85 . The upwards-downwards movement of the secondary support rods 110 , 111 causes the second level piston 86 to completely cycle within the second level air pump 85 so as to create pressurized air. This configuration allows the wave powered energy conversion system 100 to utilize large waves to drive the plurality of second level air pumps 85 . While the second level air pumps 85 are illustrated herein as being operably coupled to support rod 50 so as to be operably connected to adjacent secondary support rods 30 , it is contemplated within the scope of the present invention that the wave powered energy conversion system 100 could be configured with second level air pumps 85 such that each second level air pump 85 is operably coupled to one secondary support rod 30 . Additionally, it is further contemplated within the scope of the present invention that any quantity of second level air pumps 85 could be present. Similarly to the first level air pumps 90 , the second level air pumps 85 are operably coupled to a second air collection pipe 75 so as to distribute the pressurized air generated by the second level air pumps 85 to the tank 2 in order to further increase the air pressure within the tank 2 . The second air collection pipe 75 is flexibly coupled to the tank 2 proximate end 74 . This flexible coupling allows for maintenance of a secured connection despite any possible movement of the second air collection pipe 75 .
Still referring to FIGS. 2 and 4 , the wave powered energy conversion system 100 further includes a plurality of third level air pumps 80 . The third level air pumps 80 are operably coupled with the tank 2 via duct 88 and as described herein for the first level air pumps 90 and second level air pumps 85 function to provide increased air pressure within the tank 2 . The third level air pumps 80 include piston 81 and piston rod 82 wherein the piston rod 82 is operably coupled to the main support rod 27 . The third level air pumps 80 are designed to capture the energy of a wave that exceeds the limitations of the first level air pump 90 and second level air pump 85 . If a wave size is present such that all of the buoyant objects 40 in a exemplary quadrant area 201 are lifted generally simultaneously, the buoyant objects 40 in the quadrant area 201 move the main support rod 27 in an upwards-downwards motion as large waves cycle past the wave powered energy conversion system 100 . As the buoyant objects 40 of an exemplary quadrant area 201 are all moved generally together by a larger wave, the third level air pump 80 generates pressurized air to be distributed to the tank 2 via duct 88 so as to increase the pressure within the tank 2 . It is contemplated within the scope of the present invention that numerous different quantities of third level air pumps 80 could be present. It should further be recognized that the wave powered energy conversion system 100 could be adapted to utilize more than three categories of wave sizes. Additionally, it is contemplated within the scope of the present invention that the wave powered energy conversion system 100 could be configured in a manner wherein the transition between the levels of air pumps 199 could occur at various different wave height ranges. The configuration of the wave powered energy conversion system 100 as detailed herein facilitates the capture of waves relatively small in height, such as but not limited to twelve inches in height to wave sizes that are relatively large in height such as but not limited to seventy-two inches. The plurality of first level air pumps 90 facilitates the ability for sufficient pressure to be developed within the tank 2 even during relatively calm ocean conditions.
Referring in particular to FIG. 3 , the air supply pipe network 18 is illustrated therein. The air supply pipe network 18 is operable to supply air to the air pumps 199 . The air supply pipe network 18 includes a main air supply pipe 20 that is operably coupled to the air tower 14 . As previously mentioned herein, the air tower 14 is pneumatically isolated from the tank 2 . Air enters the air supply pipe network 18 via opening 15 and flows through the main air supply pipe 20 . The main air supply pipe 20 is operably coupled to the third level air pumps 80 via tube 119 . Tube 119 is a conventional hollow tube having a passage that allows the transfer of air from the main air supply pipe 20 into the third level air pumps 80 where the air disposed therein can be pressurized and distributed to the tank 2 . The main air supply pipe 20 additionally has operably coupled thereto a plurality of secondary air supply pipes 120 . The secondary air supply pipes 120 function to provide airflow to the second level air pumps 85 so as to permit the second level air pump 85 to function as described herein. The secondary air supply pipes 120 extend generally perpendicular from the main air supply pipe 20 and function to further transport airflow to the tertiary air supply pipes 125 . The tertiary air supply pipes 125 are operably coupled to the first level air pumps 90 and function to provide airflow thereto in order to permit the first level air pumps 90 to function as described herein. While the air supply pipe network 18 is illustrated as having a particular configuration herein, it is contemplated within the scope of the present invention that the air supply pipe network 18 could be configured in numerous different manners and achieve the desired functionality as described herein. While not illustrated herein, it is contemplated within the scope of the present invention that the air supply pipe network 18 , air collection pipes 12 are isolated with conventional valves to ensure pneumatic isolation and to provide unidirectional airflow.
Illustrated in particular in FIG. 2 , an air outlet pipe 140 is operably coupled to the tank 2 . The air outlet pipe 140 is a conventional hollow pipe constructed of a suitable durable material. The air outlet pipe 140 functions to transfer the pressurized air stored within the tank 2 to a power-generating device such as but not limited to a turbine for electricity generation. While not illustrated herein, it is contemplated within the scope of the present invention that the air outlet pipe 140 is pneumatically isolated from the tank 2 with a conventional valve, wherein the valve functions to release the air within the tank 2 subsequent a pre-determined pressure having been achieved. A delivery air pump 145 is operably coupled to the air outlet pipe 140 . The delivery air pump 145 functions to provide pressurized assistance in moving the airflow through the air outlet pipe 140 . The delivery air pump 145 functions similarly to the air pumps 199 as described herein having a piston and a piston rod (not illustrated). The delivery air pump 145 is operably coupled to rod 147 . Rod 147 is movably coupled to the support ring 24 and further includes a float 146 distal to the support ring 24 . As described herein for the air pumps 199 , the delivery air pump 145 provides additional air pressure to the air outlet pipe 140 so as to assist in the transfer of air through the air outlet pipe 145 . While an air delivery pump 145 is illustrated herein, it is contemplated within the scope of the present invention that the wave powered energy conversion system 100 could be configured without the air delivery pump 145 . Air is transferred via the air outlet pipe 140 to an alternate location or device such as a turbine generator for use in generating electrical power.
Referring to the drawings submitted herewith, a description of the operation of the wave powered energy conversion system is as follows. In use, the wave powered energy conversion system 100 would be positioned within an ocean adjacent to a coastal area. The support posts 10 are secured to the ocean floor utilizing suitable techniques. As the buoyant objects 40 traverse across the surface of the undulating movement of the waves of the ocean the air pumps 199 begin to pressurize the air stored within the tank 2 . During the presence of small waves, the first level pumps 90 will operate independently of each other such that each lever arm 35 is moved in an upwards-downwards movement by the buoyant object operably coupled thereto. This provides operation of the first level air pumps 90 . During the presence of waves of sufficient height such that all of the buoyant objects 40 operably coupled to a secondary support rod 30 are lifted simultaneously, the second level air pumps 85 are activated and generate air delivered via the air collection pipes to the tank 2 and provide increased air pressure within the tank 2 . In the event of the presence of larger waves such that the wave height is sufficient to lift the buoyant objects 40 present in an exemplary quadrant area 201 , the third level air pumps 80 are activated and provide air to the tank 2 via duct 88 . Ensuing the tank 2 meeting or exceeding a predetermined air pressure, the air pressure is transferred to a power-generating device via the air outlet pipe 140 .
In the preceding detailed description, reference has been made to the accompanying drawings that form a part hereof, and in which are shown by way of illustration specific embodiments in which the invention may be practiced. These embodiments, and certain variants thereof, have been described in sufficient detail to enable those skilled in the art to practice the invention. It is to be understood that other suitable embodiments may be utilized and that logical changes may be made without departing from the spirit or scope of the invention. The description may omit certain information known to those skilled in the art. The preceding detailed description is, therefore, not intended to be limited to the specific forms set forth herein, but on the contrary, it is intended to cover such alternatives, modifications, and equivalents, as can be reasonably included within the spirit and scope of the appended claims. | A wave powered energy conversion system operable to convert the motion of ocean waves into a usable form of energy such as electricity. The wave powered energy conversion system includes a storage tank operable to store air pressurized to a pressure greater than that of atmospheric air. A frame assembly circumferentially surrounds the storage tank and consists of sub-frame assemblies organized into quadrants. The frame assembly is movable and has operably coupled thereto a plurality of buoyant objects. A plurality of air pumps are present that are connected to the frame assembly and further connected to an air delivery pipe network. The buoyant objects are operable to move at least a portion of the frame assembly so as to operate at least a portion of the plurality of air pumps so as to produce pressurized air to be distributed to the storage tank. | 5 |
FIELD OF INVENTION
This invention relates to the field of data processing and, more particularly, to improvements in method and apparatus for automatically initializing a data processing system, such as a personal computer, so as to allow the system to be operated when feature cards or adapters have been added to, removed from, or moved within the computer system.
BACKGROUND OF THE INVENTION
Commercially available IBM (TM) PS/2 (TM) personal computers constructed in accordance with Micro Channel (TM) architecture, are provided with a Programmable Option Select (POS) function which is used to define or provide settings for the assignment of system resources to a system board and various adapters. The POS Function is generally described in "IBM Personal System/2 Hardware Interface Technical Reference", First Edition (May 1988), published by International Business Machines Corporation, to which reference may be had for a more detailed description thereof.
Adapters provide the means by which various data processing devices or optional features can be connected into and operated as part of a personal computer system. Examples of such features are displays, printers, scanners, etc. In accordance with the above mentioned architecture, an adapter has a group of programmable registers, known as the POS registers, which, by convention, must store or contain predetermined POS information. Two registers store an adapter ID that uniquely identifies the specific adapter relative to other adapters. Four additional registers store an adapter card enabling/disabling bit and option select data, and two additional registers store subaddress extensions. Before an adapter can be used, an adapter description file (ADF) must be created by the supplier of the adapter. The ADF contains data necessary for the operation of the adapter and its related option or device, the data defining the resources the adapter can use, and the associated POS settings that indicate the resource assignment.
Each system includes a Reference Diskette containing System Configuration utilities or programs that identify the installed hardware and interpret the system resources (I/O ports or address space, memory address space, interrupt levels, and arbitration levels) for each device. Normally, the files on the Reference Diskette are copied onto a backup copy which is then used to configure the system. As options are added to the system, the files needed for configuration are merged onto the backup copy. During configuration, certain files are needed, the files being an ADF and any necessary Adapter Description Program (ADP). An option diskette is supplied for each adapter and contains the necessary ADF and ADP. Such files are merged onto the backup copy before a new adapter is installed.
An ADF contains various fields of information including the following: adapter ID; adapter name; the number of POS registers to be included; an optional field indicating that an adapter option will be specified next; a prompt keyword; a choice keyword including the choice name, a POS setting which programs the adapter appropriately, and a resource setting which identifies the resources used for the particular choice; and a help keyword.
In accordance with the prior art, a system such as described above has to be configured when the system is setup for the first time and thereafter each time an adapter is added to, removed from, or moved within the system. When the system is being configured, POS data is stored in a non-volatile memory. Thereafter, whenever the system is turned on, a Power On Self Test (POST) is performed during which the POS data is retrieved from the non-volatile memory and is used to establish the system configuration. Such test also recognizes when an adapter card is added to, removed from, or moved within the system. When this occurs all other feature cards (such as the disk controller adapter) are disabled in the system, and a display message is sent to the operator or user indicating that the system must be reconfigured before it can be further operated.
The obvious drawback of this existing POS sequence is that the addition of any new card to the system (or removal from the system, or simply a change of slot) requires that the system be reconfigured before the system can again be operational. For example, the removal of an asynchronous communications attachment card will cause the hard disk subsystem to be disabled (preventing operating system initialization from the hard disk). Disabling all other devices may not be necessary and may not provide the user with the maximum function possible. This restriction can be removed by the implementation of the invention which allows the system to be operated with the features that are not disabled.
The foregoing describes in general terms the prior art being improved upon, and such prior art is also believed to be the most pertinent or relevant to the invention. However, certain prior art items are also known which describe inventions useful in configuring data processing systems. U.S. Pat. No. 4,070,704- Calle et al, for AUTOMATIC RECONFIGURATION APPARATUS FOR INPUT/OUTPUT PROCESSOR, discloses a system in which all possible memory, I/0, and processor combinations are attempted, in order to automatically reconfigure the system when a bootstrap failure occurs during system startup.
IBM TDB Vol. 20, No.9, February 1973, pp. 3501-3502, discloses a modular relocate scheme in which RAMS are partitioned on a separate card, module, or chip in such a way that a processor will operate with or without a card, module, or chip.
SUMMARY OF THE INVENTION
One of the objects of the invention is to provide a method and apparatus for testing a data processing system, such as a personal computer, and allowing the system to be operated without the system being reconfigured, even though an adapter card has been added to, removed from, or moved within the system.
Another object is to provide a POST which disables non-video adapter cards that have been added to, removed from, or moved within a data processing system, and allows continued operation of the system without requiring reconfiguration.
A further object is to provide a power on test for a personal computer constructed in accordance with the IBM Micro Channel Architecture, after which test the computer can be operated without requiring reconfiguration even though an adapter has been added to, moved within, or removed from the computer.
Still another object is to provide data processing system with a power on test function in which all expansion slots are checked to compare actual adapter IDs with IDs stored during a prior configuration, and set flags in accordance with mismatch errors to allow the system to disable any slots in which a mismatch occurs.
Briefly, in accordance with the invention, a data processing system such as a personal computer includes a Power On Self Test (POST) during which adapter IDs are checked to determine if any adapters have been added, moved or removed, since a previous system configuration. If any adapters have been so altered, the system is placed in operation with all adapters enabled except for those which were altered.
DRAWINGS
Other objects and advantages of the invention will be apparent from the following description taken in connection with the accompanying drawings wherein:
FIG. 1 is a schematic diagram of a data processing system embodying the invention;
FIG. 2 is a flow chart of a portion of the prior art being improved upon;
FIG. 3 is a flow chart of another portion of the prior art being improved upon;
FIG. 4 is a flow chart of a portion of the invention; and
FIG. 5 is a flow chart of another portion of the invention.
DETAILED DESCRIPTION
Referring now to the drawings, and first to FIG. 1, the invention is embodied in a personal computer system 10, such as an IBM PS/2 computer constructed in accordance with Micro Channel architecture, and resides in the manner in which such computer is programmed and operated. It is to be appreciated that such a computer is complex and includes many components and devices so that the description provided below is limited to only those items which are useful in obtaining an understanding of the invention. System 10 includes a microprocessor 12, such as a commercially available Intel 80386 or 80486 microprocessor, the structure and operation of which are well known to those skilled in the art. Microprocessor 12 executes programs, stored in a random access memory (RAM) 14 and a read only memory (ROM) 17 and controls the general operation of system 10.
System 10 also includes a circuit or bus network 15 operatively interconnecting the various elements of the system. A CMOS (complementary metal oxide semiconductor) RAM 16 is connected to and backed up by a battery 18 and provides a non-volatile storage in a table 19 of information used in the invention as described hereinafter. Table 19 contains a plurality of entries corresponding in number to the number of expansion connectors or slots in the system. The position in the table of each entry corresponds to the slot number for such entry. Each entry contains a first field for storing a two byte configured adapter ID, a second field indicating how many bytes of POS data are in a third field, and a third field for storing the POS data defining the system resources assigned to the adapter identified in the first field. During configuration of the system, the appropriate entries are stored in table 19. A configured adapter ID is either the actual ID of an adapter plugged into the corresponding slot and connector at configuration time, or a pseudo adapter ID indicating that such slot and connector are empty and have no adapter plugged therein. If a slot is empty, a pseudo adapter ID or default value of FFFF(Hex) is stored.
Bus network 15 is further connected to a plurality of channel connectors CC1-CCn. Such connectors are also known as expansion connectors and provide the means by which various devices or optional features can be added to the system. Such connectors are designed to receive adapters or printed circuit boards having edge connectors thereon, the adapters being plugged into slots in the connectors. The terms "adapters", "adapter cards", "feature cards", and "cards" are synonyms used interchangeably herein. Each different connector has a unique slot number Sx, the illustrated connectors being assigned slot numbers S0-S(n-1). A video adapter 20 is plugged into slot S1 of connector CC2 and is connected to a display 22. A feature adapter 24 is plugged into slot S0 of connector CC1 and is connected to a feature 26. The remaining connectors are empty, i.e. not connected to any adapter, and allow additional features to be added. Each adapter has a register A for storing an adapter ID that uniquely identifies the type of adapter, and registers B that store an enabling/disabling bit and POS data, such registers being respectively indicated by the references 20A, 20B, 24A and 24B in FIG. 1. These registers correspond to and are known as the POS registers 0-7 as defined by the above-mentioned Micro Channel architecture. During POST, the POS data from table 19 is written in the respective POS registers of the adapters.
System 10 further includes an adapter enable/setup register 28 connected to bus network 15. Register 28 is an eight bit register in which the bits are numbered 0-7. Bits 0-2 are address bits identifying the connectors by their slot numbers. Bit 3 enables or disables a card setup signal. When enabled during setup, bit 3 allows reading to and writing from the card located in the slot addressed by bits 0-2. Bits 4-6 are not used. Bit 7 is used to activate a channel reset signal sent to all connectors. Register 28 is used to scan or search through all the slots or connectors and read the actual adapter IDs of all adapters plugged into such slots. If a slot is empty, the adapter ID read operation returns a pseudo adapter ID of FFFF(hex), indicating that the slot is empty.
PRIOR ART POST OPERATIONS
The structure and operation of the system as thus far described is in accordance with the prior art, and it is felt that, for a better understanding of the invention, a short description of the prior art POST operation is useful. At the start it is assumed that the system has been correctly configured previously and that power was turned off. When system 10 is subsequently turned on, the prior art POST routine is executed. Such routine performs many different functions and only those necessary to understand the invention will be described. At some point, the POST routine performs the operations shown in FIG. 2. Step 40 initializes register 28 by setting bits 0-2 thereof to "0" to indicate the address of the first slot in the system. Step 42 then sets bit 3 of register 28 to the setup mode thus allowing step 44 to read the adapter ID from the card in slot S0. As illustrated, such action would read the ID of feature adapter 24. Step 46 reads from table 19 the adapter ID from the entry corresponding to the same slot number, and the two IDs thus read are compared in step 48. If they are the same, step 50 reads the corresponding POS data from table 19 and writes it into the appropriate POS registers B of the adapter. Step 52 determines if all slots have been so analyzed. If not, step 54 sets register 28 to the next slot address, and the loop is repeated.
If step 48 determines there is a mismatch, step 58 logs such determination as indicating an ID mismatch error has occurred. The mismatch would occur when there is a different adapter in the slot than when last configured, when there is an adapter in the slot when there was none when last configured, or when there is no adapter in the slot when there was one at the last configuration. Step 58 passes control to step 52. After all slots have been checked, the POST routine continues further operations in step 56. Later, step 60 checks to see if an ID mismatch error occurred. If none did, control is passed to step 62 and the POST routine completes as normal and finally passes control to step 64 which then boots up the operating system and allows step 65 to operate the system with all the optional features.
If an ID mismatch error occurred, step 60 branches to step 66 (FIG. 3) which turns off all the adapters in the system. Steps 70-78 then search through the adapters in the system until the video adapter 20 is located and step 74 iteratively turns off all slots other than the video adapter slot. When the video adapter is found, step 80 initializes it thereby allowing an error message to be sent to the display 22 informing the user of the need to reconfigure the system. Step 80 passes control to step 82 which then finishes off whatever other POST operations need to be done, and control passes to step 84 to send a message to the user indicating a need to reconfigure the system. The system is then reconfigured by powering up the system with the Reference Diskette in step 86 and running the system automatic configuration program in step 87.
Such prior art operations can be summarized as follows. A POS phase of POST is performed or executed during which each feature slot in the system is individually placed into card setup mode. Card setup mode is a special state (as described by the IBM Micro Channel Architecture) which allows a system feature to be configured via software. Each feature card can present its card ID when it is placed in card setup mode. This card ID is read by POST and compared to a value in a table stored in the non-volatile memory, which table is established when the system setup utility is executed. This table has the card ID and POS data information for each feature card slot in the system. If the card ID read from the feature card does not match the card ID stored in the non-volatile memory table then an ID mismatch error is logged and no further action is performed on this particular feature card slot. When the IDs do match then the POS data from the non-volatile memory table is programmed into the adapter card. By programming the POS data into the adapter card, the card is configured.
Later in POST, the ID mismatch error flag is checked to see if an ID mismatch error occurred. If an ID mismatch error occurred, then all slots are disabled and POST searches for a video adapter. All slots are disabled to insure that no addressing conflicts occur if the video adapter is found and enabled. A video adapter, if present, must be initialized to insure that error messages are displayed to the user. If a video adapter is found only the slot that contains the video adapter is enabled. This scheme leaves all cards turned off (except for a possible video card). This forces the user to rerun the IBM setup utility (from the reference diskette) before the adapter cards of the system are allowed to be operational. Once reconfiguration has been performed, the system can be restarted and the operating system loaded from disk.
THE INVENTION
A mechanism is provided which records which slots contain feature cards or adapters with IDs that correctly correspond to the IDs in POS table 19. This mechanism also identifies which slots generate an ID mismatch error. To be able to correctly identify which slot or slots are involved in a card ID mismatch, a word 101 of RAM 14 is used. This word is referred to as SLOTFLAG. Each bit in SLOTFLAG 101 corresponds to a different slot. Any unused bits can be reserved for expansion. The original functions of FIG. 2 are modified to support the SLOTFLAG designator. This modification is shown in FIG. 4.
When a card slot is found to have a feature card with an ID that does not match the ID stored in table 19, the bit position corresponding to the failing slot is set in SLOTFLAG. The functions of FIG. 3 are modified as shown in FIG. 5 to use the SLOTFLAG designator. This allows for all correctly configured slots to remain enabled if a correctly configured video card is present. All correctly configured slots will remain enabled if no video card is present. If a video card is found which also caused a card ID mismatch error, then all slots but the video slot are disabled. This disabling insures that no addressing conflicts occur.
FIGS. 4 and 5 show the improved operations of the invention. Those operations which are the same as those of the prior art are indicated with the same references as used in FIG. 2 and 3. New steps are indicated with references 100 and higher. Referring now to FIG. 4, POST routine 32 begins the improved operation with step 100 accessing SLOTFLAG 101 and clearing it by setting all bits to indicate that no adapter has been added, removed or moved. Except for step 102, all the remaining steps in FIG. 4 occur as in the prior art process previously described. Step 102 occurs when there is an ID mismatch error and it sets or marks the bit in SLOTFLAG 101, which bit corresponds to the slot number where the error arose, to indicate an error occurred in such slot. Later, as result of such error having been logged in step 58, step 60 branches to step 66 (FIG. 5).
Step 66 first disables all the adapters. Then, a series of steps places all the adapters in a setup mode and either enables or disables such adapters in accordance with the non-occurrence or occurrence of an ID mismatch associated therewith. For a non-video card, step 104 checks to see if the corresponding SLOTFLAG bit has been marked. If it has not been marked, step 106 enables such adapter. If it has been marked, step 106 is bypassed leaving such card disabled from step 66. If the card is a video card, step 108 checks to see if the corresponding SLOTFLAG bit has been marked. If such bit has not been marked, step 110 enables all other correct slots. If the bit in SLOTFLAG corresponding to the video card has been marked, step 108 branches to step 112 which turns all other cards off. Then, steps 80-87 are performed to reconfigure the system. After all slots have been checked, and upon completion of step 110, control passes to step 82 where any remaining steps of the POST are performed and a message is sent to the user in step 114 recommending that the system be reconfigured in order to get the full function from all adapters. The user can then choose to reconfigure the system by steps 86 and 87 or operate the system in step 116 using only those adapters that are enabled. Step 116 can not be done with the prior art system described above.
In summary, the invention enhances system operation in the situation where feature cards have been added to, removed from, or moved within the computer system. For minor changes, such as a printer port addition, no loss of system function is experienced. All previously operational feature cards will continue to be so. Before the invention, the system would have no operational cards except possibly the error path video adapter and hence be unusable until reconfiguration.
It should be apparent to those skilled in the art that many changes can be made in the details and arrangements of steps and parts without departing from the scope of the invention as defined in the appended claims. | A data processing system such as a personal computer includes a plurality of expansion connectors for receiving adapter cards. A non-volatile memory stores programmable option select (POS) data that is stored when the system is configured. A Power On Self Test (POST) operation is performed during which adapters are checked to determine if any have been added, moved or removed, since a previous system configuration. If any have been so altered, the system may be placed in operation with all adapters enabled except for those which were altered. | 6 |
FIELD OF THE INVENTION
[0001] The invention refers to a method for treating the pathological lesions of the skin that normally develop due to the ultraviolet (UV) radiation of the sunlight.
BACKGROUND OF THE INVENTION
[0002] Exposure of human skin to sunlight has several known unpleasant effects such as sunburn and pathological lesions leading to carcinogenesis. Due to the ultraviolet radiation of sunlight, free radicals (e.g. hydroxy radicals or nascent oxygen) form in the skin. Such free radicals can injure the DNA of skin cells and contribute to photoaging of the skin.
[0003] Photoaging is characterized by clinical, histological and biochemical changes which differ from alterations in chronologically aged but sunprotected skin [Herschenfeld, R. E. et al.: The cumulative effect of ultraviolet radiation on the skin photoaging, in Photodermatology, Hawk, J. L. M. , Ed., Arnold, London, Sydney, Oakland, 1999, 89-102]. Photoaging includes changes attributable to chronic sun exposure and results in dry skin, wrinkling, laxity or even a variety of benign neoplasms.
[0004] Free radicals having a powerful oxidizing effect can injure the membrane of cells by oxidizing the unsaturated fatty acid components of the membrane (peroxidization of lipids). Also, reactive aldehydes are formed during the oxidization. In the injury of the membrane, increased intake of calcium leads to cell death, and pathological processes are started due to the presence of the reactive aldehydes:
[0005] injury of DNA, resulting in mutation in both the cell nucleus and mitochondria;
[0006] changes in the properties of the interstitial proteins (i.e. elastin) owing to the formation of crosslinks.
[0007] It is known that the elastic structures of collagen proteins and elastin contain a lot of water. It is characteristic of the interstitial proteins that they are rich in lysine. The reactive aldehydes such as malondialdehyde result in condensation reactions with the protein side chains containing amino groups to yield crosslinks. Thus, the originally elastic structure of the skin becomes rigid and hydrophobic. During the above process, at first lipofuscin ceroids, then age pigments are formed.
[0008] The natural protective mechanism against UV radiation include bronzing due to the formation of melanin, DNA repair mechanisms, etc. Deficiency of a protective mechanism such as DNA repair, with consequent loss of the correction of the DNA injuries caused by UV radiation leads to early photoaging of the skin. Xeroderma pigmentosum is a disease characterized by deficiency of DNA repair that can be accompanied by the development of a malignant tumor. Sunburn spots caused by bronzing in early childhood are photodamage that heals, leaving an extended scar that can result in spinocellular carcinoma or even in various malignant tumors (e.g. melanoma, cerato-acanthoma, basalioma, sarcoma).
[0009] Thus, UV radiation-induced injury to the skin can be subdivided into acute photodamage (e.g. sunburn) and chronic photodamage (e.g. photoaging, actinic keratosis, and, ultimately, skin cancers).
[0010] Actinic keratosis is a common sun-induced precancerous neoplasm confined to the epidermis. It is the initial manifestation of a continuum of clinical and histologic abnormalities that progresses to invasive squamous cell carcinoma, a disorder that accounts for thousands of death in the USA each year. [Schwartz, R. A.: The Actinic Keratosis, Dermatol. Surg., 23, 1009-1019 (1997).]
[0011] Actinic keratosis has been known by a variety of names, including solar keratosis, senile keratosis, senile hyperkeratosis, keratoma senile, and keratosis senilis. The actinic keratosis is a skin-colored to reddish brown or yellowish black ill-defined round or irregularly shaped macule or papule with a dry firmly adherent scale. It is usually 1-3 mm in diameter, but varies up to several centimeters, and can be seen on sun-exposed body regions in persons with many years of solar exposure.
[0012] Since the actinic keratosis is the most common precancerous skin lesion, there is an existing demand for a method that is efficient in the treatment of the pathological lesions of the skin to avoid the formation of more severe forms e.g. actinic keratosis. As a matter of fact, with the excepton of new-born babies, parts of the skin surface of nearly everybody have been exposed to the UV radiation of sunlight for a shorter or longer time, consequently, some sorts of pathological lesions of the skin develop when a higher age is reached.
[0013] The hydroximic acid derivatives of Formula I below are known from Hungarian Patent No. 177 578 and its equivalent U.S. Pat. No. 4,308,399. The known compounds are suitable for the treatment of diabetic angiopathy.
DESCRIPTION OF THE INVENTION
[0014] The invention refers to a method for treating the pathological lesions of the skin that develops by UV radiation of the sunlight comprising applying to the affected skin surface an effective amount of a hydroximic acid derivative of Formula
[0015] wherein
[0016] R 1 is a hydrogen atom or a C 1-5 alkyl group;
[0017] R 2 is a hydrogen atom or a C 1-5 alkyl group, a C 5-7 cycloalkyl group or a phenyl group optionally substituted by a hydroxy group; or
[0018] R 1 and R 2 together with the nitrogen atom to which they are attached form a 5-to 8-membered ring that optionally comprises one or more further nitrogen or oxygen atoms, wherein said ring can be optionally condensed with a benzene ring;
[0019] R 3 is a hydrogen atom, a phenyl group, a naphthyl group or a pyridyl group wherein said groups can optionally be substituted by one or more halo atoms or C 1-14 alkoxy groups;
[0020] A is a group of Formula
[0021] wherein
[0022] R 4 is a hydrogen atom or a phenyl group;
[0023] R 5 is a hydrogen atom or a phenyl group;
[0024] m has a value of 0, 1 or 2; and
[0025] n has a value of 0, 1 or 2;
[0026] or a physiologically acceptable acid addition salt thereof in form of a composition suitable for local treatment.
[0027] The aim of the invention is to provide a method for the prevention or reduction of the pathological lesions of the skin.
[0028] It was found that the above aim is fulfilled by the method of the invention according to which the skin surface affected by the UV radiation of the sunlight is treated with a composition suitable for local treatment and containing an effective amount of a hydroximic acid derivative of Formula I or a physiologically acceptable acid addition salt thereof.
[0029] “Treating the pathological lesions of the skin” means both preventing the formation of the pathological lesions of the skin and reducing the pathological lesions of the skin. Thus, when the skin is treated with a composition suitable for local treatment and containing an effective amount of a hydroximic acid derivative of Formula I or a physiologically acceptable acid addition salt thereof before each exposure to UV radiation of the sunlight—practically no further photodamage is experienced while the skin is repeatedly exposed to UV light radiation of the usual intensity during outdoor activities or outdoor staying for a longer time i.e. years or decades.
[0030] In case of a human being practically without any signs of pathological lesion, the formation of such lesion can be prevented by the method of the invention. In case of a human being with accumulated expositions to the UV radiation of the sunlight in the past and, thus, with some degree of pathological lesion of the skin, no deterioration is experienced on further exposition to the UV radiation when the exposed skin surface is regularly treated according to the method of the invention. For example, in case of a farmer who have spent decades in outdoor work, macules of actinic keratosis may appear on the neck or forearm exposed to the UV radiation of the sun. Once these macules are removed surgically to avoid the formation of carcinoma, and the exposed skin surface is regularly treated with a composition suitable for local treatment and containing an effective amount of a hydroximic acid derivative of the formula I or a physiologically acceptable acid addition salt thereof, further macules of actinic keratosis do not develop, although, the farmer continues his earlier activities.
[0031] The pathological lesions of the skin include especially the followings:
[0032] dry skin;
[0033] actinic keratosis, purpura senilis;
[0034] polymorphic light exanthema;
[0035] toxic photopathy;
[0036] photo-allergy;
[0037] solar atrophy of skin;
[0038] puberal strias (stria migrans);
[0039] elastoma diffusum (old skin);
[0040] X-ray dermatitis;
[0041] gouty polychondritis;
[0042] decubitus (bedsore).
[0043] The term “composition” as used herein means a formulation that is suitable for local or topical treatment and which is applied to the skin surface in a conventional manner.
[0044] The composition employed according to the method of the invention comprises a hydroximic acid derivative of Formula I or a physiologically acceptable acid addition salt thereof as the active ingredient in admixture with one or more conventional carrier(s) of topical compositions that are suitable for the treatment of the skin surface.
[0045] A C 1-5 alkyl group is, for example, a methyl, ethyl, n-propyl, isopropyl, n-butyl or n-pentyl group, preferably a methyl or an ethyl group.
[0046] A C 5-7 cycloalkyl group is a cyclopentyl, cyclohexyl or cycloheptyl group, preferably a cyclopentyl or cyclohexyl group.
[0047] A 5-to 8-membered ring containing a nitrogen atom and optionally one or more further nitrogen or oxygen atoms can be, for example, a pyrrole, pyrazole, imidazole, oxazole, thiazole, pyridine, pyridazine, pyrimidine, piperidine, piperazine, morpholine, indole or quinoline ring.
[0048] A halo atom is, for example, a fluoro, chloro, bromo or iodo atom, preferably a chloro or bromo atom.
[0049] A C 1-4 alkoxy group is, for example, a methoxy, ethoxy, isopropoxy, n-propoxy or n-butoxy group, preferably a methoxy or ethoxy group.
[0050] The physiologically acceptable acid addition salts of the compounds of Formula I are the acid addition salts formed with physiologically acceptable inorganic acids such as hydrochloric acid, sulfuric acid, etc. or with physiologically acceptable organic acids such as acetic acid, fumaric acid, lactic acid, etc.
[0051] A preferred subgroup of the compounds of Formula I consists of the hydroximic acid derivatives of Formula I wherein R 1 and R 2 together with the nitrogen atom to which they are attached form a piperidino group, R 3 is a pyridyl or a phenyl group and A represents a group of the formula a , wherein m and n have a value of 0. An especially preferred compound is the following: O-(3-piperidino-2-hydroxy-1-propyl)nicotinic amidoxime (Compound “A”).
[0052] The compounds of Formula I can be prepared by the processes known from U.S. Pat. No. 4,308,399.
[0053] The composition suitable for local or topical treatment of the skin surface contains, in general, 0.1 to 30% by mass, preferably 5 to 15% by mass of a hydroximic acid derivative of the formula I or a physiologically acceptable acid addition salt thereof as the active ingredient and conventional carriers used in topical formulations. The composition used according to the method of the invention includes mainly creams and liniments based on water/oil or oil/water emulsions.
[0054] The conventional carriers used in topical formulations are basically the same ones employed in cosmetic formulations, for example, one- or two-basic alcohols having a saturated or an unsaturated carbon chain such as cetyl alcohol, stearyl alcohol, cetylstearyl alcohol, oleyl alcohol, lauryl alcohol, ethylene glycol, propylene glycol, glycerol, etc.; natural fats and oils such as olive oil, wheat-germ oil, maize-germ oil, lanolin, cocoa-butter; higher hydrocarbons such as vaseline oil, vaseline; beeswax; cellulose derivatives; emulsifiers such as sodium lauryl sulfate, fatty acid or oleic acid esters of sorbitan, fatty acid or oleic acid esters of poly(ethylene glycol), sorbitan ethers of fatty alcohols or oleic alcohols, poly(ethylene glycol) ethers of fatty alcohols or oleic alcohols, glycerides of fatty acids, etc.; preservatives such as methyl p-hydroxybenzoate, chlorohexidine gluconate, etc.
[0055] The composition employed according to the method of the invention is prepared by blending the ingredients thereof in a manner known per se. In general, the ingredients of the fatty phase and those of the aqueous phase are separately admixed, then the two phases are blended using elevated temperature, if required. The active ingredient of Formula I is added, preferably in an aqueous solution, to the fatty phase or to the mixture of the other ingredients.
[0056] The effect of the hydroximic acid derivatives of Formula I on the formation of the pathological lesions of the skin was studied in the following test.
[0057] Age-matched groups of hairless mice were pretreated with the cream of Example 3 (that contained 15% of O-(3-piperidino-2-hydroxy-1-propyl)nicotinic amidoxime monohydrochloride as the active ingredient) or the vehicle prior to UVB exposure in the uncovered area of skin surface of the back, then the pretreated areas were exposed to UVB radiation in a dose that causes minimal erythema (1 MED) to induce photoaging. A Waldmann UV 8001 K light booth (Waldmann) equipped with UV21 Philips lamps (13 tubes) was used as UVB source. The major peak of these lamps is at 313 nm. The minimal erythema dose (MED) energy of the UVB irradiation (i.e. the energy of UVB irradiation required to produce the minimally perceptible erythema reaction of the skin) was determined on six unprotected skin surface areas (0.25 cm 2 each) of animals exposed to increasing doses (0.07 to 0.32 J/cm 2 with an increment of 0.05) of UVB. All other body sites were covered. Reading was carried out 24 hours after UV exposure.
[0058] The procedures of pretreatment and UVB exposure were repeated five times weekly, and the test lasted for 32 weeks. At the end of each week, the macro- and micromorphological changes of the exposed skin surfaces were detected. The pretreated and exposed animals were compared to the untreated-unexposed control group of animals undergoing chronological aging process without photoaging. Animals were scored for skin lesions and the appearance and number of skin tumors were detected.
[0059] The first tumor appeared 18 weeks after starting UV exposure in vehicle-pretreated animals. By week 23, all animals in this group (i.e. 12 animals) had one or more skin tumors of at least 1 mm diameter. At the end of the UV treatment (week 32), all lesions were examined histologically. Histopathological changes in elastic fiber network were recognized by Orcein-Giemsa staining, thickening of the epidermis and carcinogenesis were followed by H&E staining and immunohistological reaction with p53 antibody.
[0060] In case of UV-exposed animals pretreated with the composition of Example 3, no pathological changes could be observed except a 1.5-2-fold thickening of the epidermis with hypergranulosis. Thus, it could be established that pretreatment with the tested hydroximic acid derivative protected against the manifestation of an in situ or invasive carcinoma during the 32-week study period.
[0061] It is to be noted that in case of mice, the expectation of life amounts to about 2 years i.e. 104 weeks, thus, the 32 weeks'UV exposure period corresponds to about 30% of the length of life of a mouse. In men, this means more than 20 years of UV exposure, consequently, a rather long-lasting UV exposure was simulated.
[0062] In summary, from the above test it follows that long-lasting UVB exposures of the skin surface, without suitable protection thereof, produce skin tumor, while the hydroximic acid derivatives of Formula I can prevent the incidence of pathological changes of the skin, consequently, neither precancerous skin lesions, nor skin tumor forms.
[0063] The invention is further elucidated by means of the following Examples.
EXAMPLE 1
CREAM (Oil/Water)
[0064] [0064] The cream consists of the following ingredients: compound ,,A” 5.0% by mass cetylstearyl alcohol 7.5% by mass stearic acid 9.0% by mass glycerol monostearate 2.0% by mass sodium lauryl sulfate 0.5% by mass methyl p-hydroxybenzoate 0.1% by mass distilled water 75.9% by mass 100.0% by mass
[0065] The lipophilic ingredients (cetylstearyl alcohol, stearic acid and glycerol monostearate) are melted over a water bath. The sodium lauryl sulfate and methyl p-hydroxybenzoate are dissolved in about 38% by mass of distilled water at 60 to 65 ° 0 C., the pH of the solution is adjusted by the addition of diluted aqueous sodium hydroxide solution to a value of 9 to 10, then the aqueous solution is admixed into the mixture of the lipophilic ingredients, and the emulsion obtained is stirred until cold. The active ingredient is dissolved in the remaining water, and the solution is admixed into the cooled cream.
EXAMPLE 2
CREAM (Water/Oil)
[0066] [0066] The cream consists of the following ingredients: compound ,,A” 5.0% by mass cetylstearyl alcohol 12.0% by mass white wax 10.0% by mass neutral oil 35.0% by mass Imwitor ® 780 K (partial glycerides 5.0% by mass of vegetable fatty acids) methyl p-hydroxybenzoate 0.1% by mass distilled water 32.9% by mass 100.0% by mass
[0067] The ingredients are blended using the method described in Example 1.
EXAMPLE 3
CREAM (Oil/Water)
[0068] [0068] O-(3-piperidino-2-hydroxy-1-propyl)nicotinic 15.0% by mass amidoxime monohydrochloride glycerol 6.8% by mass stearic acid 2.0% by mass cetyl alcohol 2.0% by mass white petrolatum 1.0% by mass topical light mineral oil 2.0% by mass Ceteareth ® 6 [poly(ethylene glycol)cetostearyl 0.5% by mass ether] Ceteareth ® 25 [poly(ethylene glycol)cetostearyl 0.5% by mass ether] methyl p-hydroxybenzoate 0.1% by mass propyl p-hydroxybenzoate 0.1% by mass distilled water 69.5% by mass 100.0% by mass
[0069] The ingredients of the oil phase (stearic acid, cetyl alcohol, white petrolatum, topical light mineral oil, Ceteareth® 6 and Ceteareth® 25) are heated to 75° 0 C. under stirring, thus, a melt of the oil phase is obtained. The glycerol, methyl and propyl p-hydroxybenzoate are dissolved in the distilled water while heating the solution to 75° C. In the clear solution obtained, the active ingredient is dissolved at the same temperature resulting in the aqueous phase. The oil phase is poured to the aqueous phase at 75° C. under constant stirring, then the mixture is homogenized under intensive stirring and allowed to cool under stirring. The cooled cream is filled into suitable containers.
EXAMPLE b 4
CREAM (Oil/Water)
[0070] [0070] O-(3-piperidino-2-hydroxy-1-propyl)nicotinic 20.0% by mass amidoxime monohydrochloride glycerol 6.8% by mass stearic acid 2.0% by mass cetyl alcohol 2.0% by mass white petrolatum 1.0% by mass topical light mineral oil 2.0% by mass Ceteareth ® 6 [poly(ethylene glycol)cetostearyl 0.5% by mass ether] Ceteareth ® 25 [poly(ethylene glycol)cetostearyl 0.5% by mass ether] methyl p-hydroxybenzoate 0.1% by mass propyl p-hydroxybenzoate 0.1% by mass distilled water 64.5% by mass 100.0% by mass
[0071] The ingredients are blended using the method described in Example 3. | The invention relates to methods for prevention and/or treatment of skin lesions caused by exposure to ultraviolet radiation. Exemplary condition that can be prevented or treated are actinic keratosis, dry skin,polymorphic light exanthema, photopathology, photo-allergy, solar atrophy, stria migrans, elastoma diffusum, X-ray dermatits, gouty polychondritis and decubitis ulcer. The method employs application to the skin of a composition comprising a hydroximic acid derivative of the formula | 8 |
SUMMARY
[0001] Machine and method for cold semi-continuous bending of low ductility profiles ( 3 ) of the type that comprises a horizontal bed ( 1 ) and an interchangeable tool ( 4 ) against which the bending of the profile ( 3 ) is generated.
[0002] The machine consists of a support frame ( 10 ). The tool ( 4 ) is located in an area delimited by the bed ( 1 ), vertical supports ( 5 ) of the tool ( 4 ) and a compression plate ( 7 ) operated by vertical press cylinders. The tool ( 4 ) is located in front of an operation plane defined by a double set of positioning hydraulic cylinders ( 23 ) and a pusher ( 20 ).
[0003] The bent profiles ( 3 ) can be used for tents, skylights, facade profiles, sun protection slats, or trirail bodywork for truck tarps, guaranteeing the homogeneity of the bend in all the bent profiles, without the profile being stuck in the machine during its bending.
OBJECT OF THE INVENTION
[0004] This invention belongs to the field of the technique of machinery and methods for semi-continuous cold bending of materials of low elastic limit, such as aluminium, manufactured by extrusion. It is specifically for profiles of any length, type, cross-section area and bending.
BACKGROUND OF THE INVENTION
[0005] Roller or cylinder bending machines are known in the state of the art, where a bend is generated on aluminium or other material profile by the action of three rollers located in the same plane. In this way, two rollers are placed on one side of the profile and the third roller is placed on the opposite side of the profile. This latter roller, the bending or deforming roller, is the one that exerts the transverse force on the profile (i.e. the stress in the direction of the radius of the desired bend) in order to achieve its deformation or bending; while the other two rollers serve as support and act as pull cylinders. With these machines, the profile is subjected to bending on the deforming roller in its length, thus generating a progressive deformation (as the deforming roller advancement increases) until it achieves the desired bend in the profile. This type of roller bending machines have limited use for bending of small section aluminium profiles or small or large section steel profiles because the roller support on the profile is made only on one line (line of contact). This causes that, in order to avoid deformation because of the roller “getting stuck” on the profile, the material to be bent has either to be subjected to very little stress to overcome its elastic limit and to obtain a deformation as is the case of aluminium profiles in low section profiles, or else it must be a material with high resistance to deformation, as is the case of steel profiles, that although needs more effort to generate a permanent deformation, its high resistance prevents the rollers getting stuck in the profile.
[0006] Also known in the state of the art are arch bending machines, where the bend is executed on the profile by simultaneously exerting two stresses: one perpendicular to the length of the profile against a tool which generates the bend, and another in the longitudinal direction so that between the two a deformation force can be achieved to generate a permanent deformation in the profile. This type of machines are used for open profiles and of short length since they are limited in that the size of the tool that exerts the deformation must be equal to the size of the bend to be made, therefore not allowing a bend of a semi-continuous type. Therefore, they are not valid machines for closed cross-section profiles either, since executing the two necessary forces for the process on the mentioned type of closed profile would bring to closure of the inner recess of the profile.
[0007] Also known in the state of the art is the tube bending machine, round bars and other elongated materials described in patent U.S. Pat. No. 5,862,698, which is provided with a positioning plate with a through hole for profile to pass to a bent or folded template. The folding template is connected to a pivotable element by the action of a hydraulic cylinder. This machine guides the profile to bend with nothing that would support the bent profile, which will bring to non-flat (i.e. twisted) bends due to stresses that will be generated during the bending process.
[0008] Likewise, patent US2008184758 describes a machine for bending of sharp-angled profiles thanks to operation of a rotating roller, driven by a hydraulic roller, on the profile which in turn is supported against a cylindrical matrix that allows to make a curve at the sharp angle by successive bends of the profile. This type of machine is known by the tube bending companies of the naval, petrochemical industry, and in smaller version, for pipes of domestic use, copper, water systems and heating of houses. As the cylinder rests in the line on the profile to be bent (line of contact), the increase of stress on the profile to be bent may bring to the risk of the profile “getting stuck”.
DESCRIPTION OF THE INVENTION
[0009] The machine and method object of this invention overcomes the disadvantages of the aforementioned methods in a simple and effective manner.
[0010] It is a machine that allows different types of combinations of cold bending of aluminium profiles usually made by extrusion: semi-continuous bending, single radius bending, bending with different radiuses in different sections of the profile, or bendings of variable radius. All in aluminium profiles of any length, of open or closed type, with cross-sections inscribed in a rectangle normally of dimensions of up to 450×450 mm or equivalent, and of different lengths in a single piece of 0.25 to 30 meters.
[0011] The bent profiles can be used for tents, skylights, etc., or facade profiles, including curtain walls, as well as for sun protection slats, trirail bodywork for truck tarps, etc., guaranteeing the homogeneity of the bend in all the bent pieces, without the profile being stuck in the machine during its bending or its transversal section closing in case of closed cross-section profiles.
[0012] The machine object of this invention consists of:
A horizontal bed At least one support frame on the bed and the perpendicular, with at least two feet supporting a horizontal beam raised on the bed. A tool ( 4 ) on which the bend is generated on the profile to be bent which is interchangeable, existing in different sizes/dimensions. At least one vertical support of the mentioned tool located on the bed, which can coincide with the mentioned foot of the frame. A double set of hydraulic cylinders, each set located on each side of the central axis of the machine (X) and in a plane lying on the bed, parallel to this and facing/acting on the mentioned tool; and composed of: a hydraulic pusher cylinder connected via a movable sliding point through a guide to a positioning hydraulic cylinder connected on its other hand to a vertical element operated by a point of the fixed rotating support. The mentioned guide is fixed on the bed. The pushing hydraulic cylinder may be supported by a secondary guide. The free end of the pusher cylinder supports a pusher plate. Each of these pusher cylinders ( 20 ) is equipped with a transducer. Presser cylinders perpendicular to the bed, supported by the beams of the support frame and holding a compression plate parallel to the bed for compensation of stresses made in the profile to be bent. The mentioned presser cylinders incorporate sensors for measuring the position, load, etc. to provide information on the working parameters. A single hydraulic pump activating all the cylinders (pushers, positioners and pressers) through valves connected to each cylinder. Alternatively, several hydraulic pumps, each connected to each cylinder or type of cylinder, may be installed. Indicators of various types (position, mechanical load of the cylinders, etc.) connected to sensors and transducers of the cylinders, and which allow to display the operation and control parameters and control over the process of bending on the screen (for instance, that of the control computer).
[0022] Thus, the machine has a rectangular recess of variable height, which is where the tool and the profile to be bent are located. The lateral section of this recess has a variable height delimited by the compression plate and a width delimited by the feet of the frame.
[0023] The operation plane of the positioning and pusher cylinders, parallel to the bed, is preferably placed at half the height of the tool. Therefore, it is desirable that the guide and the rotating fixed support can be adjustable in height.
[0024] Therefore, the machine object of the present invention provides a number of improvements described below:
[0025] When bending a low ductility profile on the tool selected from those of length and shape suitable for the mentioned profile (i.e. depending on the length of the desired bend, for example a standard length of 2.000 mm), the initial contact of the profile on the tool is a line (a contact line between the bent surface of the tool and the straight surface of the profile) but, however, when a minimal deformation is made on the profile, the mentioned contact line becomes a surface of contact equivalent to the length of contact line multiplied by the length of deformation produced in the profile. Thus, this contact surface increases with the increase of the deformed zone and causes the increased load on the profile to shift from elastic to plastic deformation, and, thus, the load is distributed over a larger surface of the profile without producing deformation of its section.
[0026] The operation of the machine object of the present invention can be repeated in the semi-continuous form on the profile to be bent, obtaining bends of desired length, with beginning and end points on the straight profile limited in their minor separation only by the length of the tool to bend. As the tool can be replaced by tools of larger or smaller size, you can also get: bends of different radius on the same profile, bends in a different sense changing the orientation of the profile, bends of variable radius, etc. In short, any bend that is defined to conform on the tool.
[0027] As for the quality of obtained products (i.e. bent profiles), the dimensional stability of the obtained bends will be influenced by the homogeneity of the mechanical characteristics of the profiles to be bent.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] FIG. 1 : View of the top floor of the machine and various operating positions (initial Y,Y′, intermediate W,W′ and final Z,Z′) of the profile and set of cylinders on the left side (the set of cylinders on the right side of the machine is not shown).
[0029] FIG. 2 : Side view of the machine.
DESCRIPTION OF PREFERRED FORM OF EXECUTION
[0030] In FIG. 1 , it can be observed that the pusher cylinder ( 20 ), located to the left of the central axis of the machine (X) in horizontal position on the bed ( 1 ), is connected to the positioning cylinder ( 23 ) through the movable support point ( 21 ) which moves along the guide ( 22 ). The other, free end of the pusher cylinder ( 20 ) supports a pusher plate ( 26 ) which abuts against the profile ( 3 ) to exert a perpendicular push on the profile by the pusher cylinder ( 20 ), which is driven by a hydraulic pump and after positioning the movable support point ( 21 ) at the suitable point of the guide ( 22 ) by starting the positioning cylinder ( 23 ).
[0031] As for the positioning cylinder ( 23 ), it is placed horizontally on the bed ( 1 ) and is connected to a structural element fixed to the bed via a fixed rotating support ( 24 ) on the central axis (X) of the bed. Each of these pusher cylinders ( 20 ) is equipped with a transducer which reflects on the screen the position of the movable point ( 21 ) in the guide ( 22 ). The cylinders ( 20 , 23 ) on both sides of the central axis (X) are driven by the same hydraulic pump (not shown), which starts the appropriate cylinder at each moment by means of a valve system connected to each cylinder. The hydraulic pusher cylinder ( 20 ) is supported by a secondary guide ( 25 ) fixed to the bed ( 1 ).
[0032] In FIG. 2 , hydraulic press cylinders ( 6 ) are observed, located and operating in the vertical plane of the bed ( 1 ). The upper end of each of these cylinders is fixed and anchored in a beam ( 12 ) supported by two feet ( 12 ) of the support frame ( 10 ), holding at its bottom a compression plate ( 7 ) parallel to the bed ( 1 ) for stress compensation. As can be observed in FIG. 2 , the compression plate ( 7 ) above the profile ( 3 ), and the bed ( 1 ) below the profile ( 3 ), restrain the mentioned tool ( 4 ) and profile ( 3 ) to be bent in the working position, and compensate the lateral deformation stresses to which the profile ( 3 ) is subjected when being bent. These press cylinders ( 6 ) include position, load, etc. measuring sensors in order to transmit this information relative to working parameters to a computer and/or visualization/control screen.
[0033] Therefore, as observed in both figures, on the machine bed ( 1 ), and in the operation plane formed by pusher cylinders ( 20 ) and positioners ( 23 ), and inside the operation zone of the compression plate ( 7 ), the positioning area of the tool ( 4 ) is located, on which the bending of the profile ( 3 ) will be generated. The tool ( 4 ) is placed against the vertical supports ( 5 ) made with double “T” beams with a height at least equal to that of the tool. Thus, on the bed ( 1 ), in the area defined above, the tool ( 4 ) and the profile ( 3 ) to be bent are located, with the mentioned profile ( 3 ) supported in the tool ( 4 ) by the side corresponding to the interior of the bend and with its length in the longitudinal direction of the tool ( 4 ).
[0034] Then (see FIG. 2 ), press cylinders ( 6 ) are made to start by means of a hydraulic pump (not shown), which move the compression plate ( 7 ) for fixing the tool ( 4 ) in its position and fixing the profile ( 3 ).
[0035] Subsequently (see FIG. 1 ), this profile ( 3 ) is bent by means of positioning cylinders ( 23 ) and pushers ( 20 ). Thus, initially, the positioning cylinder ( 23 ) is driven by a hydraulic pump so as to move the back (movable part ( 21 )) of the positioning cylinder ( 20 ) to the point Y (initial position) of the guide ( 22 ), at this moment, the pusher cylinder ( 20 ) is started until the pusher plate ( 26 ) is brought into contact with the profile ( 3 ) (initial state Y′). At this moment, the pusher cylinder ( 20 ) is perpendicular to the profile. The press cylinders ( 6 ) and the compression plate ( 7 ) also serve to compensate for the transverse forces to which the profile ( 3 ) would be subjected. Therefore, as it can be seen in FIG. 2 , it is important that the height of the tool ( 4 ) and of the profile ( 3 ) be the same. The positioning cylinder then advances until the movable point ( 21 ) is moved to the intermediate point W of the guide ( 22 ). Now the pusher cylinder would advance until the profile is bent to the position W′. This process goes on repeatedly until the moving point reaches the final point Z from which the profile can be carried until the desired bending (final state Z′).
[0036] The movement of the back part (movable point ( 21 )) of the pusher cylinders ( 20 ) is made so that the pusher cylinder ( 20 ) always acts perpendicularly to the profile ( 3 ) during its bending. Alternatively, this process can also be automated and done continuously with the help of additional hydraulic pumps.
[0037] Thus, as shown in FIG. 1 , the profile ( 3 ) is pressed against the tool ( 4 ) by the pusher plates ( 26 ) on each side of the central axis of the machine. Thanks to the guide ( 22 ), the pusher cylinders ( 20 ) always remain perpendicular to the zone of the profile ( 3 ) where it acts until the profile ( 3 ) in its deformation reaches the previously defined point (Z′) or the one selected for generating the desired bend.
[0038] If the requested bend length is greater than the bend length generated by the tool ( 4 ), the profile ( 3 ) is released and then is moved longitudinally to generate a new bent stretch as is described above. In this way, bent lengths are added in a semi-continuous process until the desired bend length is reached. | The invention relates to a machine and method for the semi-continuous cold-bending of sections ( 3 ) with low ductility, of the type comprising a horizontal mount ( 1 ) and an interchangeable tool ( 4 ) against which the section ( 3 ) is bent. The machine comprises a gantry support ( 10 ). The tool ( 4 ) is located in a zone delimited by the mount ( 1 ), vertical supports ( 5 ) for the tool ( 4 ), and a compression plate ( 7 ) actuated by vertical pressure cylinders. The tool ( 4 ) is positioned facing an actuation plane defined by a double set of hydraulic positioning ( 23 ) and push ( 20 ) cylinders. The bent sections ( 3 ) can be used for tents, skylights, facades, solar shading louvres, or three-rail frames for truck tarps, guaranteeing a uniform bend in all bent sections, without the section becoming pinned in the machine during bending. | 1 |
BACKGROUND OF THE INVENTION
[0001] This invention relates generally to energy systems, and more specifically to systems and methods for monitoring energy system components.
[0002] In at least some known energy systems, some components operate under high-stress conditions including high temperatures (e.g., 1050° F.) and pressures. Over time, because of continued exposure to such operating conditions, such components may sustain damage due to creep and fatigue. For example, a steam-turbine casing can sustain fatigue damage as a result of variations in pressure and temperature that occur during system startup, system shutdown, and steady-state operations of the system. However, some components can continue to operate years after a crack has developed within the component. By adjusting the operating conditions, the longevity and durability of the system's components can be extended.
[0003] In at least some known energy systems, system operation is periodically suspended so that the system's components may be inspected for damage, i.e., periodic inspections, and/or if necessary, to enable components to be replaced or repaired. However, because known methods do not accurately estimate the time intervals for suspending operations, operational costs associated with shutting down the energy system are increased through premature failures, periodic inspections, and routine outages.
BRIEF DESCRIPTION OF THE INVENTION
[0004] In one aspect, some configurations of the present invention provide a method for estimating an amount of damage sustained by a component operating in an energy system. The method includes generating a transfer function that is dependent upon at least one operating condition of the component, receiving data from at least one sensor operatively coupled to the component, the data relating to the at least one operating condition, applying the data to the transfer function of the at least one critical region to calculate at least one of a crack-initiation time and a crack propagation for the at least one critical region, and recording at least one of the crack-initiation time and the crack propagation on a memory storage device.
[0005] In another aspect, some configurations of the present invention provide a method of operating an energy system including a component that has at least one critical region which may develop a crack. The method includes developing a transfer function for the at least one critical region during a design stage of the component, the transfer function dependent upon at least one operating condition, receiving data from at least one sensor operatively coupled to the component, the data relating to the at least one operating condition, applying the data to the transfer function of each critical region to calculate at least one of the crack-initiation time and the crack propagation for the critical region, and determining at least one of an operating schedule and an operating parameter for the energy system based on at least one of the crack-initiation time and the crack propagation.
[0006] In another aspect, some configurations of the present invention provide a control system for operating an energy system. The control system includes an energy system component comprising a predetermined transfer function dependent upon at least one operating condition, and at least one sensor coupling a critical region of said energy system component to said computing system. The computing system further comprises a processor programmed to receive data from a sensor relating to an operating condition, apply the data to the transfer function of a critical region to calculate at least one of a crack-initiation time and a crack propagation for the critical region, and record at least one of the crack-initiation time and crack propagation for the critical region on a memory storage device.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 is a block diagram of an exemplary computer system that may be used to implement an energy component monitoring system;
[0008] FIG. 2 is an exemplary component that may be used in an energy system; and
[0009] FIG. 3 is a flow chart illustrating an exemplary method used to monitor energy system components.
DETAILED DESCRIPTION OF THE INVENTION
[0010] FIG. 1 is a block diagram of an exemplary energy monitoring system 100 . In the exemplary embodiment, energy monitoring system 100 is implemented via a computer system 118 that includes a display 122 , a processor 120 , a user input device such as a keyboard 128 , a pointing device 130 such as a computer mouse (other pointing devices are acceptable as a design choice), and a memory storage device (not all of which is shown in FIG. 1 , but which may include primary memory such as, but not limited to, RAM and ROM, and/or storage devices such as flash memory, EEPROM, floppy disks 126 and floppy disk drive 124 , CD-ROM, CD-R, CD-RW, magnetic tape, DVD-ROM, DVD-R, DVD-RW, DVD+R, DVD+RW, hard drives, and various types of magnetic, optical, and electronic or electrostatic storage devices and drives without limitation).
[0011] Moreover, in the exemplary embodiment, energy monitoring system 100 is operatively coupled to a power plant (e.g., steam turbine) and to one or more sensors 110 , 112 , 114 , and/or 116 that are configured to sense conditions of a corresponding set of one or more operating physical energy system components such as energy system components 102 , 104 , 106 , and/or 108 . Energy system components 102 , 104 , 106 , and/or 108 may include, but are not limited to, globe valves, gate valves, and butterfly valves. Further examples of energy system components 102 , 104 , 106 , and/or 108 include, but are not limited to, stationary structures such as a steam turbine casing or any turbomachinery component that may be subject to sustained stresses at high temperatures and may develop cracks due to accumulated creep and fatigue damage. Sensors 110 , 112 , 114 , and/or 116 that measure, for example, temperature may be coupled to energy system components 102 , 104 , 106 , and/or 108 by typical adhesion schemes including, but not limited to, welding. Further, sensors 110 , 112 , 114 , and/or 116 that measure pressure may be coupled to energy system components 102 , 104 , 106 , and/or 108 using methods including, but not limited to, insertion at appropriate locations upstream or downstream of the monitored energy system component 102 , 104 , 106 , and/or 108 .
[0012] Computer system 118 receives signals transmitted from sensors 110 , 112 , 114 , and/or 116 and processes the signals as described in detail below. In some embodiments, computer system 118 is configured to transmit signals to one or more physical energy system components 102 , 104 , 106 , and/or 108 , which may not necessarily be the same components as those being monitored by sensors 110 , 112 , 114 , and/or 116 to facilitate controlling energy monitoring system 100 . Alternatively, computer system 118 is not configured to control energy monitoring system 100 and/or to sense conditions of one or more physical energy system components 102 , 104 , 106 , and/or 108 . In such embodiments, input and/or control of energy monitoring system 100 can be provided by receiving and/or transmitting signals from, or to, one or more separate software or hardware system(s) that interact with energy system components 102 , 104 , 106 , and/or 108 of the plant and/or sensors 110 , 112 , 114 , and/or 116 .
[0013] FIG. 2 illustrates an exemplary component that may be monitored using energy monitoring system 100 (shown in FIG. 1 ). Specifically, FIG. 2 illustrates a globe valve 300 that may be monitored with energy monitoring system 100 . In the exemplary embodiment, globe valve 300 includes a valve body 308 and a valve disposed within (not shown) and is the main pressure containing structure for the valve assembly. Accordingly, in the exemplary embodiment, globe valve 300 includes an inlet port 302 and an outlet port 304 . Although globe valve 300 shows a plurality of critical regions 306 , those of ordinary skill in the art will recognize that any energy system component that is subjected to a high-stress environment and that includes one or more critical regions may be monitored with energy monitoring system 100 .
[0014] The term “critical region,” as used herein, represents a portion of an energy system component or structure that may develop a crack, and/or that may limit the life of the component or structure as a result of creep, and/or fatigue damage, and/or crack propagation due to creep and/or fatigue. The critical region of a component may be determined from the operation history of that component, and/or similar components, and/or through testing to determine which region or portion is a critical region.
[0015] During operation, globe valve 300 is exposed to fluctuations of temperature and pressure, as well as cyclic-loading due to such fluctuations. Globe valve 300 may also fluctuate as a result of other factors, including, but not limited to, piping deadweight, and/or thermal expansion. Thus, over time globe valve 300 may develop cracks in one or more critical regions 306 . Crack-initiation and crack propagation can be affected by many factors such as, but not limited to, process parameters, grain size, hold time, temperature, and/or pressure. In addition, hold time duration, and/or the operating environment (steam or air) can also affect the crack growth rate.
[0016] As a result, FIG. 3 is a flow chart of an exemplary method 200 that may be used to estimate the timing and/or amount of creep or fatigue damage to an energy system component, such as globe valve 300 shown in FIG. 2 , operating in an energy system. Method 200 may also be used to monitor existing damage to the energy system component in order to predict a future failure date.
[0017] In the exemplary embodiment, initially at least one transfer function is determined 202 for at least one critical region 306 of the energy system component being monitored. The term “transfer function,” as used herein, is a function that is applied to operating data (e.g., relating to temperature, pressure) to determine component stresses. Transfer functions are dependent upon a number of factors, including, but not limited to, material properties of the component, operating conditions, and the dimensions of the component near the critical region. Transfer functions may be determined using standard closed-formed solutions and/or elastic and creep finite element analyses. In the exemplary embodiment, a transfer function is developed at the design stage between measured temperature gradients (spatial and temporal), pressure, and combined damage due to low cycle fatigue (LCF) and creep, and subsequent crack propagation due to creep and fatigue.
[0018] The term “failure,” as applied to engineering systems or components, can be described as the non-performance of components or systems due to some deficiency that limits their service life. Failures are not uncommon in industry and can occur at any of the various stages such as fabrication, testing, transportation and service.
[0019] In the exemplary embodiment, data relevant to one or more operating conditions is recorded 204 in pre-determined intervals ranging from about thirty to about sixty seconds. Alternatively, data may be recorded in different time intervals, based on the energy system component being monitored. The operating conditions recorded may include, but are not limited to, temperature, pressure, and/or cyclic loading due to fluctuations in either temperature, pressure, or both. Those skilled in the art will recognize that other conditions that affect crack-initiation time and propagation may be recorded or monitored.
[0020] In the exemplary embodiment, energy monitoring system 100 calculates creep and fatigue damage 206 , as described in more detail below, using the predetermined transfer function 202 and the data relevant to one or more operating conditions 204 . Moreover, based on the calculations, energy monitoring system 100 can accurately estimate crack initiation and propagation in the energy system component being monitored. Specifically, in the exemplary embodiment, cumulative creep and fatigue damage is used to calculate the total amount of consumed life, in terms of crack initiation, of the globe valve 300 . Then, crack propagation data is used to estimate 208 an approximate time when crack size in the globe valve 300 will reach a predetermined critical size. At that time, operation of the energy system must be suitably adjusted until the cracked region is repaired or the energy system component is replaced by suspending operation.
[0021] To account for combined damage mechanism, the damage accumulation approach considers the damage due to creep and fatigue separately using:
[0000] where D is the total allowable creep-fatigue damage index which guides component inspection or replacement intervals, n i is the number of cycles at stress σ i , N i is the number of cycles to failure at the same stress σ I , P is the number of different cyclic loading conditions, t j is the total duration of a specific loading at elevated temperature j during the entire service life of the component, t jm is the maximum allowed time under load stress intensity, and Q is the number of different specific loading conditions. This damage parameter formulation demonstrates a linear damage rule, and based on experience for particular applications, materials, and geometries, other damage rules can be used including, but not limited to, a damage rule that assigns different weights to creep and fatigue damage.
[0022] Such a determinative number is particularly important for utilities that have inspected energy system components and have found cracks, but must continue to run the unit while waiting for a replacement part or an extended outage. This crack growth is attributed to the combined effect of fatigue crack growth and creep crack growth. The accumulated effect is determined by computing the effects separately and then by adding them together. The fatigue crack growth rate is calculated as follows:
[0000] where ΔK eff is the effective stress intensity factor (SIF) range and where both C and m are material constants. The propagation of the defect (δa i ) for the number of occurrences of cycles n i is:
where (ΔK eff ) i is the maximum effective SIF range corrected for the influence of plasticity.
[0023] Creep crack growth rates are calculated using the time-dependent C t approach or according to the guidelines of. The propagation of the defect due to creep during hold time t mi is:
[0000] where C* is the creep fracture parameter. In the exemplary embodiment, the creep fracture parameter of the following nature can be used:
where
is the line contour taken from the lower crack surface in a counterclockwise direction to the upper crack surface. W* is the strain energy rate density associated with the point stress □ij and strain rate □ij. Ti is the traction vector defined by the outward normal □, Ti=σijnjui is the displacement vector and s is the arc length along □.
[0024] The combination of the determined total consumed life of the energy system component, design limits of the energy system component, the recommended operating procedures, and the rated allowable temperature excursions enables the scheduled timing of the next planned inspection to be adjusted and/or optimized 210 . For example, if energy monitoring system 100 determines that the energy system component being monitored has been subjected to less severe temperature gradients, pressures, and/or fluctuations, then the timing of the next inspection may be extended, subject to continuous monitoring of the energy system component and normal system operations.
[0025] Conversely, if energy monitoring system 100 determines that the energy system component being monitored has been exposed to more severe temperature gradients, pressures, and/or fluctuations than recommended, but is still operating within design limits, then the system operator can be notified of a possible need to inspect the energy system component sooner than originally planned. Additionally, if a first inspection does not detect a crack in the energy system component, then the time until the next inspection may be extended to account for crack initiation and propagation using the predetermined transfer function. Thus, the system is dynamic in nature and evolves with actual system operation and findings.
[0026] The above-described methods and apparatus facilitate improving the scheduling of inspection intervals of an energy system component in a power system. Developing a transfer function at the design stage, between measured temperatures, pressures, and cumulative fatigue and creep damage allows calculation of crack initiation and life consumption of the energy system component. This calculation, when used in combination of design limits of the energy system component and recommended operating procedures of the power plant, facilitates calculating the next planned inspection. As such, if the power system operates such that the monitored energy system component is subjected to less severe operating conditions, then the timing of the next inspection of the energy system component may be extended. If, however, the monitored energy system component is subjected to more severe operating conditions, the next inspection may be scheduled sooner than originally planned. Since inspection intervals may be based on actual power system operation, the utilization of the power system and its energy system components may be optimized to allow for continued system operation during expected peak power periods.
[0027] Exemplary embodiments of methods and apparatus for monitoring energy system components are described above in detail. The methods and apparatus are not limited to the specific embodiments described herein, but rather, components of the methods and apparatus may be utilized independently and separately from other components described herein. For example, the interaction of creep and fatigue in the design stage of a system component may also be used in combination with other industrial component design and monitoring systems and methods, and is not limited to practice with only energy system plants as described herein. Rather, the present invention can be implemented and utilized in connection with many other component design and monitoring applications.
[0028] While the invention has been described in terms of various specific embodiments, those skilled in the art will recognize that the invention can be practiced with modification within the spirit and scope of the claims. | A method for estimating an amount of damage sustained by a component operating in an energy system includes generating a transfer function that is dependent upon at least one operating condition of the component, receiving data from at least one sensor coupled to the component, wherein the data relates to the at least one operating condition of the component, inputting the received data into the transfer function to calculate at least one of a crack-initiation time and a crack propagation for the at least one critical region, and recording at least one of the crack-initiation time and the crack propagation on a memory storage device. | 6 |
BACKGROUND OF THE INVENTION
The invention relates to jar openers and more particularly to automatic jar openers.
SUMMARY OF THE INVENTION
The invention relates to a fully automatic jar opener for loosening a threaded jar cap on a jar. The jar opener includes a bottom jar retainer including substantially horizontal clamps that are automatically movable along a horizontal plane between an open position and a jar clamping position. The clamps, while in the jar clamping position, hold the jar substantially without slippage when the jar cap is subjected to a twisting force. A top jar retainer holds the jar cap substantially without slippage when the twisting force is applied to the jar cap. The twisting force is applied to the jar cap by the top jar retainer. A vertical drive automatically adjusts a relative vertical position between the bottom jar retainer and the top jar retainer, the relative vertical position determines a holding force of the top jar retainer on the jar cap for a given jar size. The automatic jar opener includes one or more drivers for moving the clamps along the horizontal plane, for adjusting the relative vertical position between the bottom jar retainer and the top jar retainer, and for applying the twisting force to the top jar retainer. A controller automatically controls the action of the drivers and the movements of the clamps and enables loosening of the jar cap on a jar that has been placed in the opener with a single, discrete user command that is input on a user input device.
In particular embodiments of the invention, one of the drivers is a pneumatic actuator for moving the clamps along the horizontal plane, and one or more electric motors adjust the relative vertical position between the bottom jar retainer and the top jar retainer, and apply the twisting force to the top jar retainer. The controller sends a first control signal to a valve that controls the flow of pressurized fluid into the pneumatic actuator. Pressure changes within the pneumatic actuator activates a piston rod whose movement causes the clamps to move along the horizontal plane.
In particular embodiments of the invention, upon the discrete user command, the controller sends a first command signal to a driver resulting in movement of the clamps to the jar clamping position to hold the jar, whereupon the controller sends a second command signal to a driver resulting in movement of the vertical drive to move together the bottom jar retainer and the top jar retainer to apply the holding force to the jar cap, whereupon the controller sends a third command signal to a driver resulting in the twisting force being applied to the jar cap via the top jar retainer to loosen the jar cap.
The controller further sends a fourth signal to the driver resulting in movement of the vertical drive to separate the bottom jar retainer and the top jar retainer to release the holding force on the jar cap and a fifth signal to a driver resulting in movement of the clamps to the open position to release the jar.
In other embodiments of the invention, the fully automatic jar opener includes at least two motors, a first motor for applying the twisting force to the cap and a second motor for adjusting the relative vertical positions of the bottom and top jar retainers.
In one illustrated embodiment, the fully automatic jar opener includes three motors, a first motor for applying the twisting force to the cap, a second motor for adjusting the bottom jar retainer, and a third motor for adjusting the top jar retainer. Upon the discrete user command, the controller sends a first command signal to the second motor to move the clamps to the jar clamping position to hold the jar and a second command signal to the third motor to move the vertical drive to move together the bottom jar retainer and the top jar retainer to apply the holding force to the jar cap. After the clamps have been moved to the jar clamping position and the holding force has been applied to the jar cap, the controller sends a third command signal to the first motor resulting in the twisting force being applied to the jar cap by the top jar retainer to loosen the jar cap.
In particular embodiments of the invention, the jar includes side walls and a base and the clamps contact the jar on opposite side walls of the jar near the base of the jar. The clamps include gripping pads for contacting the jar and holding the jar substantially without slippage when the jar cap is subjected to the twisting force. The clamps define arcuate shaped jar contacting portions permitting clamping of different radii jars within a given range.
In other embodiments of the invention, the fully automatic jar opener includes a housing defining clamp pivots. The clamps are constructed and arranged to move along a horizontal plane between the open position and the jar clamping position by pivoting about the clamp pivots. The clamps are slidably received on the clamp pivots allowing removal and replacement of the clamps. The clamps include arm portions pivotably connected to the clamp pivots and jar contacting portions slidably received on the arm portions. Each jar contacting portion defines an arcuate shaped inner profile permitting clamping of different radii jars within a given range.
In one illustrated embodiment, the top jar retainer includes a cone for gripping a variety of sizes of jar caps. The cone includes a gripping pad for contacting the jar cap and holding the jar cap substantially without slippage when the twisting force is applied to the jar cap.
In other embodiments of the invention, a switch is activated when a predetermined load is applied to the jar by the clamps and another switch is activated when a predetermined load is applied to the jar cap by the top jar retainer. The jar opener includes a housing defining a chamber for placement of the jar and a door with a third switch activated when the door is closed.
The automatic jar opener of the invention can be used to easily loosen a jar cap with one, single discrete user command. The opener can be used with jars having a variety of heights, owing to the adjustment of the position between the clamps and top jar retainer, and with jars having a variety of diameters owing to the cone shape.
Other advantages and features of the invention will be apparent from the following description of the preferred embodiment and from the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic representation of an automatic jar opener according to the invention;
FIG. 2 shows a front view of the automatic jar opener of FIG. 1;
FIG. 3 shows a top view of the automatic jar opener as seen taken along lines 3 — 3 in FIG. 2;
FIG. 3 a shows a side view of a gear train of the automatic jar opener as seen taken along lines 3 a - 3 a in FIG. 3;
FIG. 4 shows a top view of the automatic jar opener as seen taken along lines 4 — 4 in FIG. 2;
FIG. 5 shows a partially cut away top view of the automatic jar opener as seen taken along lines 5 — 5 in FIG. 2;
FIG. 6 is a diagrammatic representation of some components of the automatic jar opener shown in a jar receiving position; and
FIG. 7 shows an alternative embodiment of the jar clamps of the invention.
FIG. 8 a is a diagrammatic representation of an alternative embodiment of the jar clamps of the invention.
FIG. 8 b is a diagrammatic representation of another alternative embodiment of the jar clamps of the invention.
FIG. 8 c is a diagrammatic representation of still another alternative embodiment of the jar clamps of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, an automatic jar opener 10 is shown for automatically loosening a threaded jar cap 20 of a jar 16 . A bottom jar retainer 12 for holding jar 16 includes clamps 14 , 14 a mounted for movement (indicated by arrows 13 ) in a horizontal plane between an open position, FIG. 6, and a jar clamping position, FIG. 1 . In the jar clamping position of FIG. 1, clamps 14 , 14 a apply a holding force, for example, 50 to 60 pounds, to side walls 25 of jar 16 near the base 27 of the jar. A top jar retainer 18 is mounted to move vertically (indicated by arrow 21 ) between an unloaded position, FIG. 6, and a cap loosening position, FIG. 1 . In the cap loosening position of FIG. 1, top jar retainer 18 applies a downward holding force, for example, 50 to 60 pounds, to jar cap 20 . Top jar retainer 18 also includes a cone 19 mounted to rotate about vertical axis 17 (arrow 22 ) to apply a twisting force, for example, 10 foot- pound, to jar cap 20 to loosen the cap.
Jar opener housing 23 includes a door 24 allowing access to a jar chamber 29 and platform 33 on which jar 16 is placed by the user. Door 24 includes a safety latch 26 which, upon closing door 24 , contacts a switch 28 . With door 24 closed, a single user command, for example, activating an input device such as switch 30 , instructs automatic jar opener 10 to loosen jar cap 20 .
Referring to FIGS. 2-4, clamps 14 , 14 a are mounted for movement along a rod 35 between the open position of FIG. 6 and the jar clamping position of FIG. 1 . Referring particularly to FIG. 3, clamps 14 , 14 a include slots 37 , 37 a containing threaded elements 34 , 34 a which are mounted on threaded rod ends 36 , 36 a of rod 35 . Rod ends 36 , 36 a are oppositely threaded such that rotation of rod 35 causes threaded elements 34 , 34 a to move toward or away from each other along guiding slots 31 , 31 a in a platform 33 .
Clamps 14 , 14 a are mounted to rotate about pivots 32 , 32 a . Pivots 32 , 32 a are defined by clamps through bores 132 , 132 a received on extension rods 134 , 134 a of blocks 136 , 136 a (FIG. 2 ). During movement of clamps 14 , 14 a along rod 35 and about pivots 32 , 32 a , threaded elements 34 , 34 a slide within clamp slots 37 , 37 a . The arcuate shape of jar contacting portions 47 , 47 a of clamps 14 , 14 a permit clamping of different radii jars within a range. Additionally, clamps 14 , 14 a may be slidably received on threaded elements 34 , 34 a and extension rods 134 , 134 a to permit easy replacement of the clamps to accommodate different ranges of sizes for jars 16 .
Referring particularly to FIGS. 3 a and 4 , to rotate rod 35 , a motor 40 with worm gear 42 drives a gear 44 . Axle 46 of gear 44 drives a helical gear 48 (supported by bearing 49 ) which in turn drives a helical gear 50 attached to rod 35 .
Referring to FIGS. 2 and 4, top jar retainer 18 includes a mount 60 with threaded holes 62 , 62 a received on lead screws 64 , 64 a of a vertical drive 63 . Lead screws 64 , 64 a are mounted for rotation within bearings 65 to move top jar retainer 18 vertically (indicated by arrow 66 ) between the unloaded position of FIG. 6 and the cap loosening position of FIG. 1 . To rotate lead screws 64 , 64 a , a motor 70 with worm gear 72 drives a gear 74 attached to lead screw 64 a . A belt 75 mounted on pulleys 77 , 77 a couples motion of lead screw 64 a to lead screw 64 . Idler 79 keeps belt 75 under tension.
Referring to FIGS. 2, 4 and 5 , mount 60 of top jar retainer 18 is received on a square rod 78 for rotation therewith. To rotate cone 19 , a motor 80 with worm gear 82 drives a gear 84 attached at one end 78 a of square rod 78 . At the opposite end 78 b of square rod 78 is a gear drive including gears 86 , 88 and 90 . Gear 90 is mounted to cone 19 for rotation therewith.
Referring to FIG. 3, clamps 14 , 14 a include non-slip surfaces 110 , for example, a rubberized foam such as that found on the backing of place mats or scatter rugs, to hold the jar substantially without slippage when the jar cap is subjected to the twisting force. As shown in FIG. 2, cone 19 also includes a non-slip surface 110 , which, when combined with the holding force applied by top jar retainer 18 on jar cap 20 , holds jar cap 20 substantially without slippage when the twisting force is applied to the jar cap. The inclined shape of cone 19 permits engagement between surface 110 and a variety of different sized caps.
Referring to FIGS. 3 and 4, in the illustrated embodiment, when clamps 14 , 14 a contact jar 16 and apply the holding force to the jar, an opposite force directed along arrows 140 is applied to the clamps and a related force directed along arrows 142 is applied by the clamps to rods 134 , 134 a . A slot 138 in platform 33 and slots 140 , 142 in block 136 a allow clamp 14 a and block 136 a to move in the direction of arrow 142 in response to this force. Block 136 a abuts a first end 148 of a lever 150 . Movement of block 136 a causes rotation of lever 150 about a pivot 152 . A second end 154 of lever 150 is attached to an extension spring 156 . Rotation of lever 150 acts against extension spring 156 . Extension spring 156 is set, for example, by turning an adjustment screw 158 , such that rotation of lever 150 about pivot 152 an amount necessary to activate a limit switch 160 corresponds to the desired clamp load on jar 16 . A compression spring 162 acts on block 136 a against extension spring 156 such that block 136 a is not free- floating within slots 138 , 140 and 142 when clamps 14 , 14 a are in their open position.
Referring to FIG. 2, cone 19 includes a spring 114 located within a recess 116 in housing 60 . A switch 118 located within recess 116 is activated when the spring has been depressed a predetermined distance corresponding to the desired vertical load. Motor 80 includes a potentiometer 170 for measuring the rotation of cone 19 . The cone is generally rotated about one-half turn to loosen cap 20 .
Automatic jar opener 10 includes a controller 100 for automatically controlling motors 40 , 70 and 80 . Triggering of switch 160 sends a signals to controller 100 indicating that the desired clamp force of clamps 14 , 14 a on jar 16 has been reached. Controller 100 then commands motor 40 to hold this position. Similarly, triggering of switch 118 sends a signal to controller 100 indicating that the desired vertical load of cone 19 on jar 16 has been reached. Controller 100 then commands motor 70 to hold this position. Controller 100 monitors potentiometer 170 during rotation of cone 19 and stops rotation of motor 80 when the cap has been turned about one-half turn.
Referring to FIG. 6, in use, jar 16 is placed between open clamps 14 , 14 a . Door 24 is closed with safety latch 26 contacting switch 28 . The user then pushes switch 30 sending a signal to controller 100 to loosen jar cap 20 . From this point, jar opener 10 is under automatic control. Controller 100 sends signals to motors 40 and 70 resulting in the closing of clamps 14 , 14 a and the lowering of cone 19 . When the desired loads of clamps 14 , 14 a and cone 19 on jar 16 has been reached, as determined by monitoring switches 160 and 118 , respectively, controller 100 sends a signal to motor 80 to turn cone 19 one-half-turn. Controller 100 then directs motors 40 and 70 to open clamps 14 , 14 a and lift cone 19 . Door 24 can then be opened. If door 24 is opened before completion of the cap loosening cycle, as determined by monitoring door sensor 28 , controller 100 stops all movement.
Other embodiments of the invention are within the scope of the following claims.
For example, controller 100 can monitor the current draw of motors 40 and 70 , as is well known in the art, to determine and maintain the desired loads on jar 16 . Alternatively, motors 40 and 70 can include slip clutches designed to apply only the desired loads to jar 16 . The three motors 40 , 70 and 80 can be replaced with one or two motors and appropriate drive linkages.
Cone 19 can include a serrated inner lining to aid in gripping jar cap 20 .
Referring to FIG. 7, clamps 214 , 214 a include arms 215 , 215 a and jar contacting portions 216 , 216 a . The inner arcuate shaped profiles 218 , 218 a of jar contacting portions 216 , 216 a permit clamping of a variety of sized jars. Jar contacting portions 216 , 216 a may be slidably received on rods 220 , 220 a of clamps 214 , 214 a for ease of replacement.
Referring to FIGS. 8 a - 8 c , clamps 302 and 302 a , 402 and 402 a , and 502 and 502 a are mounted to rotate about pivots 304 and 304 a , 404 and 404 a , and 504 and 504 a , respectively. Pneumatic actuators 306 , 406 , and 506 and 506 a are connected to respective fluid supply tubes 308 , 408 , and 508 for the delivery of pressurized fluid. Solenoid valves 310 , 410 , and 510 are joined to and interrupt tubes 308 , 408 , and 508 and are controlled by electronic controller 100 . Piston rods 314 , 414 , and 514 and 514 a project slidably from pneumatic actuators 306 , 406 , and 506 and 506 a , respectively.
In FIG. 8 a , clamps 302 and 302 a contain sets of engaging teeth 316 and 316 a that mesh with each other so that the movement of one of clamps 302 or 302 a causes a reciprocal movement by the other one. Piston rod 314 is connected to clamp 302 .
In FIG. 8 b , piston rod 414 has teeth 418 that mesh with engaging teeth 416 and 416 a on clamps 402 and 402 a , respectively.
In FIG. 8 c , fluid supply tube 508 is capable of delivering pressurized fluid to both pneumatic actuators 506 and 506 a . Piston rods 514 and 514 a are connected to clamps 502 and 502 a , respectively.
Actuators 306 , 406 , 506 , and 506 a have spring returns. Alternatively, the actuators could be driven in both directions by providing additional solenoid valves and providing two controlled pneumatic supplies to the actuators. | A fully automatic jar opener for loosening a threaded cap includes a bottom jar retainer including substantially horizontal clamps automatically movable along a horizontal plane between an open position and a jar clamping position. The clamps, while in the jar clamping position, hold a jar substantially without slippage and a top jar retainer holds the cap substantially without slippage when the cap is subjected to a twisting force. A vertical drive automatically adjusts the relative vertical positions between the bottom and top retainers to apply a holding force on the cap. The automatic jar opener includes at least one electrically-controllable pneumatic actuator for moving for moving the clamps along the horizontal plane, and at least one motor for applying the twisting force to the top retainer and for adjusting the relative vertical position between the retainers. A controller automatically controls the pneumatic actuator and the motor and enables loosening of the cap with one single, discrete user command. | 1 |
BACKGROUND
[0001] The statements in this section merely provide background information related to the present disclosure and may not constitute prior art.
[0002] The present disclosure relates generally to wellbore treatment and development of a reservoir and, in particular, to a system and a method for determining characteristics of the reservoir during a wellbore operation such as, but not limited to, a wellbore treatment operation, an underbalanced drilling operation, or the like.
[0003] Currently, fiber optic Distributed Temperature Sensing (DTS) technology provides a means for substantially instantaneous temperature measurement in a wellbore. DTS typically includes an optical fiber disposed in the wellbore (e.g. via a permanent fiber optic line cemented in the casing, a fiber optic line deployed using a coiled tubing, or a slickline unit). The optical fiber measures a temperature distribution along a length thereof based on an optical time-domain (e.g. optical time-domain reflectometry (OTDR), which is used extensively in the telecommunication industry).
[0004] One advantage of DTS technology is the ability to acquire in a short time interval the temperature distribution along the well without having to move the sensor as in traditional well logging which can be time consuming. DTS technology effectively provides a “snap shot” of the temperature profile in the well. DTS technology has been utilized to measure temperature changes in a wellbore after a stimulation injection, from which a flow distribution of an injected fluid can be qualitatively estimated.
[0005] The introduction of hot slugs in a wellbore is another useful technique for flow profiling with Distributed Temperature Sensing (DTS). The conventional method of generating a hot slug includes injecting a large fluid volume in the reservoir and then shutting the well in to heat the fluids above the reservoir interval. The temperature of the fluids next to the reservoir interval increase much slower as the reservoir interval is much cooler because of fluids injected previously. This differential heating creates a temperature front that can be tracked with DTS for flow profiling.
[0006] By obtaining and analyzing multiple DTS temperature traces, the characteristics and flow properties of different formation layers can be determined.
[0007] Several methods for quantitatively characterizing a reservoir and determining the flow distribution therein from a DTS measurement are discussed in detail below.
SUMMARY
[0008] An embodiment of a method for determining characteristics of a formation having a wellbore formed therein comprises the steps of: positioning a sensor within the wellbore, wherein the sensor generates a feedback signal representing a temperature therein; injecting a fluid into the wellbore; generating a data model representing temperature characteristics of the formation, wherein the data model is derived from the feedback signal; and analyzing the data model based upon an instruction set to extrapolate characteristics of the formation.
[0009] In another embodiment, a method for determining characteristics of a formation having a wellbore formed therein comprises the steps of: positioning a sensor within the wellbore, wherein the sensor provides a substantially continuous temperature monitoring along a pre-determined interval of the wellbore, and wherein the sensor generates a feedback signal representing temperature measured by the sensor; injecting a first fluid into the wellbore and into at least a portion of the formation adjacent to the interval; generating a data model representing actual thermal characteristics of at least a sub-section of the interval, wherein the data model is derived from the feedback signal; and analyzing the data model based upon an instruction set to extrapolate characteristics of the formation.
[0010] In yet another embodiment, a method for determining characteristics of a formation having a wellbore formed therein comprises the steps of:
a) positioning a distributed temperature sensor within the wellbore, wherein the sensor provides a substantially continuous temperature monitoring along a pre-determined interval of the wellbore, and wherein the sensor generates a feedback signal representing temperature measured by the sensor; b) deploying a coiled tubing into the wellbore; c) injecting a first fluid through the coiled tubing and into the wellbore; d) generating a data model representing thermal characteristics of at least a sub-section of the interval, wherein the data model is derived from the feedback signal; e) analyzing the data model based upon an instruction set to extrapolate characteristics of the formation; and f) repeating steps c) through e) for each of a plurality of sub-sections defining the interval within the wellbore to generate a profile representative of the entire interval.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] These and other features and advantages of the present invention will be better understood by reference to the following detailed description when considered in conjunction with the accompanying drawings wherein:
[0018] FIG. 1 is a schematic block diagram of an embodiment of a wellbore treatment system; and
[0019] FIG. 2 is a schematic representation of the wellbore treatment system of FIG. 2 , showing a graphical plot of an associated temperature log measured by the system.
DETAILED DESCRIPTION
[0020] Referring now to FIGS. 1-2 , there is shown an embodiment of a reservoir characterization system, indicated generally at 10 . As shown, the system 10 includes a fluid injector(s) 12 , a wellbore sensor 13 disposed adjacent a wellbore 11 , a flow sensor 14 , and a processor 15 . It is understood that the system 10 may include additional components.
[0021] The fluid injector 12 typically includes a coiled tubing 16 , which can be positioned in a wellbore, such as the wellbore 11 , formed in a formation to selectively direct a fluid to a particular depth or layer of the formation. For example, the fluid injector 12 can direct a diverter immediately adjacent a layer of the formation to plug the layer and minimize a permeability of the layer. As a further example, the fluid injector 12 can direct a stimulation fluid adjacent to a layer for stimulation. It is understood that other means for directing various fluids (e.g. drilling fluids) to various depths and layers can be used, as appreciated by one skilled in the art of drilling and wellbore treatment. It is further understood that various drilling fluids, treating fluids, diverters, and stimulation fluids can be used to treat various layers of a particular formation.
[0022] In certain embodiments, a first fluid or chemical is injected into the wellbore through the coiled tubing 16 and a second fluid or chemical is injected into the wellbore via an annulus 17 formed between the wellbore 11 the coiled tubing 16 . It is understood that the second chemical may be injected between a portion of the formation and an exterior housing of the coiled tubing 16 using another injection means or conduit.
[0023] The first chemical and the second chemical are selected to generate a hot slug when mixed. As a non-limiting example, the first chemical is sodium nitrate (NaNO2), the second chemical is ammonium chloride (NH4C1), and the chemical reaction for generating the hot slug for flow profiling with DTS is: NaNO2+NH4C1→NaC1+H2O+N2. The chemical reaction generates heat and a gaseous phase nitrogen (N2). As a non-limiting example, the reaction is highly exothermic (˜80 kcal/mol) and the reaction rate can be controlled by the pH of the system. The delta T from the reaction can be controlled by the concentration of the reactants. It is understood that the reactants sodium nitrate (NaNO2) and ammonium chloride (NH4C1) are very soluble in water. It is further understood that a surfactant may be added to the fluids/chemicals to foam-up and trap the gaseous N2 to insulate the fluids/chemicals and therefore allow monitoring for extended time.
[0024] Exothermic reactions may be expressed in the general form as:
[0000] A+B+ . . . ---(Catalyst/retarder C)->D+E+ . . . Heat
[0025] For the reaction to occur, all reactants (i.e. A and B in the above example) need to be present. It is desirable at times to control the rate of reaction, which may be altered by the presence of a catalyst or a retarder C noted above. As noted above, an example of an exothermic reaction suitable for generating the hot slug for flow profiling with DTS is: NaNO2+NH4Cl→NaCl+H2O+N2. The reaction, in this example, is catalyzed by acid and the rate of reaction (i.e. acceleration or deceleration of the reaction), therefore, may be controlled by controlling the pH of the reaction.
[0026] The reaction may be controlled by separating the reactants and/or the catalyst/retarder and then controlling the zone of mixing of reactants for targeting the release of heat to a specific area or areas. The reaction may be controlled by separated the reactants by injecting reactants from different flow paths (such as one reactant thru the coiled tubing 16 and the other reactant through the annulus 17 ). The reaction may be controlled by controlling the location of the mixing zone by changing the injection rates of A and B. The reaction may be controlled by splitting the reactants into two separate fluids and injecting the two fluids sequentially, such as into the coiled tubing 16 , with an optional buffer in the middle of the fluids. In such a situation, the size of the buffer dictates the time of reaction and the reaction will occur at the interface. The reaction may be controlled by encapsulating or generating in-situ one of the reactants, the catalyst, or retarder for the reaction. For those reactions in which the catalyst is required in small concentrations, it may be easier to separate the catalyst. For the above-mentioned reaction, the acid catalyst for the reaction (e.g. oxalic or citric acid) may be encapsulated in ethyl cellulose or paraffin (wax). If paraffin is used, it will melt as the fluids travel downhole and release the catalyst for the reaction. The reaction may also be controlled by coating the catalyst on the surface where the reaction is desired to take place, such as, but not limited to, on the exterior surface of the coiled tubing 16 . The reaction may also be controlled by injecting the reactants as a pre or post flush of a treatment, wherein the reaction and, therefore, the hot slug will be formed during flow back when the reactants mix. In a non-limiting example, NH4C1 can be injected into the coiled tubing 16 as a post flush of a stimulation treatment. The treatment fluid and post flush fluid (NH4Cl) is flowed back through the annulus 17 , followed by NaNO2 (i.e., the second reactant) injected into the coiled tubing 16 . Hot slugs will form near zones from the wellbore 11 which flow back NH4Cl when the NaNO2 reacts with the NH4CL, which may be used as an indicator for clean-up of a particular zone (i.e. if now NH4Cl is detected coming out of that layer, this would mean the zone has not cleaned-up, and a larger draw-down may be necessary, or the like).
[0027] The wellbore sensor 13 typically incorporates a Distributed Temperature Sensing (DTS) technology including an optical fiber 18 disposed in the wellbore (e.g. via a permanent fiber optic line cemented in the casing, a fiber optic line deployed using a coiled tubing, or a slickline unit). The optical fiber 18 measures the temperature distribution along a length thereof based on optical time-domain (e.g. optical time-domain reflectometry). In certain embodiments, the wellbore sensor 13 includes a pressure measurement device 19 for measuring a pressure distribution in the wellbore and surrounding formation. In certain embodiments, the wellbore sensor 13 is similar to the DTS technology disclosed in U.S. Pat. No. 7,055,604 B2, hereby incorporated herein by reference in its entirety. Other wellbore temperature sensors can be used to measure substantially real-time temperatures throughout the wellbore.
[0028] The flow sensor 14 is typically a flow meter for measuring at least the hydrocarbon production rate (i.e. gas rate) from the wellbore. However, it is understood that any sensor or device for measuring the gas rate of a particular wellbore can be used.
[0029] The processor 15 is in data communication with the wellbore sensor 13 to receive data signals (e.g. a feedback signal) therefrom and analyze the signals based upon a pre-determined algorithm, mathematical process, or equation, for example. As shown in FIG. 1 , the processor 15 analyzes and evaluates a received data based upon an instruction set 20 . The instruction set 20 , which may be embodied within any computer readable medium, includes processor executable instructions for configuring the processor 15 to perform a variety of tasks and calculations. As a non-limiting example, the instruction set 20 may include a comprehensive suite of equations governing a physical phenomena of fluid flow in the formation, a fluid flow in the wellbore, a fluid/formation (e.g. rock) interaction in the case of a reactive stimulation fluid, a fluid flow in a fracture and its deformation in the case of hydraulic fracturing, and a heat transfer in the wellbore and in the formation. As a further non-limiting example, the instruction set 20 includes a comprehensive numerical model for carbonate acidizing such as described in Society of Petroleum Engineers (SPE) Paper 107854, titled “An Experimentally Validated Wormhole Model for Self-Diverting and Conventional Acids in Carbonate Rocks Under Radial Flow Conditions,” and authored by P. Tardy, B. Lecerf and Y. Christanti, hereby incorporated herein by reference in its entirety. It is understood that any equations can be used to model a fluid flow and a heat transfer in the wellbore and adjacent formation, as appreciated by one skilled in the art of wellbore treatment. It is further understood that the processor 15 may execute a variety of functions such as controlling various settings of the wellbore sensor 13 and the fluid injector 12 , for example.
[0030] As a non-limiting example, the processor 15 includes a storage device 22 . The storage device 22 may be a single storage device or may be multiple storage devices. Furthermore, the storage device 22 may be a solid state storage system, a magnetic storage system, an optical storage system or any other suitable storage system or device. It is understood that the storage device 22 is adapted to store the instruction set 20 . In certain embodiments, data retrieved from the wellbore sensor 13 is stored in the storage device 22 such as a temperature measurement and a pressure measurement, and a history of previous measurements and calculations, for example. Other data and information may be stored in the storage device 22 such as the parameters calculated by the processor 15 , a database of petrophysical and mechanical properties of various formations, a database of natural fractures of a particular formation, and data tables used in reservoir characterization in various drilling operations (e.g. underbalanced drilling characterization), for example. It is further understood that certain known parameters and numerical models for various formations and fluids may be stored in the storage device 22 to be retrieved by the processor 15 .
[0031] As a further non-limiting example, the processor 15 includes a programmable device or component 24 . It is understood that the programmable device or component 24 may be in communication with any other component of the system 10 such as the fluid injector 12 and the wellbore sensor 13 , for example. In certain embodiments, the programmable component 24 is adapted to manage and control processing functions of the processor 15 . Specifically, the programmable component 24 is adapted to control the analysis of the data signals (e.g. feedback signal generated by the wellbore sensor 13 ) received by the processor 15 . It is understood that the programmable component 24 may be adapted to store data and information in the storage device 22 , and retrieve data and information from the storage device 22 .
[0032] In certain embodiments, a user interface 26 is in communication, either directly or indirectly, with at least one of the fluid injector 12 , the wellbore sensor 13 , and the processor 15 to allow a user to selectively interact therewith. As a non-limiting example, the user interface 26 is a human-machine interface allowing a user to selectively and manually modify parameters of a computational model generated by the processor 15 .
[0033] In use, the wellbore sensor 13 is disposed along an interval within the wellbore to provide substantially continuous temperature monitoring along the interval, wherein the wellbore sensor 13 generates a feedback signal representing temperature measured thereby. In certain embodiments, a data model is generated representing temperature characteristics of the formation derived from the feedback signal. The processor 15 analyzes the data model based on the instruction set 20 to extrapolate characteristics of the formation including a flow profile of the wellbore. As a non-limiting example, the processor 15 analyzes the data model (e.g. real-time temperature log) by comparing the temperature characteristics of the formation to at least one of a geothermal gradient, a flowing bottom hole pressure, and a well head pressure. As a further non-limiting example, the data model is compared to a data log of known or estimated petrophyscial characteristics (including natural fractures) of the formation at various depths. It is understood that the process can be repeated for each of a plurality of sub-sections defining the interval within the wellbore to generate a profile representative of the entire interval.
[0034] As an illustrative example, FIG. 2 includes a graphical plot 28 showing a substantially real-time temperature log 30 (i.e. data model) and a pre-defined geothermal gradient 32 for a formation having a wellbore formed therein. It is understood that the temperature log 30 is based upon data acquired by the wellbore sensor 13 . As shown, the X-axis 34 of the graphical plot 28 represents temperature and the Y-axis 36 of the graphical plot 28 represents a depth of the formation, measured from a pre-determined surface level. As a non-limiting example, the processor 15 analyzes the temperature log 30 based upon the instruction set 20 to identify temperature patterns such as a localized temperature decreases (i.e. sweet spots 38 ) caused by gas entry into the wellbore. By analyzing the substantially real-time temperature throughout an interval of the wellbore, a more accurate characterization of the wellbore can be achieved. An accurate characterization can improve well completion decisions (especially for hydraulic fracturing) to allow for staged completions targeting points of gas influx.
[0035] In certain embodiments, the wellbore characterization system 10 is applied to an underbalanced drilling (UBD) operation. During the UBD operation the pressure in the wellbore is kept lower than the fluid pressure in the formation being drilled. As the well is being drilled, formation fluid flows into the wellbore and to the surface. It is understood that in the underbalanced drilling of tight reservoirs there is generally no water production and typically no oil/condensate. Therefore, any cooling effect observed by analyzing the temperature characteristics represented by the data model is due to gas entry into the well bore (i.e. the Joule Thompson effect related to gas expansion). Since the temperature measurement by the wellbore sensor 13 is continuous and along an interval of the wellbore, any changes in downhole pressure results in a change in temperature, which allows for estimation of reservoir permeability.
[0036] In certain embodiments, a fluid is injected into a formation (e.g. laminated rock formation) to remove or by-pass a near well damage, which may be caused by drilling mud invasion or other mechanisms, or to create a hydraulic fracture that extends hundreds of feet into the formation to enhance well flow capacity. A temperature of the injected fluid is typically lower than a temperature of each of the layers of the formation. Throughout the injection period, the colder fluid removes thermal energy from the wellbore and surrounding areas of the formation. Typically, the higher the inflow rate into the formation, the greater the injected fluid volume (i.e. its penetration depth into the formation), and the greater the cooled region. In the case of hydraulic fracturing, the injected fluid enters the created hydraulic fracture and cools the region adjacent to the fracture surface. When pumping stops, the heat conduction from the reservoir gradually warms the fluid in the wellbore. Where a portion of the formation does not receive inflow during injection will warm back faster due to a smaller cooled region, while the formation that received greater inflow warms back more slowly.
[0037] In certain embodiments, a hot slug is created in the wellbore. Specifically, the first chemical is injected from the coiled tubing 16 into the wellbore and the second chemical is injected through the annulus 17 . A hot slug is created where the first chemical and the second chemical mix. The hot slug can be detected by the wellbore sensor 13 . However, the hot slug can also be detected by other temperature sensors. It is understood that an operator can use the hot slug temperature spike to locate the interface between the first chemical and the second chemical (the interface location is of importance in many simulation treatments).
[0038] As a non-limiting example, the first and second chemicals for creation of the hot slug are injected together; however, the time (and hence the location) for creation of the hot slug can be controlled by the reaction rate. As a non-limiting example, the reaction is auto catalytic. As a further non-limiting example, the reaction rate can be controlled by encapsulation of one of the chemicals (such as by ethyl cellulose or paraffin (wax)). Specifically, as the reaction between the first chemical and the second chemical is initiated, an increase in temperature melts the wax. With the wax partially melted, more of the first and second chemicals are released, leading to a further increase in the reaction rate which melts the wax further, thereby releasing more of the first and second chemicals. In certain embodiments, an outside wall of the coiled tubing 16 can also be coated with one of the chemicals (e.g. NaNO2). Accordingly, a “heat-up” or temperature spike will be observed where the other reactant chemical (e.g. NH4C1) comes into contact with the chemical coated on the coiled tubing 16 . Once the hot slug is generated, the well can be produced to calculate the flow profile from entry and tracking of hot slug temperate spike in the wellbore.
[0039] The system 10 and methods described herein provide a means to characterize a reservoir in various drilling operations, including underbalanced drilling. Using continuous and substantially real-time temperature tracking, in addition to other measurements (both surface and downhole), the system 10 can extrapolate reservoir properties.
[0040] The preceding description has been presented with reference to presently preferred embodiments of the invention. Persons skilled in the art and technology to which this invention pertains will appreciate that alterations and changes in the described structures and methods of operation can be practiced without meaningfully departing from the principle, and scope of this invention. Accordingly, the foregoing description should not be read as pertaining only to the precise structures described and shown in the accompanying drawings, but rather should be read as consistent with and as support for the following claims, which are to have their fullest and fairest scope. | A method for determining flow distribution in a formation having a wellbore formed therein includes the steps of positioning a sensor within the wellbore, wherein the sensor generates a feedback signal representing at least one of a temperature and a pressure measured by the sensor, injecting a fluid into the wellbore and into at least a portion of the formation adjacent the sensor, shutting-in the wellbore for a pre-determined shut-in period, generating a simulated model representing at least one of simulated temperature characteristics and simulated pressure characteristics of the formation during the shut-in period, generating a data model representing at least one of actual temperature characteristics and actual pressure characteristics of the formation during the shut-in period, wherein the data model is derived from the feedback signal, comparing the data model to the simulated model, and adjusting parameters of the simulated model to substantially match the data model. | 4 |
[0001] This application is based on and claims priority under 35 U.S.C. § 119 with respect to Swedish Application No. 0001625-3 filed on May 3, 2000, the entire content of which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention generally relates to a temperature monitoring device. More specifically, the present invention pertains to a temperature monitoring device for controlling the temperature of an object, and for possibly also indicating and/or recording abnormal temperature variations. Although not limited in this regard, the device of the present invention can be to observe the temperature conditions of a bearing in operation.
BACKGROUND OF THE INVENTION
[0003] In modern bearing technology, bearings operate best within certain temperature ranges. For different types of bearings and/or different types of bearing applications, this temperature range can vary. During operation, the temperature will vary based on variations in different parameters such as load, speed and amount of lubricant. A rise in the bearing temperature above a certain level can thus provide an indication that there are risks that the bearing assembly may be starting to break down, thus presenting the possibly of causing damage to the machine equipment and/or other components with which the bearing assembly is associated.
[0004] Different temperature monitoring devices have been developed over the years, which are often rather complex and expensive, which might incorporate for instance a bimetallic relay, and which following a temperature increase exceeding a certain numeric value, open a valve to permit injection of a small amount of lubricant in the bearing. There are also relatively simple mechanical temperature monitoring devices which, for example, use a spring element having a shape memory effect to visually indicate that the temperature has passed a certain critical temperature level. A significant problem associated with such earlier known temperature monitoring devices, such as those disclosed in U.S. Pat. No. 4,448,147, is that they must be carefully calibrated before use. Also, these devices usually also have an ability to react only when a certain numerical temperature value has been exceeded, but are not sensitive to temperature variations over large ranges insofar as such ranges do not overlap the specified temperature value.
[0005] A need thus exists for a temperature monitoring device which is relatively simple in design and relatively easy to install, while at the same time bing quite efficient.
SUMMARY OF THE INVENTION
[0006] According to one aspect of the invention, a temperature monitoring device for continuously monitoring the temperature of an object includes a housing having contact means engageable with the object for producing heat transferring contact with the object, indicating means for outputting an indication of a temperature condition of the object, a sensing member positioned in heat transferring contact with the contact means to emit a signal representative of a current temperature of the object, and a control device connected to the sensing member to receive the signal from the sensing member representative of the current temperature of the object and to emit a signal to the indicating means to output the indication of the temperature condition of the object. A power supply means supplies power to the control device, the sensing member and the indicating means, and a switch means is urged to a first condition interrupting the supply of power from the power supply means to the control device, the sensing member and the indicating means, and is movable into a second condition causing the power supply means to supply power to the control device, the sensing member and the indicating means. A portion of the housing is movable between a first position in which the switch means is urged to the first condition and a second position in which the portion of the housing contacts the switch means to cause the power supply means to supply power to the control device, the sensing member and the indicating means.
[0007] According to another aspect of the invention, a temperature monitoring device for continuously monitoring the temperature of an object includes a housing adapted to be connected to the object, a sensing member sensing a current temperature of the object by way of heat transfer when the housing is connected to the object and emitting a signal representative of the current temperature of the object, an indicator mounted on the housing for outputting an indication of a temperature condition of the object, a processor connected to the sensing member to receive the signal from the sensing member representative of the current temperature of the object and to emit a signal to the indicating means to output the indication of the temperature condition of the object, and a power supply that supplies power to the processor, the sensing member and the indicator. A switch is changeable between a first condition in which power from the power supply to the processor, the sensing member and the indicating means is interrupted, and a second condition in which power is supplied from the power supply to the processor, the sensing member and the indicating means. A mechanism is provided for changing the switch between the first condition and the second condition.
[0008] In accordance with a further aspect of the invention, a temperature monitoring device for continuously monitoring the temperature of an object includes a housing adapted to be removably connected to the object and having a contact portion to contact the object in a heat transfer manner, a sensing member mounted on the housing in heat transferring contact with the contact portion of the housing to sense a current temperature of the object by way of heat transfer when the housing is connected to the object and emitting a signal representative of the current temperature of the object, an indicator mounted on the housing which produces an output indicating a temperature condition of the object, and a processor connected to the sensing member and the indicating means to receive the signal from the sensing member representative of the current temperature of the object and to emit a signal to the indicating means causing the indicating means to produce at least a first output indicating the temperature condition of the object. The processor determines a normal operating condition temperature of the object when a steady-state temperature of the object sensed by the sensing member has been reached and determines an abnormal operating condition temperature of the object when the temperature of the object sensed by the sensing member is outside a predetermined range from the normal operating condition temperature. The processor emits a signal to the indicator upon determining the abnormal operating condition temperature of the object so that the indicator produces the first output indicating the abnormal operating condition temperature of the object. In addition, a power supply supplies power to the processor, the sensing member and the indicator.
BRIEF DESCRIPTION OF THE DRAWING FIGURE
[0009] The foregoing and additional features and characteristics of the present invention will become more apparent from the following detailed description considered with reference to the accompanying FIG. 1 which is an exploded perspective view of the temperature monitoring device of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0010] The temperature monitoring device of the present invention as shown in FIG. 1 includes an elongated rod-like housing 1 . A fitting 2 is adapted to be connected to one axial end of the housing. The fitting 2 , which forms a contact portion of the housing, includes a threaded portion 3 for attachment of the fitting and the overall device to a threaded bore in the object that is to be supervised or monitored. The opposite axial end of the housing 1 carries a cover 4 . This cover 4 is provided with at least one transparent portion. The transparent portion can be in the form of one or more transparent windows provided in the cover or can be in the form of the cover itself being made of transparent material.
[0011] As can be seen from FIG. 1, the housing 1 is in the form of a substantially cylindrically-shaped tube. The axial end of the housing that is opposite the end carrying the fitting 2 is provided with a socket or open end 5 . The housing includes a cover 4 that is adapted to be received in the socket or open end 5 of the housing. The inner surface of the housing is provided with two diametrically opposed longitudinal grooves 6 extending through the interior of the housing. A removable frame 7 is adapted to be inserted into the interior of the housing, with the side edges of the frame 7 guided in the grooves 6 in the housing.
[0012] The frame 7 supports a power supply 8 , an indicator 9 , 10 , a control device 11 , a switch member 12 and a sensor member 13 . In the illustrated embodiment of the invention, the power supply 8 is the form of a battery, the indicators 9 , 10 are constituted by light emitting diodes (e.g., two differently colored light emitting diodes, such as one green and one red), the control device 11 is in the form of a processor, and the sensor member 13 is constituted by a thermistor. The thermistor 13 is formed as a limb or arm projecting from the frame 7 . The thermistor 13 and the switch member 12 are thus rigidly interconnected by virtue of being mounted on a common frame along with the battery 8 , the light emitting diodes 9 , 10 , and the processor 11 . The power supply or battery 8 can be connected, by way of the switch member 12 , to the thermistor 13 , the processor 11 and the light emitting diodes 9 , 10 via conduits printed on the frame.
[0013] When the frame 7 is fully inserted into the housing 1 , the light emitting diodes 9 , 10 are positioned just inside the cover 4 so that they can be seen from outside the housing through the transparent portion of the cover 4 (i.e., through the transparent window(s) or through the cover itself when the cover is made of transparent material). With the frame 7 positioned in the interior of the housing, the battery 8 , the processor 11 , the switch member 12 and the thermistor 13 will be situated inside the housing 1 to thereby be protected and enclosed by the surrounding housing.
[0014] The fitting 2 has a bar-shaped portion 14 extending axially in a direction away from the threaded portion 3 of the fitting. This bar-shaped portion 14 has a non-round shape to define a generally flat surface portion, and is arranged to be received in a correspondingly shaped non-round cavity in the end of the housing 1 .
[0015] The interior of the housing 1 is further provided with two diametrically opposed and circumferentially extending short grooves 15 (only one of which is visible in the drawing FIGURE). The grooves 15 thus extend over only a short inner circumferential portion of the housing interior. In the illustrated embodiment, the two grooves are positioned at locations displaced about 90′ in relation to the internal grooves 6 in the housing.
[0016] When the device thus described is mounted, the frame 7 , including the battery 8 , the light emitting diodes 9 , 10 , the processor 11 and the switch member 12 , is pushed into the housing 1 , with the edges of the frame 7 being received in and guided by the internal longitudinally extending grooves 6 of the housing. As mentioned above, with the frame 7 mounted in the housing, the light emitting diodes 9 , 10 are located inside the transparent portion of the cover 4 . When the frame 7 is in its completely inserted position in the housing 1 , the thermistor 13 is in heat transferring engagement or contact with the bar shaped or flat surface portion 14 of the fitting 2 .
[0017] The side of the cover 4 facing the housing 1 is provided with axially extending shoulders 16 , only one of which is visible in the drawing. These shoulders are arranged to be guided in the grooves 15 in the interior of the housing so that the cover 4 , when in position, can be rotated a short distance. The cover 4 also has an axially extending internal knob 17 . This knob 17 is positioned so that at one rotational position of the cover 4 the knob 17 presses the switch 12 on the frame to thereby connect the thermistor 13 , the processor 11 and the light emitting diodes 9 , 10 with the power supply (i.e., battery) 8 for energizing these current consuming elements, whereas in the other rotational position of the cover 4 the knob 17 is out of contact with the switch 12 . The switch 12 is thus biased or positioned at a first condition to interrupt the supply of power from the power source to the current consuming elements (the processor, the thermistor and the light emitting diodes) and is movable to a second condition through engagement of the switch 12 with a portion of the housing (i.e., the knob 17 on the cover 4 ) to balance the biasing effect and cause power to be supplied from the power supply to the current consuming elements. The knob 17 and cover 4 thus form a mechanism for changing the switch member 12 between the first condition and the second condition. The rotational movement of the cover required for turning on and turning off the device can be, for example, 90 degrees or less. An O-ring seal 18 is positioned between the housing I and the cover 4 for protecting the interior of the housing from moisture and dirt.
[0018] After being turned on, the battery 8 will continue to deliver drive current to the current consuming elements for as long as the switch is kept in this position or condition. However, the switch 12 is biased by a spring load or the like towards the closed position or closed condition, and will therefore switch off the current supply to the current consuming elements if the cover 4 is turned in the opposite direction so that the knob 17 on the cover 4 is moved away from the switch 12 . It is thus possible to switch on and switch off the device by simply rotating the cover 4 .
[0019] The function and operation of the device of the present invention is as follows. In use, the fitting 2 of the device is fitted or connected to an object whose temperature is to be monitored, e.g., bearing housing. This can be accomplished by screwing the threaded portion 3 of the fitting 2 into a threaded bore in the object so that the fitting is in heat conducting or heat transferring contact with the object. The drawing FIGURE illustrates an object 20 having a threaded bore 21 for receiving the threaded portion 3 of the fitting 2 .
[0020] When the monitoring work or operation is to begin, the cover 4 is turned by an appropriate amount in the appropriate direction (for example 90° in the clockwise direction) so that the cover 4 , at the end of this rotation, will be positioned such that the knob 17 presses on the switch 12 . The current consuming elements will thus be energized or supplied with power from the battery or other appropriate power source 8 .
[0021] The current supplied from the battery 8 causes the thermistor 13 to begin metering or monitoring the temperature of the bar shaped portion 14 . The processor causes one or both of the light emitting diodes 9 , 10 to flash, thereby indicating that the device is active. This can for instance be shown as two short flashes of a green light emitting diode followed by one short flash of a red light emitting diode.
[0022] The thermistor then begins to meter or monitor the temperature, and this can be shown by an appropriate signal from one or more of the light emitting diodes, for example the green light flashing, e.g. once every 60 seconds.
[0023] The temperature in the object is sensed over an extended period of time, e.g., two hours, when the object is supposed to have reached its steady-state temperature or normal operating temperature, whereupon the processor records or stores such temperature of the object. The processor then causes an appropriate signal to be emitted from one or more of the light emitting diodes. This can involve the green light emitting diode beginning flashing, e.g. once every 30 seconds. This is the normal operating condition for the device, and this condition is maintained as long as the temperature of the object remains within a specified range from the temperature recorded or stored as the normal condition temperature.
[0024] If however the temperature should rise above a predetermined lever, for example 10° C. above this normal condition temperature, the processor causes an appropriate signal to be issued from one or more of the light emitting diodes to thus indicate an abnormal temperature condition or error condition. This can involve, for example, the red light emitting diode starting to flash, e.g., three times for every 30 seconds. The operator is thus appropriately informed of the existence of an error condition or abnormal temperature condition with the object.
[0025] The operator then controls the cause of the error condition and takes the necessary steps for removing the error. When this is done successfully and the temperature again drops to the normal condition, the red light emitting diode is turned off and the green light emitting diode resumes its flashing condition, for example once every 30 seconds, thereby indicating a normal temperature condition for the object being monitored.
[0026] If the normal operating temperature for the object increases for some reason, e.g., through an exchange or replacement of components incorporated in the object, such as bearings or the like, the cover 4 is rotated in the direction opposite to the direction in which the cover was rotated to render the device operational (e.g., counter-clockwise). The knob 17 of the cover 4 will thus move away from the switch 12 to interrupt the power supply from the battery 8 to the current consuming elements, thus causing the temperature monitoring device to become inactive.
[0027] After a rest period, e.g. 30 minutes, the cover 4 is again turned in the appropriate direction (e.g., clockwise) to initiate the operational state of the device, whereupon the same procedure as that described above is resumed. However, after the first “normalizing” time period of, for example, two hours, the device starts to function in the normal state, but at a higher basic temperature.
[0028] It is thus possible to use the same or exactly similar devices in accordance with the invention for objects where changing normal temperature conditions occur, and also for applications having rather different basic normal temperature ranges, as the device of the present invention does not control or indicate if the object being monitored exceeds a certain numerical temperature value, but instead controls or monitors if the object undergoes a temperature increase from an arbitrary temperature level exceeding a certain temperature range, e.g., 10° C.
[0029] The fitting 2 with its threaded portion 3 and its rod shaped or flat surface portion 14 are preferably made from brass or another appropriate material having good temperature conducting properties. The frame 7 and the housing 1 can be manufactured from any suitable material that is sufficiently robust to withstand rough handling during use. These materials include plastic materials, such as polycarbonate.
[0030] The principles, preferred embodiment and mode of operation of the present invention have been described in the foregoing specification. However, the invention which is intended to be protected is not to be construed as limited to the particular embodiment disclosed. Further, the embodiment described herein is to be regarded as illustrative rather than restrictive. Variations and changes may be made by others, and equivalents employed, without departing from the spirit of the present invention. Accordingly, it is expressly intended that all such variations, changes and equivalents which fall within the spirit and scope of the present invention as defined in the claims, be embraced thereby. | Temperature monitoring device for monitoring or controlling the temperature of an object, and preferably indicating and/or recording abnormal temperature variations of the object includes a housing having a contact portion for contacting the object, a sensing member in heat transferring contact with the contact portion for emitting signals representative of the object temperature, a control device that receives signals from the sensing member and actuates an indicator, a power source connectable to the sensing member, the control device and the indicator, and a switch biased to interrupt the power supply to the sensing member, control device and indicator. A portion of the housing is movable between a first position where the switch interrupts the power supply and a second position in which the housing portion urges the switch to the power supply position. | 5 |
BACKGROUND OF THE INVENTION
The present invention relates broadly to methods and apparatus for preparing and treating traveling filaments and, more particularly, to a method for continuously processing and preparing twisted, dyed and bonded filaments.
Generally, filaments for use in the textile industry for sewing and other applications are prepared for use by application of one of several treatment agents. For example, fibrous filaments may be treated with a bonding agent to reduce fibrous projections from the surface thereof to reduce breakage. These or other filaments may be dyed to produce a desired color. Often filaments will also be treated with a lubricant to enhance their performance ability during industrial sewing operations. Often, these processes are done separately with liquid applications occurring in a bath and, if heat need be applied, it is applied in a hot air oven. The result is a generally slow process for taking raw filament and preparing a fully functioning thread, yarn or other finished filament.
Other treatments may be performed on the filaments which does not involve application of treating agents but rather involves surface texturizing. This includes adding a twist to the fibers to provide bulk or other desired surface textures. Often, the twist will be performed in a jet entanglement unit which entangles multifilament bundles by the application of high-pressure air thereto. This additional process adds to the expense and time required to prepare filaments for use in industry.
There accordingly exists a need for a high-speed process to produce filaments having the desired texturizing and application of treating liquid to rapidly produce a finished filament product.
SUMMARY OF THE INVENTION
It is accordingly an object of the present invention to provide a continuous, in-line process which produces twisted, dyed and bonded filaments.
To that end, a method and apparatus is provided. An apparatus for continuously treating traveling filaments includes an arrangement for causing at least one filament to travel along a travel path, an arrangement for rotatably supporting a first filament for payout thereof responsive to the means for causing the plurality of filaments to travel along the travel path; an assembly for rotating the means for rotatably supporting the first filament at a predetermined angular velocity to form a traveling twisted filament during filament payout therefrom and an arrangement for applying treating fluid to the traveling twisted filament with the treating fluid application arrangement being disposed along the predefined travel path. It is preferred that the apparatus further include an arrangement for thermally treating the traveling twisted filament with the thermal treatment arrangement being disposed along the travel path. Preferably, the arrangement for thermally treating the traveling twisted filament includes at least one pair of rolls with at least one of the rolls being driven and an assembly for heating at least one of the rolls to a predetermined temperature for heating a traveling twisted filament trained thereabout.
It is further preferred that the arrangement for applying a treating fluid to the traveling twisted filament includes an applicator for metering a predetermined amount of treatment fluid onto the traveling twisted filament.
Preferably, the arrangement for applying a treating fluid to the traveling twisted filament includes a supply of treatment fluid including a bonding agent and a release agent. It is further preferred that the arrangement for applying treating fluid to the traveling twisted filament includes a supply of treatment fluid including a dye and, preferably, a lubricant.
The assembly for causing at least one filament to travel along the travel path includes an assembly for winding the traveling twisted filament on a bobbin.
Preferentially, the present invention further includes an assembly for supporting a second filament rotatable about an axis of rotation for payout of the second filament responsive to the assembly for causing at least one filament to travel resulting in a twisted filament bundle suitable for further filament processing. The present invention further preferably includes an arrangement for supporting a third filament rotatable about a second axis of rotation for payout of the third filament responsive to the arrangement for causing at least one filament to travel with the first filament and the second filament being directed to travel coaxially with the second axis of rotation for twisting entanglement of the first filament, the second filament and the third filament as the first filament, the second filament and the third filament are paid out responsive to the arrangement for causing at least one filament to travel resulting in a twisted filament bundle suitable for further processing.
It is preferred that the arrangement for supporting a first filament for payout includes a wound filament package in a filament package support member rotatably mounted to a base for rotation of the wound package during payout of the filament. Further, the base is preferably rotatably driven in the apparatus further includes an assembly for driving the base at a predetermined angular speed. The arrangement for driving the base at a predetermined angular speed is preferably an electric motor operationally connected to the base for driving the base into rotation during payout of the filament. Similarly, the arrangement for supporting a second filament rotatable about an axis of rotation includes a wound filament package and the assembly for rotatably supporting a second filament for payout includes a filament package support member rotatably mounted to a second base for rotation of the wound package during payout of the second filament. Further, the base is preferably rotatably driven and the apparatus further includes an arrangement for driving the second base at a predetermined angular speed, preferably an electric motor operationally connected to the second base for driving the second base into rotation during payout of the filament with the motor having a passageway formed therein coaxially with the axis of rotation for passage therethrough of the first filament for twisting engagement with the second filament.
If is further preferred that the arrangement for supporting a third filament rotatable about a second axis of rotation includes a wound filament package with the arrangement for rotatably supporting a third filament for payment includes a filament package support member rotatably mounted to a third base for rotation of the wound package during payout of the third filament. Preferably, the third base is rotatably driven and the apparatus further includes an assembly for driving the third base at a predetermined angular speed. The assembly for driving the third base at a predetermined angular speed preferably includes an electric motor operationally connected to the third base for driving the third base into rotation during payout of the third filament with the motor having a passageway formed therein coaxially with the second axis of rotation for passage therethrough of the first filament and the second filament for twisting engagement with the first filament.
According to the method of the present invention, a method for continuously treating traveling filaments includes the steps of providing a textile machine for treating the traveling filament; causing at least one filament to travel along a travel path using an arrangement for causing at least one filament to travel along a travel path associated with the textile machine; rotatably supporting a first filament for payout thereof using an assembly for rotatably supporting a first filament for payout thereof responsive to being withdrawn by the assembly for causing a plurality of filaments to travel along the travel path; rotating the assembly for rotatably supporting a first filament using an arrangement for rotating the assembly for rotatably supporting a first filament at a predetermined angular velocity to form a traveling twisted filament during filament payout therefrom with the rotating assembly being associated with textile machines; and applying a treating fluid to the traveling twisted filament using an arrangement for applying a treating fluid to the traveling twisted filament with the arrangement for applying the treating fluid being associated with a textile machine and disposed along the travel path.
The method further preferably includes the step of thermally treating the traveling twisted filament using an assembly for thermally treating a traveling twisted filament with the thermal treatment assembly being disposed along the travel path. It is further preferred that the step of thermally treating the traveling twisted filament includes the step of causing the traveling twisted filament to travel around at least one pair of rolls associated with the textile machine, with at least one of the rolls being driven and heating the traveling twisted filament to a predetermined temperature using an assembly for heating at least one of the rolls to a predetermined temperature for heating a traveling twisted filament trained thereabout.
It is further preferred that the step of applying a treating fluid to the traveling twisted filament includes providing an applicator for metering a predetermined amount of treatment fluid onto the traveling twisted filament. The treating fluid application step preferably includes applying a bonding agent, or release agent, a dye and a lubricant thereto. It will be appreciated by those skilled in the art that any combination of the bonding agent, dye and lubricant may be added as required by the end use of the finished package. The release agent, as will be explained in greater detail hereinafter, is used during processing and does not remain with the finished product.
It is preferred that the step of causing at least one filament to travel along a travel path includes using an assembly for winding the traveling twisted filament on a bobbin associated with the textile machine. It is further preferred that the present invention further include the steps of providing a second filament rotatable about an axis of rotation for payout of the second filament responsive to being withdrawn by the assembly for causing a plurality of filaments to travel, directing the first filament to travel coaxially with the axis of rotation for twisting engagement of the first filament and the second filament as the first filament and second filament are paid out responsive to being withdrawn by the assembly for causing a plurality of filaments to travel resulting in a twisted filament bundle suitable for further filament processing. Additionally, the method of the present invention may include the steps of providing a third filament rotatable about a second axis of rotation for payout of the third filament responsive to being withdrawn by the assembly for causing a plurality of filaments to travel, and directing the second filament to travel coaxially with the second axis of rotation for twisting engagement of the first filament, the second filament and third filament as the first filament, second filament and third filament are paid out responsive to being withdrawn by the assembly for causing at least one filament to travel resulting in a twisted filament bundle suitable for further filament processing.
By the above, the present invention provides a method and apparatus for rapidly and continuously producing twisted, dyed and bonded filaments.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic view of an apparatus for producing dyed, twisted and bonded filaments according to one preferred embodiment of the present invention;
FIG. 2 is a diagrammatic view of an apparatus for producing dyed, twisted and bonded filaments according to a second preferred embodiment of the present invention; and
FIG. 3 is a diagrammatic view of an apparatus for producing dyed, twisted and bonded filaments according to a third preferred embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Turning now to the drawings and, more particularly, to FIG. 1, an apparatus for producing twisted, dyed and bonded filaments in a continuous in-line process is illustrated generally at 10 in a diagrammatic manner and includes a textile processing machine 12 and a filament supply 30. The textile processing machine 12 may take on virtually any configuration with the restricting requirement being that the elements which will be described in detail presently are arranged in a particular order to define a path for travel of a filament or filament bundle thereacross. Similarly, while the filament supply is shown as a skeletal frame structure, it will be appreciated that many configurations are possible by those skilled in the art with the primary requirements being consistent with those described below.
Turning now to the filament supply 30, a skeletal frame 31 is illustrated in FIG. 1 for supporting any number of filament packages. As seen in FIG. 1, three filament packages are provided for forming a twisted bundle of three filaments. FIG. 2 illustrates a single filament which may be twisted in the manner to be described presently. FIG. 3 is another version illustrating a pair of yarn packages for providing a twisted pair of filaments for processing. As may be appreciated, the choice of one, two, three or more filament packages is based on the requirements of the end user and it will not deviate from the present invention to use virtually any number of filaments in a manner described herein.
Focusing now on FIG. 1, a first filament package 40 is illustrated mounted to a rotatable platform 38 which is in turn mounted to a base 36 in vertical arrangement. The base 36 is mounted to the frame 31. An electric motor 32 is provided and mounted to the frame 31 and joined to the rotatable base using a belt 34. It will be appreciated by those skilled in the art that such a belt drive system is possible for driving the base 38 into rotation. It is also possible to use a direct drive motor to drive the base. A second, direct drive motor 44 is mounted vertically above the first filament package 40 and includes a rotatable base 46 attached to the armature thereof. A second filament package 45 is attached to the rotatable base 46. The armature of the direct drive motor 44 is hollow providing a passageway 48 for passage of the first filament 42 therethrough. Similarly, the second filament package 45 is mounted on a hollow tube which is in registry with the aforesaid passageway 48 for passage of the first filament 42 from the first filament package to a position above the second filament package 45. A second filament 49 is withdrawn from the second filament package and trained around the first filament emerging from the passageway 48. A third filament package 52 is mounted to a rotatable base 54 which is in turn mounted to another direct drive motor 50 similar to the first direct drive motor 44. Once again, a passageway 56 is formed in the armature of the second direct drive motor 50 for passage of the first filament 42 and the second filament 49 which are, by then, interlaced. This pair emerges from a hollow tube on which the third filament package 52 is mounted. The first and second filaments 42,49 emerge from the second passageway 56 to be interlaced with the third filament 58 being withdrawn from the third filament package 52. The resulting tri-filament bundle 60 is directed from the frame 31 to a yarn guide 15 disposed on the textile machine 12.
The textile machine 12 includes a first metering applicator 16 which meters a predetermined amount of bonding agent through a bonding agent supply line 27 from a bonding agent supply (not shown). Similarly, a release agent supply line 26 supplies a release agent selectively from a release agent supply (not shown) for mixing with the bonding agent for application to the filament bundle 60 in the first metering applicator 16. Downstream from the first metering applicator, a first pair of heated rolls 22 is provided. One or both of the rolls 22 may be heated to a temperature of approximately 100° C. to 230° C. A second metering applicator 18 is mounted to the textile machine downstream from the first heated roll pair 22 and is fed dye through a supply line 25 from a dye supply (not shown). A second heated roll pair 24 is provided downstream from the second applicator 18. The second heated roll pair is heated to a temperature of approximately 220° C. to 250° C. A third applicator 20 is provided downstream from the second heated roll pair 24 and mounted to the textile machine 12. The third applicator 20 is primarily for the application of lubricant through a lubricant supply line 28 from a lubricant supply (not shown).
All metering applicators 16,18,20 are configured to apply a predetermined amount of their respective liquid agents per unit running length of filament material. The amount of a specific agent chosen is dependent on the amount which the material will effectively carry and retain upon heat application. Insufficient amounts of liquid agents can result in a poorly finished product while excess amounts of liquid agents may be splattered upon application of heat or may run, both of which can be detrimental to the finished product. A proper amount will be whatever amount, determined primarily by experimentation, necessary to fully saturate the predetermined running length of material, or that which produces the desired effect on the filament material.
Finally, a conventional winder 29 is mounted to the textile machine to wind the filament bundle 60 onto a package 14 for later use. As may be appreciated, the winder 29 provides an arrangement for causing the filament bundle 60 to travel along the predefined travel path defined by the components previously described. Further driving influence is provided to the yarn bundle 60 by the driven, heated rolls 22,24. Therefore, the apparatus of the present invention provides a continuous, in-line processing assembly for individual filaments or filament bundles.
In operation, when it is determined what type of processing and how many filaments are to be processed, the necessary filament supply packages 40,45,52 are mounted to their respective rotatable bases 38,46,54 and thread-up commences. The first filament 42 is unwound from the first package 40 and fed into the passageway 48 associated with the second filament package. It is withdrawn therefrom and a second filament 49 is withdrawn from the second filament package 45 and interlaced with the first filament 42 to form a pair of interlaced filaments which are fed into the second passageway 56 associated with the third filament package 52. It is withdrawn therefrom and a third filament 58 is withdrawn from the third filament package 52 and interlaced with the aforesaid pair to form a tri-filament bundle 60 which is wound from the frame across the necessary yarn guides and onto the textile machine 12.
Thread-up continues with the filament bundle 60 extending through the first applicator 16 and from there it is trained around the first roll pair 22 which, as may be appreciated, is not yet heated. After being trained several times around the first roll pair 22, the filament bundle 60 is directed through the dye applicator 18 and then is trained several times around the second heated roll pair 24 which, of course, is not yet heated. From the second heated roll pair 24, the filament bundle is directed to the lubricant applicator 20 and from there wound onto a bobbin for winding by the winder 29 to form the finished package 14 once operations continue.
With reference to FIG. 2, a single filament may be threaded from its package 40 through the yarn guides and onto the textile machine 12. Referring to FIG. 3, a twisted pair is formed by omitting the third filament bundle while directing the first filament 42 through the second filament passageway 48 for interlacing with a second filament 49 being withdrawn from the second filament package 45. Operations of the various number of filaments is substantially identical except for the presence or absence of the additional filaments.
Once thread-up has been completed, the operations may then commence. With the winder 29 pulling yarn through the travel path, the respective motors 32,44,50 for the filament packages 40,45,52 are energized and are driven at a predetermined angular velocity which is typically on the order of 15,000 rpm to 20,000 rpm. By way of example, a 15,000 rpm rotation provides approximately three twists per inch in a traveling filament bundle. Preferably, all three filament packages 40,45,52 are driven in the same angular direction. Since the winder 29 is propelling the filaments along the travel path, pumps (not shown) are provided to supply the bonding agent and release agent mixture to the bonding agent applicator 16. The bonding agent is typically a nylon resin but may be other bonding agents as required by the type of filament involved in the process. The release agent may be a silicon oil and is provided to prevent the filaments from sticking to the heated rolls. The first heated roll pair 22 is heated to a predetermined temperature of approximately 150° C. which removes the aqueous carrier from the bonding agent, leaving the bonding agent coating the filament. Notably, if the bonding agent is polyester, a release agent may not be needed because it has been determined that using polyester as a bonding agent allows the filament to be heated by the roll pair to approximately 150° C. without the need for a release agent. The aqueous carrier for the polyester bonding agent flashes to steam forming a steam layer intermediate the heated rolls 22 and the filament bundle 60 which prevents the aforesaid sticking.
From the first heated roll pair 22, a liquid, aqueous dye may be applied in the dye applicator 18. After the dye is applied the filament bundle 60 travels around the second heated roll pair 24 for heating to a much higher temperature to set the dye and bonding agent. The temperature of the second heated roll pair 24 is on the order of 220° C. to 250° C. From the second heated roll pair 24, the filament bundle 20 proceeds through the lubricant applicator 20 where a lubricant, preferably silicone, is applied to the filament bundle which is then wound onto a package in a finished form.
By the above, the present invention provides a method and apparatus for continuously producing a twisted, dyed, bonded filament which proceeds from the raw filament packages to a finished product which can produce the finished product at a rate of approximately 1,000 meters per minute. The use of the present invention greatly reduces the cost of producing twisted, dyed and bonded filaments and provides the flexibility necessary to add or eliminate treatment liquids as required by the end use of the finished product.
It will therefore be readily understood by those persons skilled in the art that the present invention is susceptible of a broad utility and application. Many embodiments and adaptations of the present invention other than those herein described, as well as many variations, modifications and equivalent arrangements, will be apparent from or reasonably suggested by the present invention and the foregoing description thereof, without departing from the substance or scope of the present invention. Accordingly, while the present invention has been described herein in detail in relation to its preferred embodiment, it is to be understood that this disclosure is only illustrative and exemplary of the present invention and is made merely for purposes of providing a full and enabling disclosure of the invention. The foregoing disclosure is not intended or to be construed to limit the present invention or otherwise to exclude any such other embodiments, adaptations, variations, modifications and equivalent arrangements, the present invention being limited only by the claims appended hereto and the equivalents thereof. | A method and apparatus for continuously treating traveling filaments includes an assembly for causing at least one filament to travel along a travel path and assembly for rotatably supporting one or more filaments for payout therefrom responsive to the influence of the assembly for causing the filaments to travel, an assembly for rotating the filament supports at a predetermined angular velocity to form a traveling twisted filament and an arrangement for applying treating fluid to the traveling filaments. | 3 |
This application is a continuation of Ser. No. 557,342, filed Dec. 1, 1983, now abandoned, which is in turn a continuation of Ser. No. 383,099, filed May 28, 1982, now U.S. Pat. No. 4,450,455.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an ink jet head, and, more particularly, to an ink jet head for generation of small ink droplets for recording to be used for the so-called ink jet recording system.
2. Description of the Prior Art
An ink jet head to be applied for the ink jet recording system is generally provided with minute ink discharging outlets (orifices) having apertures of several tens μ to 100μ in diameter, ink flow paths and portions for generating ink discharging pressure provided at a part of said ink flow paths.
As the method for preparing such an ink jet head, there has been known, for example, a method in which minute grooves are formed, by way of cutting or etching, on a plate of a glass or a metal, and then the plate having such grooves is bonded to another appropriate plate for formation of ink flow paths.
However, a head obtained according to the method as described above suffers from a drawback that straight driving characteristic of ink droplets discharged has frequently been impaired. This is due, after all, to the difference in wetting characteristics at the orifice peripheral for the ink, because the orifice of the head is formed of materials having different qualities.
In addition to the above fact, when discharging of an ink has been carried out for a long time or vibration is applied to a head, the ink leaked out from the orifice may be adhered to a part of the orifice circumference and then combined to form an ink pool, which will attract the ink droplets discharged toward its direction, thereby impairing straight driving characteristic of ink droplets.
In the prior art, in order to overcome such an inconvenience, it has been proposed to prepare separately a flat plate provided with orifice by forming an orifice on a flat plate (e.g., a metal plate or a photosensitive glass plate) by etching thereof (this is hereinafter referred to as "orifice plate") and then attaching the orifice plate onto a head body to give an ink jet head.
According to this method, however, an orifice is formed by etching and therefore strains may be formed in the orifices obtained due to the difference in the degree of etching, or the shapes of orifices may vary considerably, whereby it is difficult to prepare an orifice plate which is very precise. Thus, the ink jet head prepared by this method has the drawback that straight driving characteristic of the ink droplets discharged could not be sufficiently improved.
Further, in the above method, an orifice plate is required to be attached to a head body. During such an operation, dimensional precision is liable to be less. In addition, there are other disadvantages such as the adhesive employed in this operation may flow into orifices or ink flow paths which are very minute to effect clogging thereof, thus impairing the function inherent in an ink jet head.
SUMMARY OF THE INVENTION
The primary object of the present invention is to provide an ink jet head which has overcome the various drawbacks of prior art ink jet heads as described above and is also provided with a further specific feature.
One object of the present invention is to provide an ink jet head which can ensure the straight driving characteristic of ink jet droplets discharged for a long term.
Another object of the present invention is to provide an ink jet head which is precise and also very reliable.
A further object of the present invention is to provide an ink jet head having a construction which is very precise as to the ink flow paths including orifices.
Further, it is also another object of the present invention to provide a multi-orifice type ink jet head which can be produced by a simple method with good yield and has excellent durability.
According to the present invention, there is provided an ink jet head which comprises an orifice plate constituted of a hardened film of a photosensitive resin having an orifice which extends therethrough in the direction of its thickness.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 and FIG. 2 are schematic perspective views for illustration of parts of an embodiment of the ink jet head according to the present invention;
FIG. 3, FIG. 4, FIG. 6 and FIG. 7 are schematic sectional views of parts of an embodiment of the ink jet head according to the present invention, and
FIG. 5 is a perspective view of the appearance of a part of an embodiment according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the accompanying drawings, preferred embodiments of the overall present invention are to be described in detail.
FIGS. 1 through 4 are schematic drawings of an embodiment of the ink jet head and its preparation steps.
First, as shown in FIG. 1, on an appropriate substrate 1 of a glass, a ceramic, a plastic or a metal, there are arranged ink discharging pressure generating elements 2 in a desired number (two in the drawings) such as heat generating elements, piezoelectric elements and the like, and the substrate 1 is joined with another plate 3 having grooves for ink flow paths to prepare a head body 4. In the drawings, 5-1 and 5-2 are all ink discharging outlets (orifices) in the head body 4. When heat generating elements are used as the ink discharging pressure generating elements 2, ink discharging pressure is generated by heating the ink in the neighborhood of these elements with these elements. On the other hand, when piezoelectric elements are employed, ink discharging pressure is generated by mechanical displacement or vibration of these elements and electrodes not shown for signal input are connected to these elements 2.
The constitution of such a head body 4 is not related directly to the subject matter of the present invention, and therefore, any further details thereof are omitted.
Next, as shown in FIG. 2, after the end surface on the orifice side of the head body 4 is cleaned and dried (during this operation, said end surface may sometimes be roughened), a dry film photoresist 6 (film thickness: about 25μ to 100μ) heated to about 80° C. to 105° C. is pressure bonded onto said end surface at a speed of 0.5 to 4 feet/min. under pressurization condition of 1-3 kg/cm 2 . The dry film photoresist 6 is thereby fixed partially in a fusion bonded state, and will thereafter never be peeled off from the head body 4 even when a considerable external pressure is applied thereto.
Subsequently, as shown in FIG. 3, a photomask 7 having mask patterns 7a and 7b corresponding to orifices of desirable shape are superposed on the dry film photoresist 6 fixed to the end surface on the orifice side of the head body 4, and then light is projected to said mask 7. Since the patterns 7a and 7b do not transmit light, the dry film photoresist 6 in the region covered by these patterns 7a and 7b is not subjected to light exposure. In carrying out this procedure, an accurate positioning is conducted according to a conventional manner so that the centers of the mask patterns 7a and 7b may fall on the centers of the orifices 5-1 and 5-2, respectively of the head body 4. When subjected to light exposure as described above, the region except the portions corresponding to the patterns 7a and 7b, namely, the exposed photoresist 6, undergoes polymerization reaction to be hardened, thus being rendered insoluble in a solvent. On the other hand, the photoresist 6 not exposed to the light, is not hardened and remains soluble in a solvent. After such a light exposure precedure, the dry film photoresist 6 is immersed in a volatile organic solvent, for example, trichloroethane for dissolving away unpolymerized (unhardened) photoresist, whereby there are formed thru-holes 8-1 and 8-2 (FIG. 4) corresponding to the patterns 7a and 7b through the hardened photoresist film 6H. Then, for the purpose of enhancing solvent resistance of the hardened photoresist film 6H remaining at the end surface on the orifice side of the head body 4, the film is subjected to further hardening. Such a hardening may be conducted according to heat polymerization (heating at 130° C. to 160° C. for about 10 to 60 minutes), UV-ray irradiation or a combination thereof. Thus, the thru-holes 8-1 and 8-2 formed through the hardened photoresist film 6H corresponding to the orifice plate may have any desired lateral cross-sectional shape (not shown) such as circular, square shapes and the like. The longitudinal cross-sectional shapes of the thru-holes 8-1 and 8-2 may also be freely varied, as desired such as in the form tapered narrower toward the ink discharging direction, or, alternatively, in the form broadened towards the tip or in a straight form.
In this embodiment, when the mask patterns 7a and 7b were made circular with a diameter of 60μ, the thru-holes 8-1 and 8-2 actually formed through the photoresist hardened film 6H (thickness: 50μ) were obtained with a precision of about ±5μ. For the purpose of reference, when the same thru-holes as in the above embodiment were formed on a silicon flat plate by etching methods, its precision was about ±15μ.
The positional deviation between the orifices 5-1, 5-2 and the thru-holes 8-1, 8-2 was found to be about ±5μ in this embodiment, but that of the latter method was as high as ±30μ. As the result, when the shot attaching precisions of the ink jetted out from the heads provided with respective orifice plates as described above are compared between the present invention and the prior art, the shot attaching precision of the present invention was superior by about 5 times to that of the prior art.
Turning now to FIG. 1, FIG. 2 and FIG. 5 through FIG. 7, another embodiment of the present invention is to be described. The detailed description about FIG. 1 and FIG. 2 is the same as in the first embodiment previously described and therefore it is omitted in this embodiment by incorporating the corresponding description by way of reference.
As described above, after completion of the preparation step as shown in FIG. 2, on the dry film photoresist 6 fixed at the end surface on the orifice side of the head body 4 as shown in FIG. 5, there is superposed a photomask 17 having mask patterns 17a and 17b corresponding to orifices of desired shapes and a mesh-like pattern 17c around said mask patterns, followed by projecting light to said mask 17 (as in FIG. 6). Since the above patterns 17a, 17b and 17c do not transmit light, the dry film photoresist at the regions covered by these patterns 17a, 17b and 17c is not subjected to the light exposure. An accurate positioning is conducted in a conventional manner, before the exposure, so that the centers of the mask patterns 17a and 17b may coincide with the centers of the orifices 5-1 and 5-2 of the head body 4, respectively. The dry film photoresist 6 at the region covered by the mesh-like pattern 17c, is not completely masked and therefore, is slightly exposed. In addition, the peripherals of the patterns 17a and 17b corresponding to orifices are arranged so that they may be exposed in annular shapes as shown in the drawing. This is because the peripherals themselves of the orifices may otherwise be roughened in the subsequent developing treatment step (dissolving the unhardened resist), whereby straight driving characteristic of ink droplets discharged may be undesirably lowered.
When subjected to light exposure as described above, the region except the patterns 17a and 17b, namely, the exposed portion of photoresist 6, undergoes polymerization reaction to be hardened, thus being rendered insoluble in a solvent. On the other hand, the photoresist 6 not exposed to light is not hardened and remains soluble in a solvent. After such a light exposure procedure, the dry film photoresist 6 is immersed in a volatile organic solvent, for example, trichloroethane for dissolving away unpolymerized (unhardened) photoresist, whereby there are formed thru-holes 18-1 and 18-2 corresponding to the patterns 17a and 17b through the hardened photoresist film 16H, and uneven surface 19 (FIG. 7). Then, for the purpose of increasing solvent resistance of the hardened photoresist film 16H remaining at the end surface on the orifice side of the head body 4, the film is subjected to further hardening. Such a hardening may be conducted according to heat polymerization (heating at 130° C. to 160° C. for about 10 to 60 minutes), UV-ray irradiation or a combination thereof.
Thus, the thru-holes 18-1 and 18-2 formed through the hardened photoresist film 16H corresponding to the orifice plate may have any desired lateral cross-sectional shape (not shown) such as circular, square shapes and the like. The longitudinal cross-sectional shapes of the thru-holes 18-1 and 18-2 may be also freely varied, as desired, such as in the form tapered narrower toward the ink discharging direction, or, alternatively, in the form broadened towards the tip or in the straight form.
In this embodiment, when the mask pattern 17a and 17b are made circular with diameters of 60μ, the thru-holes 18-1 and 18-2 actually formed through the photoresist hardened film 16H (thickness: 50μ) were obtained with a precision of about ±5μ. For the purpose of reference, when the same thru-holes as in the above embodiment were formed on a silicon flat plate by etching methods, its precision was about ±15μ.
The positional deviation between the orifices 5-1, 5-2 and the thru-holes 18-1, 18-2 was found to be about ±15μ in case of the present invention, while that of the latter method was as high as ±30μ. As a result, when the shot attaching precisions of the ink jetted out from the heads provided with respective orifice plates as described above were compared between the present invention and the prior art, the shot attaching precision of the present invention was superior by about 5 times to that of the prior art, similarly to the foregoing embodiment.
Further, the degree of unevenness formed on the surface of orifice plate, namely the degree of roughness, can be very freely controlled depending on the mesh size in the mesh-like mask 17c (in FIG. 5) (by controlling the dosage of exposure). Such a mask for roughening the surface of an orifice plate is not limited to the mesh-like mask as employed in the above embodiment, but there may also be employed masks of radially- or parallelly-shaped patterns.
A dry film photoresist as employed in each of the above embodiments is a preferable photosensitive resin to be used in the present invention because of its easiness in handling as well as easy and accurate control of its thickness. Such film types, there are photosensitive resins sold under the trade names of, for example, Permanent Photopolymer Coating RISTON, Solder Mask 730S, 740S, 730FR, SM1, etc. produced by Du Pont Co.
As described above, the present invention has a number of effects as enumerated below:
(1) Since the orifices are formed of the same material, with extremely good dimensional precision, straight driving characteristic of ink droplets discharge is excellent with sizes of ink droplets being made uniform.
(2) The surface (face) of the orifice plate is made rough so as to exhibit uniform wettability for ink, so that an ink pool around the orifices will be difficult to form and the straight driving characteristic of ink droplets is stabilized even upon prolonged driving.
(3) Since a number of orifices with the same dimension and shape can be formed simultaneously, high density multi-array ink jet heads can be manufactured easily with excellent productivity.
(4) Orifices of a desired shape can be formed depending on the photomask to be applied.
(5) Since self-adhesiveness of a photosensitive resin is utilized, no particular adhesive is required to be used, and therefore there is no fear of clogging of ink flow paths such as orifices and the like by flowing of such an adhesive into the flow paths.
(6) Registration between the head body and the orifices formed can be done accurately and easily.
(7) Since no etching (strong acids such as hydrofluoric acid and the like) is required to be used, there is also an advantage with respect to safety and hygiene. | A method of making an ink jet head with an orifice plate having an orifice extending therethrough for ink ejection involves the steps of adhering a photosensitive plate to the ink jet head to cover the outlet of a liquid passageway in the head, aligning a pattern mask with the ink passageway, exposing the photosensitive plate in-situ to radiation through the pattern mask, and removing portions of the photosensitive plate in accordance with the radiation pattern to form in the photosensitive plate an orifice aligned with the outlet. | 1 |
BACKGROUND OF THE INVENTION
Areas of Application in Industry
The present invention concerns a method of manufacturing an organopolysiloxane containing terminal alkenyl groups. In detail, it concerns a method of manufacturing an organopolysiloxane manufactured by means of non-equilibrium polymerization and at least having an alkenyl group at one end and some specific group at the other end of the molecule.
Conventional Technology
The ring-opening polymerization of cyclic trisiloxane using an alkali metal cataylst is known in the art as an industrial technology. Also known in the art is what is termed living polymerization, which yields non-equilibrium polymerization. For example, in Macromolecules Vol. 3 No. 1 (1970), page 1, J. Saam et at. noted that, following ring-opening polymerization of hexamethyl cyclotrisiloxane using butyl lithium, the addition of vinyl chlorosilane caused polymerization to cease. This resulted in the production of an organopolysiloxane having a terminal vinyl group at one end of the molecule. Japanese Laid-open Patent No. 59-78,236 published May 7, 1984 presents a similar method for the manufacture of organopolysiloxane. This method of introducing a functional group by means of a polymerizationterminating agent containing that functional group is generally called a "termination method. "
Problems of Conventional Technology
With this type of conventional technology, chain termination at the end of the molecule is carried out when the polymer is formed. There is thus no guarantee that the reaction which introduces this functional group is completed. This is a disadvantage. A second disadvantage is that, if a functional group is not introduced at the terminal end (that is to say, at the head) of the molecule at the time of polymerization initiation, then only monofunctional organopolysiloxane will be obtained. This is also a disadvantage.
SUMMARY OF THE INVENTION
Purpose of the Invention
The inventors of the present invention undertook extensive investigations with the objective of remedying the defects in this sort of termination method. These investigations resulted in the present invention. To summarize, the objective of the present invention is to provide a method of manufacturing organopolysiloxane with alkenyl groups at least reliably introduced at the terminal end (that is to say, at the head) of the molecule during polymerization initiation by means of non-equilibrium polymerization.
The objective of the abovementioned present invention is to provide a method of manufacturing organopolysiloxane having terminal alkenyl groups as represented by the formula ##STR1## and characterized by the fact that the reaction is terminated after the polymerization of cyclic trisiloxane in accordance with the formula ##STR2## wherein the polymerization initiator is an alkali metal salt of an organosilane or organopolysiloxane as represented by the formula ##STR3## and the reaction is carried out in the presence or absence of a molecular weight regulator which is an organosilane or organopolysiloxane as represented by the formula ##STR4## wherein
R 1 represents an alkenyl group, R represents a single-charge hydrocarbon group or single-charge halogenated hydrocarbon group of the same or different type. A represents an alkali metal, m represents 0 or an integer of 1 or above, p and m represent 0 or the same or different integers of 1 or above, B represents a hydrogen atom or a single-charge group selected from among terminal ending groups, and n meets the conditions of n≧m+3, and where the molar ratio of the polymer initiator and the molecular weight regulator are in a range of 100:0-0.1:100.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In greater detail, the organosilane or organosiloxane alkali salt used as the polymerization initiating agent is characterized by the fact that it contains an alkenyl group bonded to the silicon atom at the terminal end of the molecule, and an alkali metal substituted for a hydrogen atom in the hydroxyl group bonded to the opposite terminal end (or, in organosilane, the same silicon atom). Methods of manufacturing this alkali salt of organosilane or organopolysiloxane are known in the art. For example, monochlorosilane or polysiloxane containing alkenyl groups corresponding to those described above can be carefully hydrolyzed with a dilute alkaline aqueous solution, to yield an organosilane or organopolysiloxane which simultaneously contains alkenyl groups and silanol groups. This is then reacted with an alkali metal compound to yield the corresponding alkali metal salt. The alkali metal compounds represented by A include lithium, sodium, and potassium. However, lithium is preferred, just as with usual organopolysiloxane non-equilibrium polymerization. When the silanol group becomes a lithium salt, the reaction is usually with alkyl lithium. However, the use of n-butyl lithium is preferred for the present invention.
Normally, ethylene double bonds tend toward polymerization under the influence of an alkali catalyst. However, the present invention employs a specially structured organosilane or organopolysiloxane as the polymerization initiator, so that the terminal alkenyl group of the organopolysiloxane remains stable throughout the entire manufacturing process.
Due to factors related to ease of raw material acquisition and manufacture, raw materials with alkenyl groups R 1 having a carbon number of 2 to 10 are preferred, with a carbon number of 2 to 6 are more preferred. These alkenyl groups can include vinyl groups, butenyl groups, hexenyl groups, and decenyl groups. There are no particular limitations on the position of the double bond within the alkenyl group, but with regard to the reactivity of the resulting polymer, it is best if the double bond is at the end of the alkenyl group. R represents single-charge hydrocarbon groups or halogenated hydrocarbon groups of the same or different types. For ease of manufacturing, it is best if all or most of these groups are methyl groups. Examples of bonding groups other than methyl groups include such alkyl groups as ethyl groups, propyl groups, butyl groups, pentyl groups and hexyl groups, such aryl groups as phenyl groups, tolyl groups and xylyl groups, such aralkyl groups as benzyl groups and phenetyl groups, and halogenated alkyl groups such as chloromethyl groups, chloropropyl groups and trifluoropropyl groups. If introduction of an alkenyl group within the molecular chain is desired, then R can also be an alkenyl group.
Values for m have been established as 0 or an integer of 1 or above. However, when m=0, the stability of the organosilane precursor is poor, and the hydroxyl groups are unfortunately quite prone to dehydrogenation condensation. Because organopolysiloxane precursors containing silanol groups are stable with regard to dehydrogenation, and also because of considerations of ease of manufacture, organopolysiloxanes in which m=3 to 20 are preferred.
The cyclic trisiloxane used in the present invention is known in the art as a monomer for use in non-equilibrium polymerization. The substituted group R, which is bonded to the silicon atom, is a single-charge hydrocarbon group or single-charge halogenated hydrocarbon group of the same type or a different type as that described above. If introduction of an alkenyl group into the molecular chain is desirable, then R can be an alkenyl group. Factors concerning ease of acquisition dictate that methyl groups or phenyl groups are practical choices for the substituted group R bonded to the silicon atom in the cyclic trisiloxane.
Conditions for the polymerization reaction vary depending on the monomer used. For example, when polymerizing hexamethyl cyclotrisiloxane, the reaction should be carried out for 1 to 50 hours in a solvent medium at 0° to 30° C. The solvent medium should be a non-protonating substance in which both the starting materials and the product polymer are readily soluble. Examples of solvent media include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, ethers such as tetrahydrofuran and diethyl ether, ketones such as acetone and methylethyl ketone, esters such as ethyl acetate and butyl acetate, and such other substances as dimethyl formaldehyde, dimethyl sulfoxide, and hexamethyl phosphoric triamide. Good results are also frequently obtained using a mixture of 2 or more solvents. For example, when using a solvent with low polarity, such as toluene, the reaction can be accelerated by the addition of a high-polarity solvent such as dimethyl formaldehyde, dimethyl sulfoxide, or hexamethyl phosphoric triamide.
Of the reaction conditions, it is particularly important to carefully regulate reaction temperature and time so that repartition reactions do not occur. Particular care is required when manufacturing an organopolysiloxane having an alkenyl group at only one end of the molecular chain. This is because, if the polymerization reaction changes from non-equilibrium polymerization to an equilibrium reaction with repartition, then it will no longer be possible to maintain the alkenyl group at only one end. In other words, polymers having alkenyl groups at both ends and other polymers having alkenyl groups at neither end will be produced as side products.
It is usually best to monitor the polymerization reaction by means of gas chromatography or the like to detect residual amounts of original monomer, and to terminate the reaction by means of a neutralizing operation when the reaction rate has reached a specific level. The reaction rate percentage at which the reaction should be terminated varies widely, depending on the original monomer and the target polymer, but normally falls within a range of 70 to 100%, and preferably 80 to 95%.
Before the reaction, it is necessary to reduce the water content of the solvent and the original monomer as much as possible. Water content will cause a reduction in the molecular weight of the resulting organopolysiloxane, and make it impossible to obtain the target organopolysiloxane having terminal alkenyl groups. Recommended methods for drying the solvent and monomer include distillation, heating, bubbling with drying gas, adsorption onto active alumina, silica gel, or zeolite, and dehydrogenation by an alkali metal or alkali metal compound.
Under the manufacturing method of the present invention, the molecular weight of the resulting organopolysiloxane is determined by the ratio of the polymerization initiator and the cyclic trisiloxane which is consumed in the polymerization process. The substitution reaction between the silanol group and alkali metal silanolate occurs at very high speed. It is thus acceptable to add, as a molecular weight regulator, an organosilane or organopolysiloxane containing silanol groups which are the raw material of the polymerization initiator alkali metal silanolate.
When the polymerization initiator is being produced, this molecular weight regulator causes a reaction to occur with the mole number of the alkali metal compound being lower than the mole number of silanol groups. Any combination of polymerization initiator and organosilane or organopolysiloxane having unreacted silanol groups can be used. Raw material for the polymerization initiator may also be newly added, and made up of an unrelated organosilane or organopolysiloxane with terminal alkenyl groups. There is no particular limitation on the degree of polymerization p of this molecular weight regulator, which can be the same as or different from m, as long as it is 0 or an integer of 1 or above. Preferably, however, this value will be 3 to 20, just as for m.
The quantity of alkali metal silanolate should be sufficient to produce the ring-opening reaction, with this quantity such that the mole ratio of the polymerization initiator (alkali metal) and the molecular weight regulator (silanol) is 100:0 to 0.1:100. If this ratio falls in the range 0.5:99.5 to 50:50, then a desirable polymerization speed can be attained. This is preferred with regard to production efficiency, and also conserves expensive catalyst.
The neutralizing agent used to terminate the reaction can be any material which reacts with alkali metal silanolate to form a stable alkali metal salt. Examples include hydrated carbonic acid gas, such mineral acids as hydrochloric acid and sulfuric acid, such carboxylic acids as acetic acid, propionic acid and acrylic acid, and such chlorosilanes as trimethyl chlorosilane, dimethyl chlorosilane, dimethylphenyl chlorosilane and dimethylvinyl chlorosilane. When polymerization is terminated with hydrated carbonic acid gas, mineral acid or carboxylic acid, the polymer terminating group will be a silanol group. If terminated with chlorosilane, the terminal ending group will be a silyl group from chlorosilane with the chlorine atom removed. In other words, acid should be used for termination when it is desirable to produce an organopolysiloxane with a silanol group introduced at the end of the molecule opposite to the alkenyl group. When a functional group bonded to a silicon atom is to be introduced, chlorosilane containing that functional group should be used for termination. A variety of chlorosilanes can also be added to a silanol-terminated organopolysiloxane which was previously obtained by means of acid termination, and various functional groups can be introduced by hydrochloric acid removal reaction. At this juncture, use of a hydrochloric acid supplement such as an amine is recommended. A variety of functional groups can also be introduced through reactions with silanol-group terminating organopolysiloxanes and silazanes, aminosilanes, silyl amides, or alkoxy silanes. The organopolysiloxanes obtained in this way have an n value of at least 3, an alkenyl group at one end of the molecule, and at B, on the other end, a hydrogen atom or a silyl group bonded to an alkyl group, aryl group, alkenyl group, alkynyl group or hydrogen atom.
An organopolysiloxane containing a terminal alkenyl group and produced by means of the present invention can be used in, for example, the reaction in the presence of platinum catalyst of methylhydrogen polysiloxane chain-terminated at both ends by trimethylsiloxy groups to yield a graft copolymer of organopolysiloxane. In addition, the reactivity of the alkenyl group makes it possible to easily obtain a copolymer with a polymer other than organopolysiloxane.
PRACTICAL EXAMPLES
Below, the present invention will be described with reference to practical examples of its implementation. In the examples, "Me" represents a methyl group, "Vi" a vinyl group, and "Hex" a Vi(CH 2 ) 4 --. Unless noted, characteristic values are for measurements carried out at 25° C. Insofar as possible, water was removed from the solvents and reagents before use.
PRACTICAL EXAMPLE 1
Samples of 200 g water, 200 g ice, 80 g diethyl ether, and 13 g sodium hydrogencarbonate were added to 4 flasks with mixers attached. While the mixtures were being thoroughly mixed, a mixture of 40 g of Me 2 ViSi(OSiMe 2 ) 3 Cl and 35 g diethyl ether was dripped in. After separation of the liquids, anhydrous sodium sulfate was added to dry the ether layer, and then the ether was removed by distillation to yield Me 2 ViSi(OSiMe 2 ) 3 OH. This was termed OH-1.
Into 4 flasks equipped with mixers were placed 4.97 g of OH-1, 40 ml of tetrahydrofuran and 10 ml of 1.53N hexane solution of n-butyl lithium. This was mixed to yield a lithium salt of OH-1, Me 2 ViSi(OSiMe 2 ) 3 OLi, which was termed OLI-1 (0.31 mol/liter). Into 4 mixer-equipped flasks were placed samples of 0.60 ml (0.186 mmol) OLI-1, 6.43 g (19.8 mmol) OH-1, 75 g hexamethyl cyclotrisiloxane, 75 g toluene and 1.5 g dimethyl sulfoxide. This mixture was reacted under a nitrogen atmosphere at room temperature for 5 hours. At this point gas chromatography indicated that a reaction rate of 80% had been reached, so the reaction was neutralized with dry ice. After filtration, reduced pressure distillation was used to remove the solvent and unreacted raw materials. The resulting polymer was termed VP-1. Gel permeation chromatography (GPC), Fourier transformation nuclear magnetic resonance (FTNMR), and iodometric quantification of the vinyl group were all used to confirm that VP-1 was an organopolysiloxane expressed by the following Mean Formula.
Me.sub.2 ViSiO--(Me.sub.2 SiO).sub.45 --SiMe.sub.2 OH
Molecular weight distribution dispersion (Mw/Mn) by GPC was 1.19 for the polymer.
PRACTICAL EXAMPLE 2
Into 4 mixer-equipped flasks were placed samples of 6.1 ml (5 mmol) of OLI-1 from Practical Example 1, 41.6 g hexamethyl cyclotrisiloxane and 41.6 g tetrahydrofuran. This mixture was reacted under an argon atmosphere for 3.5 hours at room temperature. At this point gas chromatography indicated a reaction rate of 89%, so 0.71 g (7.5 mmol) of dimethyl chlorosilane was added and mixed in to neutralize the reaction. After filtration, the solvent and unreacted materials were removed by reduced pressure distillation. The resulting polymer was termed VP-2. GPC and FTNMR analysis indicated that this VP-2 was an organopolysiloxane represented by the following Mean Formula.
ME.sub.2 ViSiO--(Me.sub.2 SiO).sub.98 --SiMe.sub.2 H
PRACTICAL EXAMPLE 3
Me 2 HexSi(OSiMe 2 ) 3 OH was synthesized in the same way as OH-1 of Practical Example 1, and was termed OH-2. Next, using the same methods as for Practical Example 1, OH-2 and n-butyl lithium were reacted to yield a solution of the OH-2 lithium salt termed OLI-2 (0.28 mol/liter).
Into 4 mixer-equipped flasks was placed 23.9 ml (6.7 mmol) OLI-2, 70 g hexamethyl cyclotrisiloxane, 70 g toluene and 2.5 g dimethyl sulfoxide. These materials were mixed for 24 hours at 10° C. At this point gas chromatography indicated a reaction rate of 85%, so the mixture was neutralized with 0.6 g (10 mmol) of acetic acid. After filtration, the solvent and unreacted materials were removed by reduced pressure distillation. The resulting polymer was termed HP-1. Analysis using GPC, FTNMR and iodometry indicated that this HP-1 was the following organopolysiloxane.
Me.sub.2 HexSiO--(Me.sub.2 SiO).sub.126 --SiMe.sub.2 OH
Into 4 mixer-equipped flasks were placed 50 g (5.22 mmol) HP-1, 1.26 g (10.4 mmol) dimethylvinyl chlorosilane, 2.22 g (22 mmol) triethylamine, 50 g toluene, and 40 g tetrahydrofuran. This mixture was reacted at room temperature for 24 hours. After filtration, the solvent and unreacted materials were removed using reduced pressure distillation, yielding a polymer. This polymer was termed HP-2. Analysis by GPC, FTNMR and iodometry confirmed that this HP-2 was the following organopolysiloxane.
Me.sub.2 HexSiO--(Me.sub.2 SiO).sub.127 --SiMe.sub.2 Vi
PRACTICAL EXAMPLE 4
Samples of 3.5 g (10.8 mmol) of OH-1 from Practical Example 1 were placed in 4 mixer-equipped flasks, and 1.3 ml (2.1 mmol) of 1.62N hexane solution of n-butyl lithium was added under a nitrogen atmosphere. Mixing was carried out, yielding a mixture in which 20 mol% of all lithium groups in the OH-1 were lithium-ized. To this was added 30 g hexamethyl cyclotrisiloxane, 30 g toluene, and 0.6 g dimethyl sulfonate. This mixture was reacted under a nitrogen atmosphere at room temperature for 3.5 hours, at which point gas chromatography indicated a reaction rate of 80%. Then 0.15 g (2.5 mmol) acetic acid was added and mixed in to neutralize the mixture. After filtration, the solvent and unreacted materials were removed by reduced pressure distillation. The resulting polymer was termed VP-3. Analysis by GPC and FTNMR confirmed that this VP-3 was an organopolysiloxane represented by the formula below.
Me.sub.2 ViSiO--(Me.sub.2 SiO).sub.33 --SiMe.sub.2 OH
EFFECTS OF THE INVENTION
The organopolysiloxane manufacturing method of the present invention makes it possible to easily obtain organopolysiloxane having at least an alkenyl group on one end of the molecular chain, and a specific group on the other end. The organopolysiloxane thus obtained can be used as a raw material for silicone rubber or raw material for a new graft organopolysiloxane, or for copolymerization with plastics and resins other than organopolysiloxanes. It will thus prove to be of great value in areas of chemical technology. | Polymerizing cyclic trisiloxanes using as the polymerization initiator an alkali metal salt of an organosilane or organopolysiloxane having a terminal alkenyl group, followed by termination of the reaction, produces an organopolysiloxane having an alkenyl group on one end. These organopolysiloxanes are useful for making copolymers and as additives to siloxane elastomers. | 2 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to copending U.S. provisional application entitled, “A DEVICE FOR THE DILUTION AND APPLICATION OF LIQUIDS,” having ser. No. 60/314,058, filed Aug. 22, 2001, which is entirely incorporated herein by reference.
TECHNICAL FIELD
[0002] The present invention is generally related to liquid application systems and methods. More particularly, the invention relates to an application system and method wherein a concentrate is mixed with a liquid and the resulting liquid mixture is dispersed without the use of a pump.
BACKGROUND OF THE INVENTION
[0003] The use and application of liquid substances, such as cleaning preparations, pesticides, herbicides, fertilizers, coatings, lubricants etc., often require that the substances be diluted with a liquid, such as water, and the diluted preparation applied to a surface or introduced into a container. Typically, this is a multi-step operation that first involves the dilution process, which often requires that a concentrate and diluent be measured and placed into a container, and then that the combination be adequately mixed. The liquid mixture is then transferred by use of a transfer system to either be applied to a surface or introduced into a container. Typically, a pump functions as the motive force of the liquid mixture and is powered by an electric motor, by an internal combustion engine, or other appropriate means.
[0004] Liquid application systems are frequently encountered in the paving industry. The process of paving roads, runways, parking areas and the like with asphaltic concrete (asphalt) involves the transportation of the asphalt from the manufacturing plant to the paving site. Numerous types of vehicles are employed to transport asphalt from the manufacturing plant to the paving site. These vehicles include tandem dump trucks, tri-axle dump trucks, dump trailers, live-bottom trailers, hopper trailers, center drop trailers, double trailers, and the like. The asphalt transported by these vehicles is received “hot” so that it is in a workable condition at the paving site. To prevent the asphalt from sticking or adhering to the bed of the transportation vehicle, a lubricating type material, commonly known as an asphalt release agent, is applied to the truck bed prior to loading the asphalt.
[0005] The most common form of release agents are liquids which are sprayed, splashed, or otherwise applied to the vehicle truck beds. One common method of applying the release agent to the truck bed is by the use of a pump-up sprayer. In such applications, a measure of release agent is placed into the tank of the pumping unit, diluted as required (typically with water), agitated, and then pressurized to a sufficient air pressure to spray the bed of the truck. The spraying is conducted by the vehicle operator or personnel at the asphalt plant by controlling a wand or a nozzle to direct the flow of the spray unit. This method is somewhat ineffective in that the sprayers generally do not spray uniformly, and encounter decreasing air pressure while they are being used.
[0006] Other conventional spray units typically employ a pump to urge the diluent through the system, thereby both creating a liquid mixture including the diluent and the release agent and supplying the necessary pressure to spray the diluted release agent through an appropriate nozzle. Such units tend to suffer from a lack of control over the release agent concentration, and a lack of uniformity of application due to variability of the output pressure of the pump.
[0007] Accordingly, there is a need for a system and method of applying various liquid solutions wherein the concentration and application of the liquid solution can be controlled without the use of a pump.
SUMMARY OF THE INVENTION
[0008] Embodiments of the present invention provide a system and method for the mixing and the application of liquids to various surfaces. Briefly described, one embodiment of the system includes a primary tank having a liquid fill fitting, a gas fitting, and an outlet. A pressurized gas source is in fluid communication with the primary tank by way of the gas fitting and a mixing device is in fluid communication with both the outlet and a concentrate reservoir. The mixing device is arranged and configured to mix the liquid and the concentrate into a liquid mixture. The system is configured such that the pressurized gas source expels the liquid through the outlet and the mixing device, thereby creating the liquid mixture.
[0009] The present invention can also be viewed as providing methods for of mixing and dispensing a liquid mixture. The method includes the steps of filling a primary tank to a desired level with liquid, pressurizing the primary tank to a desired pressure with a pressurized gas source, and passing the liquid through a mixing device, thereby mixing the liquid with a concentrate to create a liquid mixture.
[0010] Other systems, methods, features, and advantages of the present invention will be or become apparent to one with skill in the art upon examination of the following drawings and detailed description. It is intended that all such additional systems, methods, features, and advantages be included within this description, be within the scope of the present invention, and be protected by the accompanying claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] Many aspects of the invention can be better understood with reference to the following drawings. The components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of the present invention. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.
[0012] [0012]FIG. 1 is a schematic diagram of an embodiment of a liquid application system of the present invention.
[0013] [0013]FIG. 2 is a schematic diagram of an embodiment of a liquid application system of the present invention.
[0014] [0014]FIG. 3 is a schematic diagram of an embodiment of a liquid application system of the present invention.
[0015] Reference will now be made in detail to the description of the liquid application system illustrated in the drawings. While the liquid application system will be described in connection with these drawings, there is no intent to limit it to the embodiment or embodiments disclosed therein. On the contrary, the intent is to cover all alternatives, modifications and equivalents included within the spirit and scope of the liquid application system as defined by the appended claims.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0016] Referring now in more detail to the drawings, FIG. 1 illustrates an embodiment of a liquid application system 100 . Preferably, the system includes a primary tank 110 , a pressurized gas source 120 , a mixing device 130 , a concentrate reservoir 147 , and a flow activation device 150 . As shown, the primary tank includes a liquid fill fitting 112 , a gas fitting 114 , an outlet 116 , and a liquid fill control device 118 . The pressurized gas source 120 is in fluid communication with the primary tank 110 by way of the gas fitting 114 . Preferably, the gas fitting 114 is a three way valve that can be used to line-up the pressurized gas source 120 to the primary tank 110 during pressurization, isolate the primary tank 110 from the pressurized gas source 120 , and vent the primary tank 110 to atmosphere during liquid fill operations or simply to de-pressurize the primary tank 110 . The liquid fill fitting 112 is preferably a valve that is used to either line-up the primary tank 110 to a liquid source (not shown) during fill operations or isolate the primary tank 110 from the liquid source during pressurization of the tank with the pressurized gas source 120 . The liquid fill control device 118 is used to determine the amount of liquid in the primary tank 110 and thereby indicate when the flow of liquid into the tank should be secured. However, the system 100 need not include the liquid fill control device 118 as the amount of liquid to be added to the primary tank can be pre-determined before fill operations.
[0017] Preferably, the mixing device 130 is a venturi having an inlet side 142 , an outlet side 146 , a suction 144 , and an activation valve 145 . The inlet side 142 is adjacent the outlet 116 of the primary tank 110 and the suction 144 is in fluid communication with the concentrate reservoir 147 . The activation valve 145 is used to prevent the flow of liquid through the venturi 140 until desired. The activation valve 145 need not be a part of the venturi 140 , but instead can be on the upstream or downstream side of the venturi 140 . Preferably, a ratio selector 148 is disposed in the suction 144 between the venturi 140 and the concentrate reservoir 147 . Although not necessary to the present invention, the ratio selector 148 permits the ratio of concentrate to liquid to be adjusted, or allows the concentrate reservoir 147 to be isolated from the venturi 140 . A flow activation device 150 , a trigger activated wand 151 is shown, is frequently disposed on the outlet side of the venturi 140 to allow manual application of the liquid mixture to a desired surface. Alternatively, the venturi 140 may deliver the liquid mixture to an automatic spray device (not shown) rather than a manual one.
[0018] Although the system 100 can be operated manually, embodiments are envisioned wherein an electronic controller 160 is used to automatically operate the system. For example, as shown, electronic controller 160 can be used to operate some, or all, of the liquid fill fitting 112 , the gas fitting 114 , the activation valve 145 , and the ratio selector 148 . The electronic controller 160 can be used to activate/de-activate the pressurized gas source 120 as well as receive inputs from the liquid fill control device 118 . The electronic controller can be either a programmable logic controller (PLC) or a device such as a timer/relay.
[0019] As shown in FIG. 2, other embodiments include a reservoir gas tank 170 disposed between the pressurized gas source 120 and the primary tank 110 . The reservoir gas tank 170 includes an inlet and an outlet, each typically fitted with a gas fitting 114 similar to those found on the primary tank 110 . The reservoir gas tank 170 adds flexibility to the system 100 in that the primary tank 110 can be pressurized although the pressurized gas source 120 has been secured. The reservoir gas tank 170 can be lined up to multiple primary tanks 110 .
[0020] As shown in FIG. 3, other embodiments include a receiver tank 180 disposed on the downstream side of the venturi 140 . Typically, the receiver tank includes a liquid fill fitting 112 , a gas fitting 114 , and an outlet 116 , similar to those found on the primary tank 110 . The receiver tank 180 functions as a storage area for the liquid mixture after it has been prepared, but prior to application. The liquid mixture is introduced into the receiver tank 180 through the liquid fill fitting 112 while the gas fitting 114 is used to vent the receiver tank 180 . Once the liquid mixture is in the receiver tank, the liquid fill fitting 112 is used to isolate the receiver tank 180 from the primary tank 110 and the gas fitting 114 is used to pressurize the receiver tank 180 with the pressurized gas source 120 . With the receiver tank pressurized, the liquid mixture is then dispensed either through a flow activation device 150 (FIGS. 1 and 2), or an automatic spray device (not shown). Each primary tank 110 can be lined up with one or more receiver tanks 180 . As well, the primary tank can have one venturi 140 lined up to multiple receiver tanks 180 , or rather, have an individual venturi 140 dedicated to each receiver tank 180 . This permits a single primary tank 110 to be used to prepare and store multiple liquid mixtures of varying concentrations, depending upon the settings of each venturi 140 and contents of each concentrate reservoir 147 , either independent of each other or simultaneously. Because each receiver tank is pressurized independently, the liquid mixtures contained in multiple receiver tanks may also be dispensed either simultaneously or independently. Embodiments are envisioned that include both reservoir gas tanks 170 (FIG. 2) and receiver tanks 180 .
[0021] One embodiment does not utilize a pressurized gas source 120 , but rather, utilizes a positive displacement pump (not shown), such as a diaphragm, gear or piston type, to introduce liquid into the primary tank 110 . As liquid is pumped into the primary tank 110 with all fittings closed with the exception of the liquid fill fitting 112 , the primary tank 110 becomes pressurized as the gas present in the tank is compressed. Because no pressurized gas source 120 is required for operation, the gas fitting 114 can be omitted from this embodiment.
Operation
[0022] Operation of the embodiment as shown in FIG. 1 will now be addressed. While filling the primary tank 110 with the desired liquid (preferably water), the primary tank 110 is vented through the gas fitting 114 to facilitate the operation. The liquid fill control device 118 detects and controls the amount of liquid introduced into the primary tank 110 , preferably, the amount of liquid introduced into the tank is approximately 30-95% of the volume of the primary tank 110 . Alternately, a pre-determined amount of liquid can be introduced into the primary tank 110 , thereby negating the use of the liquid fill control device 118 . Liquid may be introduced into the primary tank 110 by any suitable means, such as gravity, pumping, or pressure from a community water system. Once the primary tank 110 has been filled to the desired level, the liquid fill fitting 112 is placed in the closed position to isolate the primary tank 110 from the source of the liquid. The primary tank 110 is next pressurized by placing the gas fitting 114 into a position that secures venting of the primary tank 110 and lines the tank up with the pressurized gas source 120 . Preferably, the pressurized gas source 120 , such as a compressor, remains lined up to the primary tank 110 during operation of the system 100 , however, the gas fitting 114 may be used to isolate the primary tank 110 after the tank has been pressurized.
[0023] After the primary tank 110 has been pressurized, the liquid contained therein is passed through a mixing device 130 that mixes the liquid with a concentrate stored in the concentrate reservoir 147 . As shown, the venturi 140 is the preferred mixing device. The venturi 140 may be either a fixed concentration venturi or a variable concentration venturi. To initiate flow through the venturi 140 , the activation valve 145 , such as an air actuated ball valve or a solenoid valve, is opened, thereby allowing liquid to flow into the inlet side 142 of the venturi 140 . As the liquid flows from the inlet side 142 to the outlet side 146 of the venturi 140 , concentrate from the concentrate reservoir 147 is drawn through the suction 144 and entrained in the flow of liquid. The ratio selector 148 is used to adjust the amount of concentrate entrained for a given flow rate, and therefore to adjust the concentration of the resulting liquid mixture. As shown, the flow of liquid through the venturi 140 is controlled by a trigger activated wand for manually applying the liquid mixture to a desired surface. Alternately, the liquid mixture can be directed to an automatic spray device (not shown) or a receiver tank 180 (FIG. 3).
[0024] As previously noted, an electronic controller 160 can be used to operate the system 100 . When such a device is used, the operation of the pressurized gas source 120 , gas fittings 114 , liquid fill fittings 112 , liquid fill control device 118 , and activation valve 145 are all synchronized so that the system functions in an automatic fashion. Although all embodiments of the present system 100 can be operated in an automatic fashion, the system of FIG. 1 is discussed herein. Upon an operator activating the system 100 , the controller places the gas fitting 114 in position to vent the primary tank 110 to atmosphere and the liquid fill fitting 112 in position to fill the primary tank 110 . Sensing and control lines 162 of the controller are represented by dashed lines. Once the liquid fill control device 118 detects the desired volume of liquid in the primary tank 110 , the controller 160 isolates the primary tank 110 from the liquid supply source by repositioning the liquid fill fitting 112 and subsequently re-positions the gas fitting 114 such that the pressurized gas source 120 pressurizes the primary tank 110 to the desired pressure, preferably from approximately 50 pounds per square inch (psi) to 2000 psi.
[0025] Once the primary tank 110 has been pressurized, the controller 160 operates the activation valve 145 , thereby allowing liquid to flow into the venturi 140 . Flow is initiated through the venturi 140 by activating the flow activation device 150 . As shown, this is accomplished by manually pulling a trigger 152 on a wand applicator 151 . In other embodiments, flow through the venturi will initiate when the controller 160 opens the activation valve 145 , such as when the venturi is lined up to a receiver tank 170 (FIG. 3) or an automatic nozzle system (not shown). Once a pre-determined volume of liquid has passed through the venturi 140 , the controller 160 will close the activation valve 145 , vent the primary tank 110 to atmosphere, and line up the liquid fill fitting 112 to fill the primary tank in preparation for the next application operation.
[0026] It should be emphasized that the above-described embodiments of the present liquid application system 100 , particularly, any “preferred” embodiments, are merely possible examples of implementations, merely set forth for a clear understanding of the principles of the liquid application system 100 . Many variations and modifications may be made to the above-described embodiment(s) of the liquid application system 100 without departing substantially from the spirit and principles of the liquid application system 100 . All such modifications and variations are intended to be included herein within the scope of this disclosure and the present liquid application system 100 and protected by the following claims. | A system and method for the mixing and the application of liquids to various surfaces. The system includes a primary tank having a liquid fill fitting, a gas fitting, and an outlet. A pressurized gas source is in fluid communication with the primary tank by way of the gas fitting and a mixing device is in fluid communication with both the outlet and a concentrate reservoir. The mixing device is arranged and configured to mix the liquid and the concentrate into a liquid mixture. The system is configured such that the pressurized gas source expels the liquid through the outlet and the mixing device, thereby creating the liquid mixture. | 8 |
[0001] This invention pertains to assemblies for mounting wheels to the underside of a skateboard deck or roller skate boot. More specifically it relates to a novel yoke, base, grommet, wheel and bearing combination in a skate truck to deliver high precision steering, advanced steering control, and more precise wheel alignment.
[0002] Conventional skateboards and roller skates are equipped with steering mechanisms known as trucks. The trucks are mounted on the underside of the board or boot opposite to each other, one in the front and one in the rear. Each truck carries two wheels, one at each end of the truck's axle. Each wheel is fitted with two bearings that fit into pockets integrated into the wheel body. The bearings are separated by a small gap in the middle of the wheel. This gap may be filled with a metal spacer that partially stabilizes and aligns the bearings.
[0003] Competition-level skateboarding and roller skating takes many forms, such as streetstyle, ramp riding, bowl riding, freestyle, slalom racing, and downhill racing. The equipment used by advanced skaters must meet exacting performance requirements. The truck or wheel chassis determines many of the most crucial performance characteristics.
[0004] Skate trucks serve four main purposes: 1) to connect the wheels to the deck or boot; 2) to provide wide-ranging steering response, whereby the wheel axles swivel to create a finite turning radius when, by means of lateral weight shifts, the skater tilts the deck or boot about its longitudinal axis; 3) by means of a resilient suspension system, to smoothly and predictably resist the skater's varying lateral weight shifts, thus stabilizing linear rolling motion and providing control over the steering response; and 4) by means of the same resilient suspension system, to return the deck or boot to the neutral, non-turning position after the skater discontinues a lateral weight shift. Skate wheel bearings serve the obvious purpose of aligning the wheels to the axles and minimizing rolling resistance.
[0005] Conventional skate trucks follow a basic design in which an axle pivots about an arm attached at one end to the center portion of the axle. The other end of this pivot arm is loosely fitted, at angles typically measuring 30° or 45°, into a plastic pivot cup mounted in a baseplate, thus forming a ball-like joint. A pair of doughnut-shaped grommets, usually made of rubber or urethane plastic of varying hardnesses, is mounted on a kingpin fixed at various angles in the baseplate on the side of the axle opposite the plastic cup. These grommets grasp a ring within, or extending from, the axle body so that the axle is suspended between the ball joint and the grommets. By adjusting the kingpin, the tension on the grommets may be increased or decreased, thereby varying the balance between turning stability and turning ease. Examples of this standard design are shown in U.S. Pat. No. 3,862,763, issued Jan. 28, 1975, to Gordon K. Ware; and in U.S. Pat. No. 4,109,925, issued Aug. 29, 1978 to Williams et al.
[0006] In these standard designs, the kingpin and the grommets do not precisely stabilize the axle body about the steering axis theoretically defined by the pivot arm rotating inside the plastic cup. The angle of the pivot axis tends to deteriorate as the axle tilts, so that tight turns may be difficult to achieve. The axle body is also substantially free to waiver sideward in response to side loads encountered during turns or straight-ahead riding. Steering control, range and overall performance are thereby compromised.
[0007] Furthermore, the standard design for the flexible plastic grommets results in poor steering control. Skaters control the tilt angle of the deck or boot, and thus the size of the turns they make, via lateral weight shifts of varying degree. Regardless of their hardness and no matter how they are adjusted, the conventional donut-shaped grommets do not offer an optimal or consistent pattern of resistance to such weight shifts. The result is that skaters cannot easily predict or measure how far to shift their weight to achieve turns of varying radii.
[0008] Finally, the bearings used in standard skate wheels require tolerance between their inner races and the truck axles. This means they are free to sit or rock out of alignment if one or more of the following conditions are met: the wheel bearing seats are not perfectly level; the wheel bearing seats are not precisely spaced; the spacer between the bearings is not perfectly dimensioned; no bearing spacer is used; the axle nut is not properly tensioned; and/or axle diameter and straightness are flawed. Bearings manufactured with an extended inner race element have been repurposed for skate wheels to partially address the aforementioned issues. But even these can sit or rock out of alignment if: the wheel bearing seats are not perfectly level; the wheel bearing seats are not precisely spaced; the axle nut is not properly tensioned; and/or axle diameter and straightness are flawed. The alignment distortion that may result can compromise bearing performance and longevity, directly impacting wheel rolling speed and traction.
SUMMARY OF THE INVENTION
[0009] In the present invention a high level of precision is provided to the trucks' steering action. This is accomplished by way of a cylindrical bearing which is seamlessly integrated between the axle hanger, i.e., the yoke which supports the axle on which the truck's wheels are mounted at either end, and novel grommets. The “positive” or male portions of the cylindrical bearing are formed on the grommet seats of the axle body, and to save weight this portion is made hollow, like a tube, between the pivot tip and the axle (See FIG. 5 ). The “negative” or female portions of the cylindrical bearing are formed on the surfaces of the two grommets that meet the hanger. These portions may be formed directly on the main body of the grommets, or else formed as separate elements, preferably using low friction material, and then joined to the main body of the grommets. The cylindrical bearing assembly constrains the axle body to pivot very precisely about the axis defined by the pivot arm and cup, with minimal up-down or side-to-side wavering.
[0010] The present invention improves steering control of the skateboard with novel contouring and construction of the grommets. The grommets do not feature the round doughnut shape with flat faces that is typically seen. Rather, they incorporate a substantially hexagonal shape and significantly more material on the sides, as well as a taper from broader faces that meet the hanger to narrower faces that meet the base plate and the tension nut, respectively, of a truck assembly. In addition, the narrower faces have beveled sides and join to hard end caps. Throughout a skater's turning stroke, these beveled contours constrain compressive forces to act in a substantially perpendicular orientation along the grommets' tapering outside walls, which are wider, taller and more voluminous compared to the side portions of conventional doughnut-shaped grommets. This ensures more direct and orderly resistance to compressive forces, as well as a longer compressive stroke and thus a larger steering range. In addition, the grommet's tapering sides minimize excessive “packing” of the flexible grommet material so as to create a more optimal steering control profile.
[0011] Empty pockets may be optionally formed within the grommet assemblies, for example between the grommet body and the end caps or along the sides of the female bearing portion, to further refine the steering resistance profile. Resilient elements such as wave springs may be optionally molded within the grommet bodies to enhance rebound or energy return. Laterally-flexing features may be optionally added between the female bearing elements and the grommet bodies to provide controlled speed-sensitive steering, whereby the increased side loads encountered during high speed turns will gradually move the hangers into positions of less steer.
[0012] The hard end cap joined to the lower grommet forms a mechanical lock with the contours of its seat on the base plate, thus eliminating the need for the separate round cap washer which is conventionally seen. The beveled interface between the hard end caps and the main grommet body also discourages the compressible material from flexing over the sides of its seat.
[0013] The present invention also includes bearings with integral half-spacers ending in wide flat flanges which square up and self-stabilize inside the wheels. The wide flat flanges form a self-aligning system which corrects flaws in bearing seat levelness, bearing seat spacing, axle diameter and axle straightness. The superior alignment results in reduced friction within the bearings, longer bearing life, faster rolling, and enhanced wheel grip.
[0014] Other objects and advantages of this invention will become apparent from a consideration of the following drawings and detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] For a more complete understanding of this invention, reference should be made to the accompanying drawings in which:
[0016] FIG. 1 is a perspective view of the underside of a skateboard, partially broken away, including a depiction of the trucks of the present invention mounted on the underside of the board and movable to various positions including the positions shown in phantom;
[0017] FIG. 2 is an elevational view of the skateboard shown in FIG. 1 when a skateboarder's weight is moved toward the viewer of FIG. 2 and showing the trucks with the foreground wheels moved closer to the deck of the skateboard to accomplish a right turn of the skateboard;
[0018] FIG. 3 is a perspective view of the rear truck assembly shown in FIGS. 1 and 2 , viewing the axle hanger upwardly from underneath the skateboard deck and showing the wheels of the truck aligned in a straight ahead position;
[0019] FIG. 4 is an enlarged, exploded view of the rear truck assembly shown in FIG. 3 , with the wheel portions partially broken away;
[0020] FIG. 5 is an enlarged view, partially in perspective, of an assembled portion of the rear truck assembly shown in FIG. 5 sectioned in the direction of the arrows 5 - 5 shown in FIG. 4 ;
[0021] FIG. 6 is an enlarged and partially assembled view of the base plate and grommet assembly of the rear truck assembly shown in FIG. 4 , with the axle hanger assembly omitted;
[0022] FIG. 7 is an exploded view of elements of the axle hanger assembly of the rear truck assembly shown in FIG. 4 ;
[0023] FIG. 8 is an exploded and perspective view of central portions of the rear truck assembly shown in FIG. 4 engaged on a portion of the skateboard in a form of mounting which is an alternative to the form of mounting shown in FIG. 1 ;
[0024] FIG. 8A is an enlarged portion of the rear truck assembly and skateboard portion shown in FIG. 8 ;
[0025] FIG. 9 is an enlarged and exploded view, partially broken away, of a wheel portion of the rear truck wheel assembly shown in FIG. 4 ;
[0026] FIG. 10 is a perspective view, partially broken away, of the wheel portion of the rear truck assembly shown in FIG. 9 after the wheel portion has been assembled;
[0027] FIG. 11 is an enlarged perspective view of the assembled bearings in the wheel portion shown in FIG. 10 ;
[0028] FIG. 12 is a perspective view of one of the wheel bearings shown in FIG. 11 , broken away along the line 11 - 11 shown in FIG. 11 ;
[0029] FIG. 13 is a head on view of the broken-away face of the wheel bearing shown in FIG. 12 ; and
[0030] FIG. 14 is an elevational view of a roller skate with truck assemblies of the present invention mounted on the underside of the boot.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0031] In the drawings, one preferred embodiment of the invention is shown which is a skateboard 10 supported upon a pair of novel trucks 12 and 14 . While the preferred embodiment is a skateboard, it should be understood that the invention, including its various elements, will also be applicable to other rolling platform vehicles, such as a roller skate, which are powered by the rider, or by gravity, or by some combination thereof. Also, in the following paragraphs the truck 12 which is mounted toward the rear of the skateboard will be the truck principally described, but it will also be understood that the truck 14 which is mounted toward the front of the skateboard has an identical construction.
[0032] However, the kingpin, or post, 20 on which the rear truck wheels 22 articulate has a longitudinal axis extending toward the rear end, or tail, 24 of the skateboard deck 26 . The kingpin, or post 30 in truck 14 mounted toward the front, or nose 32 of the skateboard has a longitudinal axis which extends toward the nose of the skateboard, and the front truck wheels 34 articulate on this post. The front and rear trucks, 14 and 12 respectively, are thus oppositely disposed to each other.
[0033] As shown in FIG. 1 in solid lines, wheels 22 and 34 of the rear truck 12 and front truck 14 , respectively, are in a straight-forward attitude when the axles, such as axle 36 of the rear truck 12 , are normal to a straight-line path incorporating the longitudinal axis of the skateboard 10 . The skateboarder's weight, if one were present on top of the skateboard, would normally be equally distributed toward both outer edges of the skateboard. As shown in phantom in FIG. 1 , and in solid lines in FIG. 2 , the trucks are turned to execute a right turn, with a skateboarder's weight predominantly on the side of the skateboard closest to the viewer in FIG. 2 . With the skateboarder's weight thus distributed, the weight on the right side of the skateboard pressing downwardly in the direction of arrows 42 causes the wheels on the right side of the skateboard to move closer together. The nose of the board swings in an arc toward the right and the tail of the skateboard swings in an arc out to the left to orient the longitudinal axis of the skateboard deck in a right turn.
[0034] Rear truck 12 is illustrated in FIG. 3 in its assembled state with wheels 22 mounted on axle 36 . An exploded view of the truck 12 is shown in FIG. 4 . A yoke, or hanger, 44 supports the axle 36 and connects the entire truck and wheel bearing assembly to the skateboard 10 . The body portion 46 of the yoke is supported on its pivot tip 50 in a pivot cup 52 which is, in turn housed in a pocket in one end of truck base plate 54 . The pivot cup is usually made of a lubricious plastic so that the pivot tip 50 can easily turn in a multitude of directions within it as the yoke 44 moves in an arcuate path about the base plate 54 to dispose the wheels 22 from one position to another.
[0035] A first aperture 56 is formed in a central portion of the yoke 44 , spaced apart from the pivot tip 50 , so that the yoke 44 may also be mounted on the kingpin 20 . A cylindrical bearing member 60 , which is part of the yoke, is located adjacent to the first aperture. The size of the opening through that aperture is somewhat larger than the diameter of the kingpin, or post, 20 so that the yoke 44 is able to be fitted to the post during assembly and tilted in various attitudes while the yoke is maintained on the post. As shown in FIG. 5 , the post 20 has a head portion 62 lodged in the base plate 54 and extends through the first aperture 56 to a distal end 64 where it is engaged by a tension nut 66 . Preferably, the tension nut is threadably engaged on the post's distal end 64 so that pressure on the elements of the yoke mounting assembly between the head of post 20 and its distal end 64 can be adjusted.
[0036] A resilient first grommet 70 is engaged on the post 20 and the bearing member 60 on the underside of the yoke 44 . Grommet 70 has a first face 72 which is engaged on the cylindrical bearing member 60 adjacent the first aperture 56 . The outer surface of the bearing member 60 is cylindrical, and a cylindrically shaped groove bearing surface 73 in first face 72 is configured for complementary engagement with the cylindrical surface of the bearing member 60 in the yoke. Such an engagement precisely regulates and restricts the arcuate movement of the yoke. The bearing member is able to rotably slide through its interface with the first face of the grommet as the flat surface adjacent the bearing member 60 compresses the flat surface on the grommet adjacent the bearing groove 73 .
[0037] In the body portion 46 of yoke 44 there is a recessed area 74 which has perimeter walls adjacent to the bearing member 60 . A collar section 76 of the first grommet is sized and configured to be fitted within those walls, and thus the walls of the recess grasp and hold the grommet in place. Preferably, the configuration of the walls forms a hexagonal recess, but similar configurations of the walls which intercept the collar section 76 may be used.
[0038] The first grommet 70 has sides which taper from a larger end of the grommet adjacent to the first face 72 to a smaller end adjacent to a second face 80 . Those sides form a cone from the first face 72 at the larger end of the grommet which is configured for engagement with the bearing member 60 to the second face 80 at the smaller end of the grommet which is configured for proximate engagement with the tension nut 66 . Preferably the second face 80 is beveled. An end cap 82 which has a beveled surface 84 complementary to the second face 80 is interposed on post 20 between the grommet and the tension nut. The end cap 82 is also made of a harder material than grommet 70 , thus forming a hard, stable point of connection for the grommet at its second face 80 . The sides of the grommet are provided with external fissures 86 , and on the interior, as will shortly be described, the sides are internally hollow.
[0039] These configurations of grommet 70 produce improved results for a skater. The contours of the beveled second face 80 constrain compressive forces to act in a substantially perpendicular orientation along the tapering outside walls, which are wider, taller and more voluminous compared to the side portions of conventional doughnut-shaped grommets. This insures more direct and orderly resistance to compressive forces, as well as a longer compressive stroke and thus a larger steering range. The tapering sides minimize excessive packing of the flexible grommet material so as to create a more optimal steering control profile.
[0040] In the first face 72 , the cylindrical bearing member 60 may be formed directly on the main body of grommet 70 , or else formed as a separate element, preferably using low friction material, and then joined to the main body of the grommet. The cylindrical bearing assembly constrains yoke 44 to pivot very precisely about the axis defined by the pivot tip 50 and the pivot cup 52 with minimal up-down or side-to-side wavering. At the same time the cylindrical bearing assembly resists the increased side loads encountered during high-speed turns more progressively compared to conventional constructions. As side loads increase, the female bearing portion of the bearing in the first face, i.e., cylindrically shaped groove 73 , will gradually, rather than suddenly, flex under pressure from the male bearing portion in the yoke, i.e., cylindrical bearing member 60 , thereby allowing the yoke 44 to gradually move into positions of progressively slower steering, which is a desirable speed-sensitive steering effect.
[0041] As shown particularly in FIG. 5 , the cylindrical bearing member 60 includes a cylindrical side 60 a across the aperture 56 from the first grommet 70 . Side 60 a of the cylindrical bearing faces the base plate 54 . A second grommet 90 , which is quite similar to first grommet 70 , has a cylindrically shaped bearing surface 92 with which the second grommet engages the bearing surface 62 a . There is a recessed area 94 on the base plate side of the yoke into which a first face 96 of the second grommet fits in a non-rotating manner like the first grommet does on the other side of yoke 44 . When first face 96 is so inserted, the second grommet engages its bearing surface 92 with the bearing 60 .
[0042] As shown in FIGS. 4 and 6 , fissures 100 are formed on the outside walls of the second grommet, and the interiors of the grommet walls are hollowed out as at hollows 102 . A second face 104 on the second grommet, spaced apart from the second grommet's first face 96 , contains a plurality of first locking members 106 . An end cap 110 , which is disposed on post 20 , has a plurality of second locking members 112 arranged for complementary engagement with the first locking members 106 . The surfaces of the locking members may be ridged, and the surfaces 114 of the second grommet and 116 of the end cap 110 which engage each other beveled, as illustrated in FIG. 6 . The end cap 110 also includes a face 118 opposite the second locking members 112 which can be fixed on the base plate 54 , as by incorporating a cup 120 which is arranged to match the configurations 122 on the base plate.
[0043] The second grommet, like the first, incorporates a substantially hexagonal shape and significantly more material on the sides, as well as a taper from broader faces that meet the yoke to narrower faces that meet the base plate. The narrow second face has beveled sides that join the hard end cap. Throughout a skater's turning stroke, these beveled surfaces constrain compressive forces to act in a substantially perpendicular orientation along the second grommet's tapering walls, which are wider, taller and more voluminous compared to the side portions of conventional doughnut-shaped grommets. This insures more direct and orderly resistance to compressive forces, as well as a longer compressive stroke and thus a larger steering range. In addition, the grommet's tapering sides minimize packing of the flexible grommet material so as to create a more optimal steering control profile.
[0044] The end cap 110 forms a mechanical lock with the contours of its seat on the base plate, thus eliminating any need for a separate round cap washer in an assembly that is conventionally seen. The beveled interface between the end cap and the second grommet body also discourages compressible material from flexing over the sides of its seat.
[0045] A normal type of mounting for a truck such as truck 12 onto the underside of a skateboard is shown in FIG. 1 , that is, to fasten the flanges 126 to the underside of deck 26 with screw or bolts inserted through the mounting holes 128 in the flanges. An alternative type of mounting is shown in FIG. 8A , known as a “dropthrough” mounting. In that alternative, skateboard deck 132 is provided with an opening 134 which is arranged to fit the footprint of a truck structure beyond the flanges, i.e., a socket into which the superstructure of the truck fits. Truck 136 is mounted this way in FIG. 8A . The superstructure 138 of the truck extends through the deck 132 , leaving flanges 140 on the other side, i.e., the top side of the deck. The truck is fastened in place using one or more bolts 142 . The deck-engaging surfaces of flanges 140 feature a convex contour to provide complementary engagement in the “dropthrough” mounting on the top surface of the deck, which normally has a concave contour. Small circular flat areas are preserved in the corners of the base plate's top surfaces to form stable seats for the mounting nuts when the truck is assembled onto the deck in the normal manner shown in FIG. 1 .
[0046] The wheel bearing assembly 150 shown in FIGS. 9 through 13 is also an important part of the entire truck 12 for accomplishing smooth and improved control of a skateboard or roller-skate. In wheels 22 , shown in an enlarged, broken-away view in FIG. 9 , first and second ball bearings are enclosed in casings 152 and 154 . On the first casing, 152 , there is a bell 156 on the exterior of the casing, and on the second casing 154 there is a second bell 160 . The bells 156 and 160 meet, as shown in FIGS. 10 and 11 , when the casings 152 and 154 are assembled on axle 36 and disposed in their respective housings 164 and 166 . The bells 156 and 160 are slideably disposed on each other but may also be positively joined inside the wheel.
[0047] More particularly, the wheel bearing assembly 150 for wheel 22 on axle 36 incorporates a first ball bearing casing 152 which has an inner casing portion 170 for bearing balls in a first race 172 and an extension section 174 beyond the first race. At the extremity of the extension section there is a first flange 176 which extends outwardly from axle 36 when the axle is disposed in channel 180 through the bearing. The second ball bearing casing 154 mirrors casing 152 , with an inner, second race and culminating in a flange beyond the second race which extends outwardly from axle 36 . The first and second flanges are disposed against each other within the wheel when they are assembled in their housings, or bearing seats, and disposed on axle 36 . When so disposed, the two flanges square up and self-stabilize. They form a self-aligning system which compensates for flaws in bearing seat levelness, bearing seat spacing, axle diameter and axle straightness. This assembly results in reduced friction within the bearings, longer bearing life, faster rolling, and enhanced wheel grip.
[0048] As shown in FIG. 14 , the truck and wheel bearing assembly more particularly described above may be mounted on the underside of a roller-skate deck 184 to which a skater's boot 186 is affixed. Rear truck 12 A and front truck 14 A are illustrated with their rear and front wheels 22 A and 34 A, respectively, turned in the same attitude as the wheels illustrated in FIG. 2 are turned beneath a skateboard.
[0049] Those skilled in the art will readily see that while numerous detailed variations of the above-described embodiments if this invention may be made, the true scope of the invention is to be determined by the following claims. | An improved skateboard or roller-skate truck and wheel bearing assembly is disclosed containing an axle bearing yoke, base, grommet, and wheel and bearing combination which delivers improved steering precision, steering control, and wheel alignment. A grommet in the truck includes a bearing surface on a face which engages a bearing member in the yoke and restricts arcuate movements of the yoke and wheels. The contours of the grommet are also unique and contribute to steering control. The wheel and bearing combination incorporates paired bearing casings with bell-shaped members in their ends which meet each other inside a wheel of the board or skate and self-adjust to accommodate imperfections in the bearing seat levelness, bearing seat spacing, axle diameter and axle straightness. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of Korean Application No. 2002-83522, filed Dec. 24, 2002, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a pump for an inkjet printer, and more particularly, to a pump for an inkjet printer which squeeze a tube to generate a suction force, thereby sucking ink from an inkjet head nozzle.
[0004] 2. Description of the Related Art
[0005] An inkjet printer using a permanent head, which can be permanently used and refilled (replenished) with ink, and a semi-permanent head, generally includes a pump. The pump for the inkjet printer performs a sucking operation in order to remove air that may enter during the replenishing of the ink and to open a head nozzle when the head nozzle is blocked by dried ink.
[0006] Pumps used in inkjet printers are generally divided into piston type pump apparatuses and rotor type pump apparatuses. The rotor type is more commonly used. The rotor type utilizes the rotation of a rotor to squeeze a plastic tube and thus generate a pressure difference which causes ink to be ejected from an inkjet head nozzle.
[0007] Several inventions relating to such a rotor type pump apparatus have been patented and have been put to practical use, one example of which is disclosed in U.S. Pat. No. 5,910,808. Operation of that pump apparatus as disclosed will be briefly described with reference to FIG. 1.
[0008] As a rotor of the pump apparatus rotates in a counterclockwise direction, a roller 14 squeezes a tube 10 . Due to a pressure difference to an atmosphere pressure occurring as the tube 10 is squeezed, the squeezing results in a negative pressure differential relative to the ambient. This negative pressure differential causes ink in an inkjet head nozzle (not shown) to be sucked into the tube 10 an end of which is connected to the inkjet head nozzle.
[0009] After the suction of the ink, when the rotor rotates in a clockwise direction, the roller 14 comes into contact with a damper plate 16 made of rubber as shown in FIG. 2. This contact moves the roller inward along a cam groove 12 . In this state, the roller 14 does not squeeze the tube 10 so as to allow the tube 10 to return to its original (i.e. uncompressed) state. That is, the conventional rotor type pump apparatus varies the position of the roller 14 within the cam groove 12 by using the damper plate 16 when the rotor is rotated in the counterclockwise and the clockwise directions, whereby the tube 10 is squeezed and relaxed and thus the sucking operation is performed.
[0010] However, since in the conventional rotor type pump apparatus the position of the roller 14 is changed within the cam groove 12 by using the rubber-made damper plate 16 when the tube 10 is contracted and relaxed, the damper plate 16 is periodically subjected to an alternate shock load. Accordingly, when the pump apparatus is used for a long time, the properties of the rubber-made damper plate 16 such as elasticity and surface friction coefficient are deteriorated and thus reliability of the sucking operation is reduced.
[0011] Also, the collision of the roller 14 with the damper plate 16 when the damper plate 16 changes the position of the roller 14 in the cam groove 12 causes noise. When the tube 10 is disposed on a right-angled wall, the rotation of the roller 14 causes the tube 10 to ascend.
[0012] Still further, since the conventional pump apparatus requires many parts such as a plurality of gears, the damper plate, and the like manufacture and/or assembly can be complicated.
SUMMARY OF THE INVENTION
[0013] The present invention has been developed in order to solve the above problems in the related art. Accordingly, an aspect of the present invention is to provide a pump apparatus for an inkjet printer capable of preventing a reliability of sucking operation from being lessened even in the case that it is used for a long time.
[0014] Also, another aspect of the present invention is to provide a pump apparatus for an inkjet printer capable of preventing a collision noise from occurring during the rotation of a roller and a tube from ascending.
[0015] Also, still another aspect of the present invention is to provide a pump apparatus for an inkjet printer providing an effect that the number of parts can be decreased.
[0016] Additional aspects and/or advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
[0017] According to an aspect of the present invention there is providing a pump for an inkjet printer applying a negative pressure to an inkjet head nozzle, including: a tube connected to the inkjet head nozzle and being U-shaped; a plurality of rollers which contact an inner arch of the tube and having a tapered shape; and a rotor to which the plurality of rollers are rotatably mounted. When the rotor rotates in a direction, at least one of the plurality of rollers rotate and squeeze the tube. When the rotor stops rotating, the plurality of rollers return to a state in which the plurality of rollers do not squeeze the tube due to a recovering force of the tube. The squeezing of the tube generates the negative pressure in the inkjet head nozzle.
[0018] The plurality of rollers may be tapered. Also, the plurality of rollers may be a pair of rollers disposed symmetrically to each other.
[0019] According to another aspect of the present invention there is a pump for an inkjet printer applying a negative pressure to an inkjet head nozzle, including: a fixing shaft; a driving gear rotatably assembled to the fixing shaft; a stopper protruding from a side of the driving gear; a ratchet wheel rotatably assembled to the fixing shaft, having a driving ratchet formed in a lower end thereof and a cam recess; a rotor assembled to the fixing shaft, movable in an axial direction, and having a driven ratchet formed in an upper end thereof which is engagable with the driving ratchet; a plurality of rollers rotatably disposed at the rotor and having tapered sides; and a tube disposed to contact the plurality of rollers and connected to the inkjet head nozzle. The driving gear is rotatable in a direction and rotation of the driving gear causes the rotor to move along the fixing shaft so that at least one of the plurality of rollers squeezes the tube.
[0020] When the driving gear stops rotating or is rotated in the reverse direction, the rotor may move along the driving shaft in a reverse direction due to a recovering force of the tube to return the tube to an original state.
[0021] The plurality of rollers a pair of rollers disposed symmetrically to each other.
[0022] The tube may be disposed in a housing accommodating the rotor, the ratchet wheel and the driving gear, and the housing may be provided with a rotor stopper protruding from an inner side thereof which encourages the plurality of rollers to maintain contact with the tube when the rotor is not rotating.
[0023] The driving ratchet and the driven ratchet may be inclined and cooperate so that a load of the plurality of rollers applied to the tube by the driving ratchet when the ratchet wheel rotates in a reverse direction opposite the direction is smaller than the recovering force of the tube.
[0024] According to still another aspect, there is provided a pump which pumps ink from an ink source, including: a shaft; a driving gear surrounding the shaft and rotatable in a direction about the shaft; a stopper integrally formed on a side of the driving gear and having at least one protrusion; a ratchet rotatable about the shaft, movable about an axial direction, having one or more cam recesses formed on an upper side each of which receive a projection, and having a driving ratchet formed at a lower side; a rotor rotatable about the fixing shaft, movable about an axial direction, and having a driven ratchet formed on an upper side; and two or more rollers extending from a lower side of the rotor and which orbit the shaft when the rotor rotates.
[0025] Also, according to the pump apparatus of the present invention, the collision noise does not occur during the operation, and the tube is prevented from ascending over the rollers.
[0026] Also, according to the pump apparatus of the present invention, the number of the components of the apparatus can be reduced.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] The above aspects and/or other advantages of the present invention will be more apparent by describing a preferred embodiment of the present invention, in which:
[0028] [0028]FIG. 1 is a cross-sectional view showing a conventional pump apparatus for an inkjet printer;
[0029] [0029]FIG. 2 is a cross-sectional view showing the damper plate of the pump apparatus for the inkjet printer of FIG. 1;
[0030] [0030]FIG. 3 is a perspective view showing a pump apparatus for an inkjet printer according to a first embodiment of the present invention;
[0031] [0031]FIG. 4 is a perspective view showing the housing assembled with the pump apparatus for the inkjet printer of FIG. 3;
[0032] [0032]FIG. 5 is an exploded perspective view showing the pump apparatus for the inkjet printer of FIG. 4;
[0033] [0033]FIG. 6 is a perspective view showing the ratchet wheel of the pump apparatus for the inkjet printer of FIG. 4;
[0034] [0034]FIG. 7 is a cross sectional view showing the pump apparatus for the inkjet printer of FIG. 4 in the non-operation;
[0035] [0035]FIG. 8 is a cross sectional view showing the pump apparatus for the inkjet printer of FIG. 4 when it rotates in a direction of squeezing the tube.
[0036] [0036]FIG. 9A is a perspective view showing the pump apparatus for the inkjet printer of FIG. 3 in a non-operational mode;
[0037] [0037]FIG. 9B is a perspective view showing the driving ratchet and the driven ratchet engaged with each other when the pump apparatus for the inkjet printer of FIG. 9A rotates; and
[0038] [0038]FIG. 9C is a perspective view showing the plurality of rollers squeezing the tube when the pump apparatus for the inkjet printer of FIG. 9A rotates further than the state of FIG. 9B.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0039] Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout. The embodiments are described below in order to explain the present invention by referring to the figures.
[0040] Hereinafter, a pump apparatus for an inkjet printer according to an embodiment of the present invention will be described with reference to the accompanying drawings.
[0041] Referring concurrently to FIGS. 3 to 6 , the pump apparatus for the inkjet printer according to a first embodiment of the present invention includes a fixing shaft 30 , a driving gear 40 , a ratchet wheel 50 , a rotor 60 , a tube 80 , and a housing 90 .
[0042] The fixing shaft 30 is fixed to a frame 20 of the inkjet printer in which the pump apparatus is disposed, and guides the rotation of the driving gear 40 and the rotor 60 .
[0043] [0043]FIG. 5 shows that the driving gear 40 is rotatably disposed on the fixing shaft 30 and engaged with a driving force transmitting gear 22 for transmitting a driving force from a motor (not shown). A stopper 42 protrudes from one end of the driving gear 40 . The stopper 42 is formed in a hollow shape to be assembled with the fixing shaft 30 and has a projection 44 protruding from a sidewall thereof. The stopper includes two projections 44 . However, while two projections are shown and described, more projections may be provided and, when multiple projections 44 are provided in pair, they are symmetrically disposed to each other as shown in FIG. 5 for smooth operation.
[0044] The ratchet wheel 50 is hollow-shaped as shown in FIG. 6 and has a driving ratchet 54 at one end thereof (the upper end in FIG. 6) and a cam recess 52 at the other end (the lower end in FIG. 6) thereof. The ratchet wheel 50 has an inner diameter sufficient to smoothly rotate with respect to an outer diameter of the stopper 42 . The cam recess 52 is defined in a circumference of the lower end of the ratchet wheel 50 and has a bottom gradually inclined from one side 52 a to the other side 52 c . The projection 44 of the stopper 42 is inserted into the cam recess 52 and the rotation of the stopper 42 causes the bottom of the cam recess 52 to be pushed, so that the ratchet wheel 50 moves in a lengthwise direction on the stopper 42 . When the projection 44 is positioned at side 52 a of the cam recess 52 , the driving ratchet 54 is disengaged from the driven ratchet 64 so that the roller 70 does not squeeze the tube 80 . On the other hand, when the projection 44 is positioned at the other side 52 c of the cam recess 52 , the driving ratchet 54 is engaged with the driven ratchet 64 so that the roller 70 squeezes the tube 80 . When the projection 44 is positioned at the other side 52 a of the cam recess 52 , the driving ratchet 54 is not in contact with the driven ratchet 64 . That is, the lower surface of the driving ratchet 54 and the upper surface of the driven ratchet 64 are spaced apart by a gap so that the driving ratchet 54 avoids coming into contact with the driven ratchet 64 . The rotor 60 rises due to a recovering force of the squeezed tube 80 on the non-operation of the driving gear 40 , causing the ratchet wheel 50 to be rotated in the reverse direction. The gap is to prevent the reverse rotation of the rotor 60 caused by the reverse rotation of the ratchet wheel 50 . The reverse rotation of the rotor 60 may causes a noise and abrasion.
[0045] The driving ratchet 54 is formed of a series of triangular teeth with one side 54 a being right-angled to a parallel line and disposed along the circumference of one end of the ratchet wheel 50 . An inclined surface 54 b of the driving ratchet 54 is formed in a manner so that it allows the ratchet wheel 50 to move in a lengthwise direction of the stopper 42 as the rotor 60 moves upwardly due to a recovering force of the tube 80 on the non-operation of the driving gear 40 and thus the driven ratchet 64 pushes the driving ratchet 54 . Also, the inclined surface 54 b of the driving ratchet 54 is formed in a manner so that when the driving gear 40 rotates in a direction that it does not squeeze the tube 80 , a force the driving ratchet 54 applies to the driven ratchet 64 is not greater than a force applied to the driven gear 64 due to the recovering force of the tube 80 .
[0046] Turning back to FIG. 5, the rotor 60 is shaped as a hollow cylinder and one end 62 thereof moves in an axial direction with respect to the fixing shaft 30 . Around an outer circumference of the hollow cylinder is formed the driven ratchet 64 to be engaged with the driving ratchet 54 . At the other end of the rotor 60 are provided two rollers 70 . The two rollers 70 are tapered, orbit the rotor 60 as it rotates, and freely and independently rotate with respect to the rotor 60 . However, while two rollers are shown and described, it is to be understood that more than two rollers may be provided. A tapered portion of the roller 70 completely squeezes the tube 80 as the rotor 60 is moved to the maximum degree by the stopper 42 . Also, the size of the driven ratchet 64 is identical to that of the driving ratchet 54 . At a center portion of the other end of the rotor 60 may be provided a guide shaft 66 for supporting the rotation of the rollers 70 and guiding the straight forwarding movement of the rotor 60 with respect to the fixing shaft 30 . One end of the guide shaft 66 is inserted into the housing 90 to guide the straight forwarding movement of the rotor 60 .
[0047] The tube 80 is disposed at a position to come into contact with at least one of the rollers 70 that orbit as the rotor 60 rotates. Although not shown, one end of the tube 80 is connected to an inkjet head nozzle. Generally, the tube 80 is disposed around the rollers 70 to come into contact with one roller 70 in a half orbiting circle of the plural rollers 70 . Accordingly, when the rotor 60 is rotated by the driving gear 40 , only one roller 70 rotates, squeezing the tube 60 . The tube 80 is made of material having a high elasticity so that it easily recovers its original state from a squeezed state. That is, the tube 80 has to have a recovering force powerful enough to push the rotor 60 and the ratchet wheel 50 toward the driving gear 40 .
[0048] As FIG. 4 shows, the housing 90 accommodates the above-described components to prevent foreign materials from going into the pump apparatus, and especially firmly secures the tube 80 thereto. The housing 90 is provided with a guide hole 92 formed in one end thereof. Into the guide hole 92 is inserted the guide shaft 66 of the rotor 60 . Also, the housing 90 is provided with a rotor stopper 94 ( shown in FIG. 7) protruding from an inner side thereof. The rotor stopper 94 supports one end of the rotor 60 in order for the roller 70 to preload upon the tube 80 when the driving gear 40 is in the non-operation. The roller 70 preloads upon the tube 80 to prevent the rotor 60 from idle-rotating when the rotor 60 is rotated due to the ratchet wheel 50 . Accordingly, the degree of preload is set to an extent so that the tube 80 is not squeezed so as to generate a negative pressure and a friction force is generated between the roller 70 and the tube 80 ( shown in FIG. 7).
[0049] Hereinafter, operation of the pump apparatus for the inkjet printer according to an embodiment of the present invention will be described in detail with reference to FIGS. 7 to 9 C.
[0050] When the driving force transmitting gear 22 (not shown) is rotated by the motor (not shown), the driving gear 40 surrounding the fixing shaft 30 is rotated in a direction on the fixing shaft 30 . In conjunction with the rotation of the driving gear 40 , the stopper 42 integrally formed with the driving gear 40 is rotated in the same direction. If the stopper 42 is rotated in a counterclockwise direction (an arrow direction of FIG. 9A), the ratchet wheel 50 is separated from the rotor 60 as shown in FIG. 9A is moved downwardly by the projection 44 of the stopper 42 . When the projection 44 is moved to a position 52 b of the cam recess 60 ( shown in FIG. 6), the driving ratchet 54 of the ratchet 50 is engaged with the driven ratchet 64 of the rotor 60 . If the rotation of the projection 44 continues, the ratchet wheel 50 and the rotor 60 are pushed downwardly so that the plural rollers 70 squeeze the tube 80 . When the projection 44 reaches the other side 52 c ( shown in FIG. 6) of the cam recess 52 , the tube 80 is completely squeezed by the roller 70 as shown in FIGS. 8 and 9C. That is, the inner diameter of the tube 80 is completely compressed. If the projection 44 continues to rotate, the ratchet wheel 50 is also rotated in association with the projection 44 . The rotation of the ratchet wheel 50 causes the driven ratchet 64 engaged with the driving ratchet 54 of the ratchet wheel 50 to rotate. Accordingly, the rotor 60 is rotated so that the plural rollers 70 disposed at the rotor 60 orbit the rotor 60 , squeezing the tube 80 . The two rollers 70 are both initially pressing the tube 80 . However, when the rotor 60 is rotated, one roller of the two rollers 70 is rotated, squeezing the tube 80 , while the other one is rotated, about the rotor and away from a contact with the tube 80 . While the rotor 60 rotates, one roller is moved from the contact with the tube 80 as the other roller comes into contact with the tube 80 . Accordingly, as the rotation of the rotor 60 continues, the two rollers 70 rotate, alternately squeezing the tube 80 . When the roller 70 squeezes the tube 80 , there is generated a negative pressure in the tube 80 . Due to the pressure difference between the negative pressure and an atmosphere pressure, the tube 80 performs sucking operation of ink from the inkjet head nozzle.
[0051] After the sucking operation, the motor stops operating and thus the driving force transmitting gear 22 stops rotating. Accordingly, the driving gear 40 stops rotating. When the driving gear 40 stops rotating, the rotor 60 is released from the load applied by the projection 44 of the stopper 42 disappears. Then, due to the recovering force of the tube 80 , the tube 80 recovers its original state and pushes the rollers 70 upwardly. On receipt of the upward load, the rotor 60 is moved along the fixing shaft 40 in an axial direction. As the rotor 60 is moved upwardly, the driven ratchet 64 and the ratchet wheel 50 are concurrently moved upwardly to thus return to the initial state as shown in FIG. 9A. That is, when the driving gear 40 stops rotating, the rotor 60 and the ratchet wheel 50 are moved upwardly due to the recovering force of the tube 80 , so that the tube 80 automatically recovers its original state in which it is not squeezed.
[0052] Alternatively, the motor is rotated in the reverse direction to move the ratchet wheel 50 and the rotor 60 upwardly, whereby the tube 80 returns to its original state. This embodiment requires the cam recess 52 of the ratchet wheel 50 to be modified so that when the stopper 42 is rotated in the reverse direction, the ratchet wheel 50 is upwardly moved.
[0053] As described above, since the pump apparatus for the inkjet printer according to the present invention does not require the damper plate, the reliability of the sucking operation is improved and the collision noise does not occur even in the case that the pump apparatus is used for a long time. Also, since the tapered rollers 70 is constantly in contact with the tube 80 , the tube 80 is prevented from ascending over the rollers 70 , and the number of the components can be reduced.
[0054] Although a few embodiments of the present invention have been shown and described, the present invention is not limited to the disclosed embodiments. Rather, it would be appreciated by those skilled in the art that changes and modifications may be made in this embodiment without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents. | A pump for an inkjet printer applying a negative pressure to an inkjet head nozzle, includes: a tube connected to the inkjet head nozzle and being U-shaped; a plurality of rollers which contact an inner arch of the tube and having a tapered shape; and a rotor to which the plurality of rollers are rotatably mounted. When the rotor rotates in a direction, at least one of the plurality of rollers rotate and squeeze the tube. When the rotor stops rotating, the plurality of rollers return to a state in which the plurality of rollers do not squeeze the tube due to a recovering force of the tube. The squeezing of the tube generates the negative pressure in the inkjet head nozzle. | 1 |
OF THE INVENTION
1. Field of the Invention
The invention relates to ball locking devices; and, more particularly, a ball locking device having interchangeable handles.
2. Description of the Prior Art
Quick connect ball locking devices are well known in the prior art. Such devices generally include a plurality of detents, such as balls, trapped within a tube but protruding out openings therein. A ball actuator is reciprocal within the tube and movable from a first position wherein the balls are retracted substantially within the tube or moved outwardly a sufficient distance to lock the balls within a mating receptacle.
Generally, such prior art ball locking devices have a stainless steel head integral with the actuating member (generally of one-piece).
In use, such devices generally have differing heads or handle portions, or even different colored handles, depending upon the application, use or desire of the customer. However, the actuating mechanism, i.e., the tube, balls and actuating member portion, are the same regardless of the configuration of the head or handle portion.
There is a need for an improved ball locking device that can be quickly and easily assembled from stock resulting in a device having a head or handle portion to the customer's specifications. This would cut down on inventory and provides faster delivery to the customer.
SUMMARY OF THE INVENTION
It is an object of this invention to provide a ball locking device having interchangeable handles.
These and other objects are preferably accomplished by providing a ball locking device having a ball locking mechanism adapted to be releasably attachable to a receptacle to lock the device thereto until released. The device has a handle which is removably attached to the device so that the handle can be changed for another. The handle may be of a plastic material while the locking mechanism may be of metal.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an elevational sectional view of a locking pin in accordance with the teachings of the invention;
FIG. 2 is a detailed sectional view of a portion of the pin of FIG. 1 showing one type of handle installed thereon;
FIG. 3 is a detailed sectional view of a portion of the pin of FIG. 1 showing the same in a ball unlocking position;
FIG. 4 is a vertical sectional view of another type of handle which can be installed on the pin of FIG. 1;
FIG. 5 is a view taken along lines 5--5 of FIG. 4;
FIG. 6 is a vertical sectional view of still another type of handle which can be installed on the locking pin of FIG. 1; and
FIG. 7 is a vertical cross-sectional view of a fourth modification of a handle which can be installed on the locking pin of FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1 of the drawing, a locking pin 10 is shown having an elongated generally cylindrical barrel 11 with a throughbore 12. A plurality of spaced openings 13, 14, such as two, are provided through barrel 11 adjacent one end 15 thereof. A plurality of detents, such as balls 16, 17, are provided in openings 13, 14. The areas of barrel 11 surrounding openings 13, 14 may be peened, as is well known in the art, to retain balls 16, 17 in openings 13, 14.
An elongated ball, actuator 18 is reciprocally mounted in throughbore 12. Actuator 18 has a head 18' and reduced diameter section 19 into which balls 16, 17 may move which actuator 18 is moved to the right in FIG. 1. This allows balls 16, 17 to be disposed within barrel 11 of sufficient distance to release pin 10 from a receptacle (not shown) as is well known in the ball locking art.
Barrel 11 terminates at the end opposite end 15 in a threaded end 20. An enlarged head 21 is fastened to end 20 in any suitable manner, such as by knurling the same, or by thread means. Thus, as seen in FIG. 1, head 21 is secured by threading having internal mating threads 22. As seen in FIG. 2, end 20 of barrel 11 has an annular groove 23 adjacent end 20 adapted to receive therein an annular flange 24 on head 21 forming by swaging the same into areas 23. In addition, enlarged head 21 has means for retaining the same to a handle, such as handle 33 (FIG. 2). In the embodiment shown, threads 37 are used to secure head 21 to handle 33 but other means, such as knurling, may be used.
Actuator 18 extends through a chamber 24' in head 21 to a push button 25. End 26 of actuator 18 is thus press-fit into a hole 27 in push button 25. Push button 25 being retained to head 21 by engagement of annular flange 28 with shoulder 29 of head 21 as shown. In lieu of a preformed shoulder 29, formed by counterboring head 21, the terminal end of head 21 may be swaged inwardly to provide a stop or shoulder. Actuator 18 is secured to push button 25 by swaging end 100 of push button 25 into groove 101 as seen in FIG. 2. This swaging operation retains push button 25 to spindle end of actuator 18.
A chamber 30 is formed internally of pin 10 between push button 25 and barrel 11. A coil spring 31 is disposed within chamber 30 abutting against push button 25 and barrel 11 normally biasing push button 25 away from barrel 11. When push button 25 is pushed internally against the bias of spring 31, actuator 18 is moved in the direction of arrow 32 in FIG. 2. As seen in FIG. 3, this moves reduced diameter section 19 to the right in FIG. 1 allowing balls 16, 17 to move back into barrel 11 in the release position shown in FIG. 3.
Head 21, barrel 11 and push button 25 may be made of stainless steel and head 21 is integral with barrel 11 either by being threaded or otherwise swaged or knurled thereto or integral therewith.
An actuating handle, such as L-shaped handle 33 (FIG. 2) may be secured to push button 25. Handle 33 has a first elongated gripping portion 34 extending from a center portion 35 having a central threaded aperture 36. Enlarged head 21 has mating threads 37 on the outside thereof threadably mating with threaded aperture 36. A shorter gripping portion 38 extends from center portion 35 on the side thereof opposite gripping portion 34. If desired, a hole 45 may be provided in portion 34 for securing a strap or the like (not shown) thereto.
Thus, an operator can grip portions 34, 38 and push inwardly on push button 25 thereby moving actuator 18 as heretofore discussed.
Thus, handle 33 may be made of plastic and/or may be color coded. By threading it to head 21, it can be quickly and easily removed therefrom. The stainless steel head 21 integral with stainless steel barrel 11 carries the tension loads and allows the use of plastic handles which may be color coded. The use of plastic cuts down on costs and a desired color can be molded into the handle 33 during the manufacturing process. This eliminates a secondary process, such as cadmium plating or anodizing, necessary in making such locking pins heretofore, which processes pollute the environment. Thus, colored handles, needed to coordinate with a customer's application, can be molded in the handle. Such coloring is also aesthetically appealing.
Although a particular handle 33 is shown in FIG. 2, other handles may be interchangeably threaded on to head 21. Thus, as seen in FIG. 4, a button handle 39 may have a generally cylindrical main body portion 40 having an outer enlarged annular gripping portion 41 and a threaded throughbore 42. The threads of throughbore 42 mate with threads 37 of enlarged head 21 which, when handle 39 is threaded thereto, extends outwardly thereof similar to the orientation of handle 33 and push button 25 in FIG. 2. As seen in FIG. 5, an extension portion 46 may be integral with gripping portion 41 having hole 47 therethrough for receiving a strap or the like (not shown).
Another handle 43 in the form of a T is shown in FIG. 6. Handle 43 has a central generally cylindrical main body portion 44 and integral elongated gripping portions 48, 49 extending outwardly on each side thereof. A hole 50 may be provided in one of the gripping portions, such as portion 48, for receiving a strap or the like (not shown) therein. Main body portion 44 has a threaded throughbore 51 adapted to mate with threads 37 of enlarged head 21 as heretofore discussed with respect to handles 33 and 39.
Still another handle 52 is shown in FIG. 7. Handle 52 has a generally cylindrical main body portion 53 with an outer annular integral flange 54. Flange 54 has a pair of opposed holes 55, 56 receiving therein legs 57, 58, respectively, of a gripping ring 59. Ring 59 is of a resilient material, such as wire, and legs 57, 58 snap fit into holes 55, 56. A threaded throughbore 60 extends through main body portion 53 and flange 54 adapted to mate with threads 37 of head 21 as heretofore discussed. Obviously, a strap or the like (not shown) can be secured directly to ring 59. Ring 59 can be grasped while pushing on push button 25 when handle 52 is assembled thereto as heretofore discussed.
It can be seen that the handles of FIGS. 2, 4, 5, and 7 can be quickly and easily interchanged. All of the handles can be made of plastic and colored as heretofore discussed. This cuts down on inventory and allows quick delivery to the customer.
Although ball locking devices of the type discussed herein have many uses, they are particularly useful as quick release mechanisms in the aircraft industry such as the mechanisms disclosed in my U.S. Pat. Nos. 3,948,549 and 4,404,714. These patents, commonly assigned, and the teachings of which are incorporated herein by reference, disclose similar ball locking pins adapted to releasably engage locking receptacles, such as receptacle 73 in wall 74 of U.S. Pat. No. 3,948,549, and keeper pins, such as pin 14 of U.S. Pat. No. 4,404,714.
Although a particular embodiment of the invention has been disclosed, variations thereof may occur to an artisan and the scope of the invention is only to be limited by the scope of the appended claims. | A ball locking device having a ball locking mechanism releasably attachable to a receptacle to lock the device thereto until released. The device has a handle which is removably attached to,the device so that the handle can be changed for another. The handle may be of a non-metallic material whereas the main components of the ball locking mechanism may be of metallic material. | 8 |
FIELD OF THE INVENTION
The present invention relates to a method and apparatus for cardiac pacing and, more particularly, for Atrial-His-Ventricular sequential pacing to improve sinoatrial node dysfunction or heart block superior to the His bundle. As a derivative, His-Ventricular sequential pacing can be employed to treat permanent atrial fibrillation.
BACKGROUND OF THE INVENTION
The sinoatrial (SA) node represents the natural pacemaker that controls the rhythmic electrical excitation in a normal human heart. At an appropriate time, an electrical impulse arising from the SA node is transmitted to the right and left atrial chambers. This impulse causes muscle tissue surrounding the atrium to depolarize and contract which generates an electrical signal known as a P-wave. The same electrical impulse arising from the SA node also travels to the right and left ventricles through the atrioventricular (AV) node and atrioventricular (AV) bundle. The AV node, situated in the lower portion of the right atrium, receives the impulse to contract. The impulse is then transmitted through the AV bundle comprising Common Bundle of His (His bundle), right and left bundle branches, and Purkinje fibers that cover most of the endocardial surface of the ventricles. The ventricular muscle tissue depolarizes, generating an R-wave, then contracts. This forces blood held in the ventricles through the arteries and to various body locations. This action is repeated in a rhythmic cycle in which the atrial and ventricular chambers alternately contract and pump, then relax and fill.
Disturbances of impulse formation by the sinus node and/or AV conduction block due to disease and aging are commonly treated by artificial pacing. An artificial pacemaker is an implantable medical device that monitors the activity of the heart for the occurrence of P- and/or R-waves. When a P- or R-wave is not sensed after a prescribed period of time, the pacemaker electronically generates stimuli in order to force the depolarization of the atria and/or ventricles. A pacemaker-generated stimulus that is delivered to the atria is known as an A-pulse, whereas a stimulus delivered to the ventricles is a V-pulse.
Different methods of artificial pacing have been employed including single or bi-ventricular pacing and dual chamber pacing. In single ventricular pacing, a pacing lead connected to an electrode is typically implanted in the apex of the right ventricle to deliver electrical impulses to the ventricular muscle tissue. However, this type of pacing results in the loss of synchronous mechanical contraction of the right and left ventricles due to the interventricular delay in impulse propagation to the left ventricle. This results in an immediate decrease in cardiac output along with potential deterioration of ventricular function over the long term as permanent changes occur in myocardial perfusion and structure. A method to pace both ventricles, bi-ventricular pacing, has been demonstrated to restore substantially simultaneous contraction of both ventricles and is accomplished by placing one pacing lead in the apex of the right ventricle and another pacing lead through the coronary sinus into a vein on the left ventricular wall. The surgical procedure used to implant the pacing lead in the coronary sinus however may be complex and a long pacing lead is needed to connect the electrode to the pulse generator thus requiring a higher voltage resulting in a large drain on the power source generating the pulses. In dual chamber pacing (DDD/R), electrodes connected to pacing leads are placed in the atria (for example the right atrium) and one or both of the ventricles. Under this method, ventricular synchrony can be achieved when electrodes are placed in both ventricles and an optimal delay between the A pulse and V pulse (AV delay) is utilized. However, this still does not produce a similarly coordinated contraction as compared to natural AV bundle activation.
Patients with SA node dysfunction or heart block superior to the His bundle, due to their conditions, suffer from a delay in the electrical response from the atria to the ventricles. According to current practice, patients with these conditions typically receive a DDD/R pacemaker. Many of these patients however still have normal ventricular contraction and thus are unnecessarily ventricularly paced due to pacemaker programming restrictions and/or prolonged AV conduction times. Because of this unnecessary ventricular pacing, these patients experience a decrease in cardiac efficiency due to the uncoordinated contraction sequence and eventually exhibit adverse long-term effects. Therefore, it's desired to develop a pacing system for these patients, that is more tailored to their cardiac condition, without utilizing ventricular pacing means.
It has recently been shown in U.S. Pat. No. 5,320,642 (Scherlag) that a pacing lead can be implanted near the His bundle, just below the AV node to pace the ventricles as an alternative to ventricular pacing. When the ventricles are paced through this natural conduction system, the ventricles contract in a more coordinated fashion as compared to pacing the ventricles themselves thus improving cardiac output. Also, patients receiving ventricular pacing who do not need to be ventricularly paced are spared from the long term harmful hemodynamic effects that occur from continuous ventricular pacing. However, there is a risk that the electrode may become dislodged from the His bundle or that the patient may subsequently experience heart block inferior to the His bundle. Therefore, it's desired to utilize this more natural His bundle pacing system in order to obtain a more coordinated contraction sequence, yet retain the option to ventricularly pace should the His bundle pacing lead fail or heart block below the His bundle occur.
SUMMARY OF THE INVENTION
The present invention is directed to a pacing apparatus and method for sequentially pacing the atria, His bundle and ventricles to provide synchronous mechanical contractions to improve cardiac output and prevent long term hemodynamic effects caused by unnecessary ventricular pacing. The pacing apparatus includes pacing leads extending from a pacer that lead to prescribed positions in the atria, AV septum and ventricle of the heart. The pacing leads have electrodes attached to their distal ends for measuring and delivering electrical impulses. The pacing leads leading to the atria and ventricles are programmed to deliver electrical pulses, on a demand mode basis, if natural electrical signals are not measured within a predetermined period of time. The pacing lead leading to the AV septum delivers continuous electrical pulses to the His bundle immediately following the sensing of atrial activity. These electrical pulses then travel through the right and left bundle branches and to the Purkinje fibers causing the ventricles to depolarize and contract. By utilizing this natural conduction system, the ventricles contract in a more coordinated manner as compared to ventricular pacing thus improving cardiac output and performance.
In one embodiment of the present invention, the pacing apparatus is provided for patients who suffer from sino-atrial (SA) node dysfunction or heart block superior to the His bundle. Because these patients typically have normal ventricular contraction, continuously pacing the His bundle results in electrical pulses being sent from the atria to the ventricles to travel more quickly thus allowing the ventricular pacing lead to remain dormant during the pacing cycle. The ventricular pacing is provided only for emergency situations such as, for example, inter alia, if the His bundle pacing lead should fail or if heart block inferior to the His bundle should occur.
In another embodiment of the present invention, the pacing apparatus is provided for patients who suffer from permanent atrial fibrillation. The His bundle pacing lead is implanted following AV node ablation to provide electrical pulses to the ventricles causing depolarization and contraction. Again, a ventricular pacing lead is provided but remains dormant and is activated only in emergency situations.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic representation of one embodiment of the pacing system in accordance with this invention whereby pacing leads are provided, the leads being shown with electrodes positioned in the heart.
FIG. 2 is a block diagram of one embodiment of the implantable pacemaker system.
FIG. 3 is a logic control diagram for pacing patients suffering from sinoatrial node dysfunction or superior His bundle heart block.
FIG. 4 is a logic control diagram for pacing patients suffering from heart block at the AV node.
FIG. 5 is a logic control diagram for pacing patients suffering from permanent atrial fibrillation.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The following description is of the best mode presently contemplated for carrying out the invention. This description is not to be taken in a limiting sense, but is made merely for the purpose of describing the general principles of the invention.
Referring to FIG. 1, there is shown a schematic representation of a pacing system 10 in accordance with one embodiment of the present invention. The pacing system 10 comprises an implantable pacemaker (pacer) 11 , from which three leads, 12 A (atrial), 12 H (AV bundle) and 12 V (ventricle) extend. It is recognized that actual lead packaging may vary, but at least three functional conductive leads must originate in pacer 11 to direct energy to various locations in the cardiac tissue. The pacing leads 12 A, 12 H and 12 V, in this embodiment, enter the heart through the superior vena cava 13 . Each pacing lead provides electrodes at or proximate to their distal ends for pacing and sensing electrical stimuli. A plurality of electrodes can be placed at the distal ends of each lead for measuring and delivering pulses, however for simplicity it's assumed each lead has one electrode for the following discussion. Pacing lead 12 A is anchored or otherwise positioned generally in the right atrium just below the SA node 14 for contacting the right atrium. Pacing lead 12 H is positioned distal to the blocked or slowly conducting AV node and in the AV septum 15 for contacting the AV bundle comprising His bundle 16 , right and left bundle branches 17 , and the Purkinje fibers 18 . The His bundle 16 is a structure of cardiac muscle through which all impulses from the atria are conducted to the ventricles of the heart. Pacing lead 12 V is positioned so that its distal end is anchored in the apex of the right ventricle 19 . The electrodes are stabilized or fixed in their respective positions in a manner well known in the art.
Referring then to FIG. 2, a block diagram of pacer 11 is illustrated. The pacer is adapted to interface with the atria, His bundle and ventricles of the heart. Those portions of pacer 11 that interface with the atria, His bundle and ventricles, and the corresponding portions of control system 35 are commonly referred to as the atrial, His bundle and ventricular channels, respectively.
Pacer 11 generates electrical pulses that are transmitted through pacing leads 12 A, 12 H and 12 V. Control system 35 controls pacer 11 . The control system includes timing circuitry and a microprocessor for carrying out logical steps in analyzing received signals, and determining when pace pulses should be initiated, with particular sequences and locations comprising part of the present invention. The leads 12 A, 12 H, and 12 V carry the stimulating pulses to electrodes 20 , 21 and 22 from an atrial pulse generator A-PG, His bundle pulse generator H-PG and a ventricular pulse generator V-PG 27 , respectively. An electrical pulse generated by A-PG is known as an A-pulse; an electrical pulse generated by H-PG is known as an H-pulse; and an electrical pulse generated by V-PG is known as a V-pulse. Further, natural electrical signals from the atria (P-waves) are carried from the electrode 20 , through lead 12 A, to the input channel of an atrial channel sense amplifier P-AMP. Likewise, natural electrical signals from the ventricles (R-waves) are carried from electrode 22 , through the lead 12 V, to the input terminal of a ventricular sense channel amplifier R-AMP. Thus, when a P-wave or R-wave is generated by the heart, it is sensed by electrodes 20 or 22 and amplified by P-AMP or R-AMP. The control system 35 receives the output signals from P-AMP over signal line 25 . The control system 35 also receives the output signals from R-AMP over signal line 26 . The control system 35 also generates trigger signals when needed that are sent to A-PG, H-PG and V-PG over signal lines 27 , 28 and 29 respectively. These trigger signals are generated each time that an electrical pulse is to be generated by the respective pulse generator.
Referring now to FIG. 3, there is shown a logic control flow diagram for controlling the system of this invention to pace a patient with SA node dysfunction or AV conduction block superior to the His bundle. The assumption is that the right and left ventricles are functioning normally but that sinus signals from the SA node to the AV Bundle are not occurring or are being delayed from the atria to the ventricles within the AV node. As shown at 51 , the pacer monitors the right atrium and measures a P-wave generated by the SA node. As shown in 54 , once a P-wave is sensed, the pacer transmits an H-pulse through the pacing lead to an electrode located distal to the AV node to stimulate the His bundle. The H-pulse is transmitted through the His bundle to the right and left bundle branches of the heart and then to the Purkinje fibers to cause ventricular depolarization. Then, the pacer senses the right ventricle for an R-wave. As shown in 55 , if an R-wave is not sensed following atrial activity plus some predescribed period of time, the right ventricle is electrically paced with a V-pulse generated by the pacer. In 56 , a subsequent P-wave is sensed in the right atrium. As shown in 57 , if a P-wave is not sensed following ventricular activity plus some prescribed period of time, the pacer generates an electrical stimulus, or A-pulse, to the right atrium. An H-pulse is generated immediately following atrial activity and sent to the electrode located near the AV bundle and the right ventricle is again monitored for ventricular depolarization as the cardiac cycle continues. The advantage to this system is that both the atrial and ventricular pacing leads remain dormant throughout the cardiac cycle unless a P-wave or R-wave is not sensed within a prescribed period of time. This eliminates the harmful hemodynamic effects suffered by patients who are currently unnecessarily ventricularly paced. In addition, using the natural conduction system of the SA node, the His-bundle, right and left bundle branches and Purkinje fibers as a pacing pathway generates a more natural synchronous mechanical ventricular contraction to improve cardiac output.
In another embodiment of the invention, shown in logic control flow diagram FIG. 4, it's assumed that the patient suffers only from heart block located in the AV node. In 61 , the pacer measures a P-wave generated by the SA node. To increase conduction time from the SA node to the ventricles, an electrode is placed distal to the AV node to stimulate the His bundle. Then, in 64 , the pacer sends an H-pulse to this electrode immediately following the sensing of a P-wave. As shown in 65 , the ventricular pacing lead remains dormant throughout this cycle unless an R-wave is not sensed following atrial activity plus a prescribed period of time, after which the pacer would generate a V-pulse to force the ventricles to contract.
Referring to FIG. 5, there is shown a logic control flow diagram for controlling the system of this invention to pace a patient with permanent atrial fibrillation. It's assumed that the patient suffers from a fast and unreliable ventricular response. According to current practice, these patients are treated by ablating the AV node and placing a permanent single-chamber pacemaker with the lead tip in the right ventricle to restore normal ventricular rhythm. However, this can cause hemodynamic deterioration and death in some patients. In order to provide these patients with improved long-term pacing, AV node ablation can be followed by permanent His bundle pacing. As shown in 71 , AV node ablation is preceded by implanting a pacemaker distal to the AV node to stimulate the His bundle. Continuous H-pulses are transmitted to the His bundle via the electrode located at the AV bundle, to cause the ventricles to depolarize as shown in 73 and 74 . Because there is a risk that the AV bundle lead could become dislodged or that the patient could suffer heart block inferior to the AV bundle lead, a second pacing lead is anchored in the apex of the right ventricle to provide V-pulses when necessary. As shown, if an R-wave is not sensed within a prescribed time following an H-pulse, a V-pulse is generated by the pacer and transmitted to the right ventricle causing the ventricles to contract. The subsequent H-pulse is generated according to the operating pacing rate to continue the cardiac cycle. Thus, a V-pulse is generated only on an emergency basis, i.e. when heart block occurs inferior to the His bundle.
While the invention herein disclosed has been described by means of specific embodiments and applications thereof, numerous modifications and variations could be made thereto by those skilled in the art without departing from the scope of the invention set forth in the claims. | A method and apparatus for cardiac pacing and, more particularly, for Atrial-His-Ventricular sequential pacing to improve sino-atrial node dysfunction or heart block superior to the His bundle. As a derivative, His-Ventricular sequential pacing can be employed to treat permanent atrial fibrillation. | 0 |
FIELD OF THE INVENTION
The invention relates to an air diffuser, in particular for a motor vehicle.
BACKGROUND OF THE INVENTION
In motor vehicles, the supply of conditioned air into the passenger compartment is often felt by the passengers to be an unpleasant sensation if this feed takes place in the form of a concentrated jet which strikes the passengers' bodies. This is the case in particular if the space within the passenger compartment is restricted.
To avoid a concentrated jet, it is known to provide a large number of small outlet openings for example in the center console, in the roof or in the B/C pillars. Outlet openings of this type are in widespread use in particular in means of public transport, such as buses, railway carriages or aircraft. However, the provision of a large number of outlet openings is relatively expensive.
EP 1 223 061 A2 has disclosed an air diffuser, in particular for vehicle air-conditioning, having a frame, a plurality of lamellae, which are arranged such that they can pivot about a first axis, and, at least one coupling element, to which each of the lamellae is coupled, the coupling element being adjustable relative to the first axis between a neutral position, in which the lamellae are parallel to one another, and a comfort position, in which at least some of the lamellae can be pivoted in opposite directions to one another. The air diffuser is arranged in front of an air duct from which an air stream emerges; the direction of this air stream can be set with the aid of the air diffuser. The air stream can be made to fan out with the aid of the lamellae which have been pivoted in opposite directions to one another, so as to produce a divergent air stream in which the flow velocities are lower than in an air stream with a constant cross section, so that even with a high throughput of air it is possible to prevent the emerging air stream from coming into contact with a vehicle passenger at a high velocity. However, even an air diffuser of this type still leaves something to be desired.
SUMMARY OF THE INVENTION
It is an object of the invention to provide an improved, in particular less expensive, air diffuser, which as a result of its outflow characteristic provides the maximum possible comfort in the passenger compartment.
According to the invention, an air diffuser, in particular for a motor vehicle, is provided with at least one air-guiding element which is arranged in a flow duct and imparts a swirl to the air stream as it passes from an air duct into the air diffuser, a flow body being formed along the longitudinal center axis of the flow duct. The flow body is preferably of solid configuration with a circular cross section, although for reasons of weight or material saving the flow body may also be of hollow configuration, although the air stream should not be able to flow through it. The air diffuser in this case distributes the air over a very large area, resulting in a complete absence or at least a minimization of drafts.
It is particularly advantageous for an air diffuser of this type to be arranged shortly after a bend, since in this case, if no swirl is imparted to the air stream, a very irregular flow profile is present in the air diffuser, which gives rise to a draft effect which can be virtually or completely eliminated by the application of a swirl. This allows an air diffuser of this type to be more versatile in use, since even if the air diffuser is in an unfavorable position, for example just after a bend, a draft effect can be avoided or at least minimized, thereby considerably enhancing comfort.
To optimize the way in which the air stream is swirled up as it emerges from the air diffuser, the flow body and/or the flow duct in which the flow body is arranged has a cross section which, in the longitudinal direction of the flow duct, changes over the longitudinal direction.
It is preferable for the air-guiding element arranged in the air diffuser to be of helical configuration. In this case, it is also possible for a plurality of helically configured air-guiding elements to be provided at equidistant intervals from one another and in the form of a multi-lead thread.
It is preferable for the pitch of the air-guiding element(s) to be constant, but it is also possible for this pitch to change in particular in the air inlet region of the air diffuser or in the outlet region thereof. For example, the pitch may in particular be greater in the inlet region than in the outlet region. In a further advantageous configuration of an air diffuser, the latter has an air-guiding element pitch which increases or decreases in the direction of flow. The swirl imparted to the flow can be influenced by the change in cross section in the flow path and the resulting acceleration or deceleration of the flow.
To increase passenger comfort, the air diffuser preferably has a direction-setting device, so that the mean direction of flow of the air stream which emerges in diffuse form from the air diffuser can be set.
It is preferable for the air diffuser with direction-setting device to have an outer flow duct, in which case the direction-setting device is arranged in the outer flow duct. In this case, it is preferable for the flow body to be formed in the direction-setting device along the longitudinal center axis of the inner flow duct. The air-guiding element for generating swirl is preferably arranged helically around the flow body.
The outer flow duct preferably has a cross section which widens as seen in the direction of air flow, thereby boosting the diffusion of the air stream.
It is preferable for all the pivot axes of the direction-setting device to be arranged centrally with respect to the longitudinal extent of the inner flow duct. However, in particular in the case of relatively large adjustment angles, it may be expedient for this point to be offset toward the direction of the air stream.
BRIEF DESCRIPTION OF THE DRAWINGS
In the text which follows, the invention is explained in detail on the basis of three exemplary embodiments with variants, in part with reference to the drawing, in which:
FIG. 1 diagrammatically depicts the cross section of an air diffuser in accordance with the first exemplary embodiment,
FIG. 2 shows a section on line II-II in FIG. 1 ,
FIG. 3 diagrammatically depicts the cross section of an air diffuser in accordance with the second exemplary embodiment,
FIG. 4 shows a section on line IV-IV in FIG. 3 ,
FIG. 5 diagrammatically depicts the cross section of an air diffuser in accordance with the third exemplary embodiment, and
FIG. 6 shows a section on line VI-VI in FIG. 5 .
DETAILED DESCRIPTION
An air diffuser 1 by means of which conditioned air coming from an air-conditioning system can be fed with a swirl to a passenger compartment has, in its swirl zone, a flow duct 2 with a circular cross section which, in its longitudinal center axis, has a flow body 3 with a guiding element 4 . The flow body 3 , which is solid in form, has a circular cross section, and the guiding element 4 extends helically in the radial direction with a constant pitch between flow body 3 and inner lateral surface 5 of the flow duct 2 .
The air which is fed to the air diffuser 1 via an air duct (not shown) has a type of screw motion imparted to it by the guiding element 4 , so that the air stream enters the passenger compartment with a swirl and therefore in diffuse form. On account of the absence of a spot jet, the diffuse air stream is not considered an unpleasant sensation even if it comes into contact with a passenger.
According to a variant of the first exemplary embodiment which is not illustrated in the drawing, the air diffuser has two guiding elements, which are each formed in the same way as the air-guiding element 4 of the first exemplary embodiment but are arranged offset through 180° with respect to one another.
FIGS. 3 and 4 show the second exemplary embodiment, according to which what is provided is an air diffuser 1 with a flow body 3 and flow duct 2 whose shape deviates from the corresponding components in the first exemplary embodiment. The solid flow body 3 and the flow duct 2 have a contour which deviates from the cylindrical shape and influences the outlet characteristic of the air stream so as to optimize the way in which the swirl is imparted. In the present case, the flow body 3 has a streamlined thickened portion 11 in a region before the outlet region, and the flow duct 2 has a widened portion 12 in the outlet region.
According to a variant of the second exemplary embodiment which is not shown in the drawing, the flow body in the outlet region has a thickened portion which approximately corresponds to the increase in the diameter of the flow duct in the outlet region, following a profile corresponding to that of the second exemplary embodiment. The widening in the cross section of flow with a slight diversion outward (and inward on leaving the flow duct) in the outlet region of the air diffuser in this case makes a contribution to swirling of the air stream and therefore to optimizing the diffusion of the air stream as it emerges.
The air diffuser 1 in accordance with the third exemplary embodiment is in two-part form. The air diffuser 1 has an outer flow duct 21 which widens toward its end lying in the direction of air flow and also has a direction-setting device 22 . The shape of the direction-setting device 22 substantially corresponds to that of the air diffuser 1 , i.e. it has an inner flow duct 2 with a circular cross section, a flow body 3 running in the longitudinal center axis of the flow duct 2 and a guiding element 4 , this inner flow duct 2 together with flow body 3 and guiding element 4 being mounted such that it can pivot over a small angle in any desired direction within the outer flow duct 21 , so that the main outlet direction of the air stream which emerges in diffuse form can be set within a certain angular range. The direction-setting device 22 according to the third exemplary embodiment is configured in such a manner that the inner flow duct 3 is mounted in its center, so that in the event of any desired pivoting movement the associated pivot axis runs through this center point.
An air diffuser according to the exemplary embodiments described above is suitable in particular for conditions in which space is limited and in which it is necessary to feed air into the passenger compartment without the risk of a draft when the air comes into direct contact with a passenger. Suitable applications are in particular air diffusers in the B/C pillars, although an air diffuser of this type may also be used at any other desired positions in a vehicle, aircraft, ship or any desired air-conditioned space.
To control the air stream, it is possible for a flap to be arranged in front of the air diffuser; this flap can be actuated by means of an operating device arranged in the passenger compartment. In its simplest possible form, the flap may simply have an open and shut position, whereas in its most complicated form it can provide continuously variable adjustment of the air stream.
LIST OF REFERENCE DESIGNATIONS
1 Air diffuser
2 Flow duct
3 Flow body
4 Guiding element
5 Inner lateral surface
11 Thickened portion
12 Widened portion
21 Outer flow duct
22 Direction-setting device | An air outlet, in particular for a motor vehicle, includes at least one air guide element in a flow duct for inducing a swirl in the airflow on introduction of air into the air outlet from an air duct and a flow body embodied along the longitudinal axis of the flow duct. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Patent Application No. 61/362,134 filed Jul. 7, 2010, the disclosure of which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates generally to digital image-processing systems for the transmission and reception of depth information along with color information (e.g., RGB data), and more particularly, to a method and a digital image-processing system for receiving and using depth information and color information transmitted by a first digital image-processing system to render one or more three-dimensional (3D) views (e.g., stereoscopic or auto-stereoscopic views).
BACKGROUND OF THE INVENTION
[0003] Three-dimensional (3D) video and image transmission systems and 3D television (3D-TV) in particular have gained market acceptance in recent years. In order to present a 3D stereoscopic image to a viewer according to prior art systems, it is necessary to generate at least two separate views, with one intended for the viewer's left eye, and the other intended for the viewer's right eye. Certain prior art 3D-TV systems and methods have been designed to provide compatibility with existing television transmission standards. Examples include frame-compatible packing methods, one of which is described in “Overview of MPEG Standards for 3DTV,” Motorola Corporation, 2010 obtained from http://www.mpegif.org/m4if/bod/Working%20Groups/WP_MPEG_Standards_for — 3 DTV.pdf on Aug. 11, 2010, which is incorporated herein by reference in its entirety. If not directly stated, all documents/papers/articles referenced in the specification are herein incorporated by reference in their entirety.
[0004] In essence, a frame-compatible packing method operates by packing two stereoscopic views (i.e., the right-eye view and the left-eye view) into a normal-resolution frame, such as in a side-by-side or over-under configuration. While this method certainly permits transmission of 3D TV content over existing channels, unfortunately, a viewer with an older 2D television will see a packed frame that is not viewable without a 3D-TV, or at least a 3D-aware set-top box or TV. Additionally, this prior art method suffers from significant resolution degradation, as half of the resolution per-frame is sacrificed in order to squeeze two stereoscopic frames (i.e., left-eye and right-eye) into one. In addition to resolution degradation, television system operators such as broadcasters, cable, and satellite operators employing this conventional system/method are required to deploy a new set of transponders, increased bandwidth, or additional channels to broadcast 3D-TV in this manner, leading to significant expenses.
[0005] Another drawback to the frame-compatible packing transmission method is that the amount of disparity between each eye is fixed at the time of transmission, causing displays of varying sizes at the receiver system to exhibit vastly varying disparities. The end user has very little opportunity to adjust real disparity to compensate for these problems. At best, baseline disparity may be adjusted, in theory, by displacing a left eye presentation relative to the right eye presentation as images are viewed on a 3D-TV. Unfortunately, inter-object disparity cannot be adjusted.
[0006] Other methods known in the art address many of the foregoing issues by encoding view-to-view prediction out-of-band, as described in an amendment to the H.264/AVC video compression standard for Multiview Video Coding (i.e., “ ISO/IEC 14496-10 , Advanced Video Coding, Annex H: Multiview Video Coding” ). Many compatibility issues have been ameliorated by encoding a second (or other) view in a bitstream in such a way that an older codec will discard the extra data, thus rendering a single 2D view. Broadcasts encoded this way benefit by not requiring new channels to be allocated; the same channel may be used to transmit 2D and 3D broadcasts. However, like frame-packing methods, the end user has no granular control over disparity at the point of viewing. As before, at best, the viewer could theoretically control baseline disparity, but not real inter-object disparities.
[0007] Furthermore, overhead associated with such coding schemes for a stereo broadcast is 25 to 35 percent, and therefore requires significant bandwidth upgrades for operators. Present bandwidth allocation in video distribution of this kind will therefore grow accordingly. Additionally, such overhead costs impose incremental costs on backhaul—for example, the same video channels cannot use the same number of satellite transponders. Another major problem with methods based on H.264/AVC is that it is assumed that the entire infrastructure is built out upon H.264/AVC, which is not the case. Most U.S. domestic video distribution infrastructure is still based upon MPEG2. As such, the transmission of H.264/AVC video requires a major upgrade to broadcast and distribution encoding infrastructure for those still using MPEG2, a very expensive proposition. Further, it requires that operators absorb significant costs associated with upgrading customer-premise equipment to support the new standard for anyone wishing to receive 3D-TV broadcasts, resulting in an additional capital expense that frame-compatible methods do not impose.
[0008] Accordingly, what would be desirable, but has not yet been provided, is a system and method for transmitting stereoscopic image data at low or no incremental bandwidth cost, with complete backward compatibility with existing transmission chains, including, but not limited to, MPEG2 encoding and decoding, and for providing a method for a high quality reconstruction of the transmitted stereoscopic image data at a receiver system.
SUMMARY OF THE INVENTION
[0009] The above-described problems are addressed and a technical solution is achieved in the art by providing a transmitter and a computer implemented method configured to transmit three-dimensional (3D) imagery, comprising the steps of extracting a depth map (i.e., a Z channel) and color data from at least one 3D image; reducing bandwidth of the depth map to produce a reduced bandwidth depth map; inserting the reduced bandwidth depth map into the color data to produce a reduced bandwidth 3D image; and transmitting the reduced bandwidth 3D image into a transmission channel for delivery to a display. As used herein, the term “Z channel” describes a depth map of a single channel of image data, where each pixel of the data represents the range or distance of each pixel of a corresponding color image.
[0010] According to an embodiment of the present invention, reducing bandwidth of the depth map comprises retaining at least one region of the depth map comprising at least one discontinuity that corresponds to at least one object boundary in the color data. Reducing bandwidth of the depth map may further comprise removing depth values associated with a modality in a distribution representing depth values in the depth map. According to an embodiment of the present invention, the method may further comprise identifying the modality by: generating a histogram of depth values in the depth map, and performing a modal analysis on the histogram. The method may further comprise applying a grayscale morphological closing operation on the histogram to remove 0.0 or 1.0 depth values. The term “modality” is intended to refer to a principal component in the frequency of occurrence of a value, such as in a frequency histogram of the depth values. Such a modality would be indicated by large local maxima of the frequency distribution(s). When referring to 0.0 or 1.0 depth (Z) values, what is intended is a normalized depth map or depth map having a range from 0.0 to 1.0, where 0.0 indicates a distance at infinity, 1.0 represents a point arbitrarily close to the camera, and 0.5 represents the natural convergence point of the camera system.
[0011] According to an embodiment of the present invention, the method may further comprise filtering the depth map with a median image processing filter. The median image processing filter may be a 5×5 median filter.
[0012] According to an embodiment of the present invention, the method may further comprise performing a spatial decimation operation on the depth map, and applying a lossless method of statistical coding on the depth map. Performing a spatial decimation operation on the depth map may comprise at least one of applying a cubic reduction filter to the depth map and performing a repeated succession of one-octave bicubic reductions. Applying a lossless method of statistical coding on the depth map may further comprise at least one of: transforming the depth map to a 7-bit-per-pixel representation and encoding statistically with a Huffmann encoding scheme, applying arithmetic coding to the depth map, and applying a two-dimensional codebook encoding scheme to the depth map.
[0013] According to an embodiment of the present invention, inserting the reduced bandwidth depth map into the color data may further comprise adding the depth map to color data as a watermark.
[0014] The above-described problems are addressed and a technical solution is achieved in the art by also providing a receiver and a computer implemented method for receiving three-dimensional (3D) imagery, comprising the steps of: receiving a reduced bandwidth 3D image comprising a reduced bandwidth depth map and color data; and applying a filter that employs a statistical domain of the color data to restore bandwidth of the reduced bandwidth depth map. The filter is configured to restore discontinuities in the reduced bandwidth depth map by matching discontinuities of the color data containing at least one object boundary. The method may further comprise applying a depth-image-based rendering (DIBR) method to warp the restored depth map and the color image to construct at least one view suitable for stereoscopic or auto-stereoscopic 3D displays.
[0015] According to an embodiment of the present invention, the at least one filter is a RGBZO filter. The RGBZO filter employs two radiosity weighting functions provided by the reduced bandwidth depth map as a first domain, the color data as a second domain, and a spatial weighting function.
[0016] According to an embodiment of the present invention, the method may further comprise the step of repeatedly subjecting the reduced bandwidth depth map to iterations of one-octave bicubic up-scaling followed by application of the RGBZO filter until a first octave up-scaled depth map is produced. Repeatedly subjecting the reduced bandwidth depth map to iterations of one-octave bicubic up-scaling followed by application of the RGBZO filter may minimize an error function comprising a difference between an edge gradient of the depth map and a color edge gradient of the color data to regularize output of the up-scaled depth map.
[0017] According to an embodiment of the present invention, the method may further comprise the step of applying a lossless decoding method to the reduced bandwidth depth map before said step of repeatedly subjecting the reduced bandwidth depth map to iterations of one-octave bicubic up-scaling followed by application of the RGBZO filter.
[0018] According to an embodiment of the present invention, step of applying a (DIBR) method may further comprise the steps of: applying an optical flow method to the color data; applying motion compensation and image warping to the color to produce a table of motion compensated pixels; applying one of temporal predictions and spatial predictions of candidate occluded pixels from the table of motion compensated pixels; applying a statistical in-painting procedure to the candidate occluded pixels; and warping pixels obtained from the statistical in-painting procedure to obtain left and right eye views of images for display. The method may further comprise the steps of: classifying disocclusions from the depth map to inform spatial predictions of candidate occluded pixels; and applying a Z smoothing method to the depth map to produce a processed depth map. The step of warping is informed by the processed depth map.
[0019] According to an embodiment of the present invention, the transmitter and/or receiver may be implemented using an application-specific integrated circuit (ASIC).
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] The present invention will be more readily understood from the detailed description of exemplary embodiments presented below considered in conjunction with the attached drawings in which like reference numerals refer to similar elements and in which:
[0021] FIG. 1 depicts a block diagram of an exemplary 3D digital processing system, according to an embodiment of the present invention;
[0022] FIG. 2A is a hardware block diagram of an exemplary transmitter of FIG. 1 for stereoscopic displays, according to an embodiment of the present invention;
[0023] FIG. 2B is a hardware block diagram of an exemplary receiver of FIG. 1 for stereoscopic displays, according to an embodiment of the present invention;
[0024] FIG. 3A is a block diagram illustrating exemplary steps of an RGB plus Z transformation and transmission method, according to an embodiment of the present invention;
[0025] FIG. 3B is a more detailed block diagram of FIG. 3A , according to an embodiment of the present invention;
[0026] FIG. 4 is a block diagram illustrating exemplary steps of a reception and transformation method for stereoscopic displays, according to an embodiment of the present invention;
[0027] FIG. 5 is a block diagram illustrating exemplary steps of a reception and transformation method for multi-view auto-stereoscopic displays, according to an embodiment of the present invention;
[0028] FIG. 6 is a block diagram illustrating exemplary steps of an exemplary depth-image-based rendering (DIBR) method employed by the receiver system of FIG. 2B , according to an embodiment of the present invention;
[0029] FIG. 7 shows an example of a left and right eye stereoscopic image pair;
[0030] FIG. 8 shows a RGB plus Z pair corresponding to the stereoscopic image pair of FIG. 7 ;
[0031] FIG. 9 shows the Z channel after treatment by a preprocessing step of the present invention;
[0032] FIG. 10 shows a magnified view of the Z channel after treatment by the decimation step of the present invention.
[0033] FIG. 11 shows the Z channel after a naive elliptical smoothing function has been applied;
[0034] FIG. 12 shows the Z channel after statistical processing and restoration utilizing the RGB data as a domain;
[0035] FIG. 13 shows a naïve reconstructed left and right eye stereoscopic image pair utilizing the decimated Z channel after up-scaling, via an exemplary depth-image-based rendering method according to an embodiment of the present invention;
[0036] FIG. 14 shows a naïve reconstructed left and right eye stereoscopic image pair utilizing the decimated Z channel after up-scaling and processed by a smoothing function, via an exemplary depth-image-based rendering method according to an embodiment of the present invention; and
[0037] FIG. 15 shows a reconstructed left and right eye stereoscopic image pair utilizing the restored Z channel according to the preferred embodiment, via an exemplary depth-image-based rendering method.
[0038] It is to be understood that the attached drawings are for purposes of illustrating the concepts of the invention and may not be to scale.
DETAILED DESCRIPTION OF THE INVENTION
[0039] The present invention relates to a computer implemented image processing method and system for transmitting and receiving three-dimensional (3D) images. FIG. 1 depicts a block diagram of an exemplary 3D digital processing system 100 , according to an embodiment of the present invention. The system 100 includes a computer-implemented receiver 102 , a computer implemented transmitter 104 , an optional depth-image-based rendering (DIBR) module 108 to be described hereinbelow, and an optional display 110 . The system 100 does not include but employs a network 104 communicatively connected to the transmitter 102 and the receiver 104 . The transmitter 102 receives 3D stereoscopic image data comprising color data (e.g., RGB, YUV, etc.) from a transmission chain 101 or generates the 3D stereoscopic image data within the transmitter 102 . The transmitter 102 reduces bandwidth depth information (i.e., the Z channel) of the 3D stereoscopic image data at low or no incremental bandwidth cost, with complete backward compatibility with the existing transmission chain 101 , including, but not limited to, MPEG2 encoding and decoding.
[0040] The color data and reduced bandwidth Z channel is transmitted by the transmitter 102 over the communicatively connected network 104 to the computer-implemented receiver 106 that reconstructs stereoscopic images from the color data and the reduced bandwidth Z channel using a filter according to an embodiment of the present invention to be described hereinbelow. The optional depth-image-based rendering (DIBR) module 108 , to be described hereinbelow, is configured to warp the restored Z channel and the color data to construct at least one view (e.g., a left-eye image or right-eye image) suitable for stereoscopic or auto-stereoscopic 3D displays 110 . The term “depth-image-based rendering” refers to a technique for creating a novel view from the input of an image, and a depth map. There are many depth-image-based rendering methods known in the art—a typical process employs a horizontal pixel offset for each pixel of an input image. The offset's magnitude is calculated to be in proportion to the depth map pixel value in concert with an assumed convergence point, where a given depth map value (say, 0.5) is assumed to present a zero offset. Depth values more or less than this convergence point value are assigned leftward or rightward pixel offsets, respectively.
[0041] According to an embodiment of the present invention, the receiver 106 may further transmit the reconstructed stereoscopic images back through the transmission chain 101 .
[0042] The term “computer” or “computer platform” is intended to include any data processing device, such as a desktop computer, a laptop computer, a mainframe computer, a server, a handheld device, a digital signal processor (DSP), an embedded processor (an example of which is described in connection with FIGS. 2A and 2B hereinbelow), or any other device able to process data. The term “communicatively connected” is intended to include any type of connection, whether wired or wireless, in which data may be communicated. The term “communicatively connected” is intended to include, but not limited to, a connection between devices and/or programs within a single computer or between devices and/or separate Computers over a network. The term “network” is intended to include, but not limited to, OTA (over-the-air transmission, ATSC, DVB-T), video over packet-switched networks (TCP/IP, e.g., the Internet), satellite (microwave, MPEG transport stream or IP), direct broadcast satellite, analog cable transmission systems (RF), digital video transmission systems (ATSC, HD-SDI, HDMI, DVI, VGA), etc.
[0043] The transmitter 102 may comprise any suitable video transmission device, such as, for example, cameras with embedded transmission functions, camera transceiver systems, a video encoding appliance, a video statistical multiplexing appliance (statmux), computers with video capture cards, computers with attached cameras media servers that are spooling/streaming video files, PCs that are spooling/streaming video files, etc. The receiver 106 may comprise any suitable 3D video reception device, including optionally, the DIBR module 108 and the display 110 . Suitable 3D video reception devices may comprise, for example, PCs, tablets, mobile phones, PDAs, video decoding appliances, video demultiplexing appliances, televisions, television distribution Devices (e.g., AppleTV™), television set-top boxes, and DVRs.
[0044] If the Z channel data is embedded in-band (i.e., within a 3D color image to be transmitted), for example using a steganographic method, then certain embodiments of the system 100 provide fully backward and forward-compatible 2D and 3D video signaling and transmission. The term “steganographic” generally refers to hiding information in images. Within the context of the transmission system 102 , the term “steganographic” refers to a means of embedding or hiding a Z channel within the color image data in such a way as to not be visible or apparent to a human viewer.
[0045] Still further, if the display 110 is an autostereoscopic display, no glasses are required to view the 3D imagery on the display 110 .
[0046] FIG. 2A depicts a block diagram of an exemplary transmitter 102 , according to an embodiment of the present invention. By way of a non-limiting example, the transmitter 102 receives digitized 3D video or still images comprising a depth map (i.e., a Z channel) and color data (collectively referred to as “a 3D image”) from one or more data storage systems 111 , and/or one or more image capturing devices 112 (e.g., one or more still or video cameras, shape cameras, LIDAR or IR photogrammetry-generated range devices), and/or from the existing transmission chain 101 . According to an embodiment of the present invention the one or more 3D images may be synthetically estimated, or calculated from stereo image pair disparity values, such as the example shown in FIG. 7 . Optionally, the digitized video or still images may be received via a network 113 , such as the Internet. According to an embodiment of the present invention, the transmitter system 102 includes a computing platform 116 , and may also optionally include a digital video capture system 114 . The digital video capturing system 114 processes streams of digital video, or converts analog video to digital video, to a form which can be processed by the computing platform 116 . The digital video capturing system 114 may be stand-alone hardware, or cards such as Firewire cards which can plug directly into the computing platform 116 . According to an embodiment of the present invention, the image capturing devices 112 may interface with the video capturing system 114 /computing platform 116 over a heterogeneous data link, such as a radio link (e.g., between a satellite and a ground station) and a digital data link (e.g., Ethernet, between the ground station and the computing platform 116 ). The computing platform 116 may include a personal computer or work-station (e.g., a Pentium-M 1.8 GHz PC-104 or higher) comprising one or more processors 120 which includes a bus system 122 which is fed by video data streams 124 via the one or more processors 120 or directly to a computer-readable medium 126 . Alternatively, the computing platform 116 may be implemented as or part of an integrated circuit, such as a graphics processing unit (GPU) or digital signal processor (DSP) implemented in an field-programmable gate array (FPGA) or an application-specific integrated circuit (ASIC).
[0047] The computer-readable medium 126 may also be used for storing the instructions of the transmitter system 102 to be executed by one or more processors 120 , including an optional operating system, such as a Windows or the Linux operating system. The computer-readable medium 126 may further be used for storing and retrieving video clips of the present invention in one or more databases. The computer-readable medium 126 may include a combination of volatile memory, such as RAM memory, and non-volatile memory, such as flash memory, optical disk(s), and/or hard disk(s). Portions of a processed video data stream 128 may be stored temporarily in the computer-readable medium 126 for later output to a network 104 , such as the Internet, and/or to the transmission chain 101 .
[0048] FIG. 2B is a block diagram of an exemplary 3D receiver 106 , according to an embodiment of the present invention. By way of a non-limiting example, the receiver 106 receives digitized and processed 3D video or still images comprising color data and a reduced bandwidth Z channel (collectively referred to as “a reduced bandwidth 3D image”) from the transmitter via a network 104 , such as the Internet, and/or from the existing transmission chain 101 . The receiver 106 may also include a computing platform 216 . The computing platform 216 may include a personal computer or work-station (e.g., a Pentium-M 1.8 GHz PC-104 or higher) comprising one or more processors 220 which includes a bus system 222 which is fed by video data streams 224 via one or more processors 220 or directly to a computer-readable medium 226 . Alternatively, the computing platform 216 may be implemented as or part of an integrated circuit, such as a graphics processing unit (GPU) or digital signal processor (DSP) implemented in an FPGA or ASIC.
[0049] The computer-readable medium 226 may also be used for storing the instructions of the receiver 106 to be executed by one or more processors 220 , including an optional operating system, such as a Windows or the Linux operating system. The computer-readable medium 226 may further be used for the storing and retrieving of processed video of the present invention in one or more databases. The computer-readable medium 226 may include a combination of volatile memory, such as RAM memory, and non-volatile memory, such as flash memory, optical disk(s), and/or hard disk(s). Portions of a processed video data stream 228 comprising a “restored” depth map (i.e., the restored Z channel) and color data (collectively referred to as “a restored 3D image”) temporarily in the computer-readable medium 226 for later output to a monitor 230 configured to display the restored 3D images. Optionally, the monitor 230 may be equipped with a keyboard 232 and/or a mouse 234 or other like peripheral device(s) for an analyst or viewer to select objects of interest (e.g., user-interface elements that permit control of input parameters to the receiver 106 ). Alternatively, the restored 3D images may be passed to the transmission chain 101 .
[0050] Embodiments of the present invention are directed toward solving the problems of the prior art by employing depth maps associated with stereo or multiview imagery in order to transmit depth information economically. There are a variety of methods for generating depth maps from stereo or multiview imagery that are out of scope of a description of the present application; however, the teachings in an article by of Yang et. al., titled “ Improved Real - Time Stereo on Commodity Graphics Hardware,” Proceedings of the 2004 Conference on Computer Vision and Pattern Recognition Workshop (CVPRW'04) Volume 3, 2004, and in an article by Diaz et. al., titled “ Real - Time System for High - Image Resolution Disparity Estimation,” IEEE Trans Image Process., 2007 January; 16(1):280-5, are instructive and are incorporated herein by reference in their entirety. Depth maps have peculiar statistical properties that may be advantageously employed by a suitable encoding process. In an article by Morvan et al., titled “ Platelet - based coding of depth maps for the transmission of multiview images,” in Stereoscopic Displays and Virtual Reality Systems XIII. Edited by Woods, Andrew J. et al., Proceedings of the SPIE, Volume 6055, pp. 177-188 (2006), statistical properties are explored in more detail. Exemplary statistical properties include extremely strong tendencies towards piece-wise linearity characteristics. In other words, depth images contain large regions of gradual, linear changes bounded by sharp discontinuities that coincide with object boundaries in a color image.
[0051] With knowledge of these properties, according to an embodiment of the present invention, the transmitter 102 is configured to reduce the bandwidth of the depth maps (i.e., the Z channel) on the order of 500 to 1. Furthermore, the receiver 106 is configured to according to an embodiment of the present invention to produce a restored 3D image for display. This results in a depth-image-based rendering method which synthesizes one or more views at high quality for a stereoscopic or multiview auto-stereoscopic display. A particular advantage of systems designed according to embodiments of the present invention is that a resulting reduction in bandwidth is achieved which permits crude methods of digital watermarking to be employed to embed depth data (i.e., Z channel data) within RGB data of the view images themselves, robustly, even in the face of aggressive low-bit rate compression with codecs such as MPEG2.
[0052] A primary object of embodiments of the present invention is to reduce the bandwidth of the Z channel to a degree such that it can be transmitted via digital watermarking, in-band, within the RGB data, without affecting RGB quality. Furthermore, a suitably large reduction of bandwidth of the Z channel renders the problem of in-band transmission more amenable to perceptual coding of RGB data as compared with MPEG2 or H.264. This, in turn, solves a major problem—by decoupling the Z channel from the transmission method and bitstream, complete backwards compatibility with the existing broadcast and transmission chain is achieved. This is only possible with a drastic reduction of the overall transmission bandwidth of the Z channel. It will be appreciated by those skilled in the art that other methods of in-band and out-of-band transmission of Z channel data may be employed, such as supplemental audio channel data.
[0053] FIG. 3A shows a block diagram illustrating exemplary steps of an RGB plus Z (i.e., a color plus Z channel) transformation and transmission method according to an embodiment of the present invention. FIG. 3B presents the steps/blocks of FIG. 3A in further detail.
[0054] For the steps illustrated in FIGS. 3A and 3B , it is assumed that the RGB data and the Z channel data are inputs to the transmitter 102 and/or the receiver 106 as described above in FIGS. 2A and 2B and further illustrated in FIG. 8 . Referring now to FIGS. 3A and 3B , at step 302 , a preprocessing step is performed on the Z channel data. In a preferred embodiment, the preprocessing step 302 includes sub-step 302 a wherein a histogram of depth values is generated, and sub-step 302 b wherein a modes analysis of the generated histogram is performed for identifying whether there is a significant modality in the distribution surrounding the 0.0 or 1.0 depth Z values. If sub-step 302 b indicates that such a modality exists, then at sub-step 302 c , a well-known grayscale morphological closing operation is performed to eliminate 0.0 and 1.0 clamped outliers (otherwise, the method passes on to step 302 d hereinbelow). At sub-step 302 d , the filtered data is processed by a median image processing filter one or more times in succession, which may be, for example, a 5×5 median filter run for two to three iterations. An example of a preprocessed depth map is shown in FIG. 9 . The preprocessing sub-steps 302 a - 302 d eliminate noise and outliers associated with numerical singularities and occlusion/disocclusion artifacts common in IR photogrammetry and disparity-estimated depth maps. Advantageously, preprocessing step 302 alters the Z channel to more fully match the piecewise-linearity assumption, without destroying useful range/depth data.
[0055] At step 304 , a spatial decimation operation is performed on the Z channel step 302 . According to an embodiment of the present invention, step 304 may be implemented in a single step, such as the application of a cubic reduction filter. According to another embodiment of the present invention, a preferred, but slightly more expensive operation preserves more intermediate-scale details, namely, in sub-steps 304 e - 304 h , to perform a repeated succession of one-octave bicubic reductions (e.g., the performance of four reductions which, reduces the data associated with the Z channel by a factor of 256). FIG. 10 depicts such a decimated Z channel. A person skilled in the art will appreciate that while the bandwidth of the Z channel has been drastically reduced, so has all or a portion of the fine-structure information—most importantly, the placement and orientation of object edges has been lost. A primary object of embodiments of the present invention is to restore this information at the reception end.
[0056] At step 306 , an additional reduction in dynamic range followed by a lossless method of statistical coding may further reduce the dataset. In one preferred embodiment, the Z channel is transformed to a 7-bit-per-pixel representation and encoded statistically with a Huffman scheme. The overall data reduction ratio approaches 500 to 1 for typical Z channel video sequences. According to other embodiments of the present invention, application of a lossless method in step 306 , may include, but is not limited to, other statistical coding schemes, such as arithmetic coding, and two-dimensional codebook schemes. According to one preferred embodiment, further reductions are possible with temporal prediction, and DCT-domain quantization of the decimated, dynamic-range reduced Z channel data.
[0057] At step 308 , the reduced Z channel data may be steganographically added to the RGB data as a watermark. With the Z channel data transformed to a representation having approximately 500 times smaller bandwidth than the original RGB, it is now possible to use standard watermarking techniques to transmit the Z channel data within the RGB data as a digital watermark. Such standard watermarking techniques can be very robust to low-bitrate perceptual coding, such as MPEG2. A preferred embodiment encodes each of the 7 bits of a given decimated depth map value within the chrominance of the 4th-octave Z value's associated 16×16 RGB block. It will be understood by those skilled in the art that many existing watermarking embedding methods may be employed that are very robust so long as certain conditions are met, namely, the bandwidth of the watermark data itself is a significantly smaller bandwidth than the carrier data, otherwise the carrier data will be affected in a visible way. Additionally, a high bandwidth of the watermark payload relative to the carrier may expose the watermark to losses when downstream transformations are applied, such as perceptual encoding, cropping, scaling, and color gamut remapping. Embodiments of the present invention are directed to treating the Z channel data with sufficient reduction so as to allow any contemporaneous watermarking method to be employed successfully.
[0058] At step 310 , the baseband video or image RGB data with the embedded watermark data is then treated as a normal RGB image or video signal that may be transmitted throughout the rest of a transmission chain.
[0059] A person skilled in the art will appreciate that direct utilization at a receiver of a transmitted, in-band, watermarked RGB data signal such a decimated Z channel, without some sort of restoration, is problematic. Utilizing such a Z channel as a depth map directly in a depth-image-based rendering framework may result in significant artifacts, as shown in FIG. 13 . Noticeable blocking artifacts are visible in synthesized views. One method of restoration may simply smooth the decimated Z channel preferentially along the horizontal axis, after up-scaling according to any suitable technique, such as, for example, the technique described in an article by Tam et al., titled “ Non - Uniform Smoothing of Depth Maps Before Image - Based Rendering,” in Three-Dimensional TV, Video, and Display III, Edited by Javidi, Bahram; Okano, Fumio, Proceedings of the SPIE, Volume 5599, pp. 173-183 (2004). The results of this approach are shown in FIG. 14 , which demonstrates that significant geometric distortions of foreground objects are visible. These distortions are caused primarily when Z channel data crosses actual object boundaries. In fact, if sufficient smoothing is applied to completely eliminate the blocking artifacts, all spatial coherency between the Z channel and RGB channel is lost, causing severe geometric warping. Geometric disparities and shape dislocations between left and right eye views of this sort have been found to cause severe distress in viewers as taught in an article by Emoto, et al., titled “ Working Towards Developing Human Harmonic Stereoscopic Systems,” in: Three-Dimensional Imaging, Visualization, and Display, edited by B. Javidi et al. (Springer-Verlag, New York, 2008) pp. 417-466.
[0060] Recalling the peculiar spatial characteristics of depth maps, namely, a tendency towards piecewise linearity, it may be observed that the sharp boundaries of an original depth map correlate strongly to object boundaries of a corresponding RGB image, transmitted according to the embodiment described above in connection with FIGS. 3A and 3B . According to an embodiment of the present invention, a two-domain bilateral filter (denoted by “RGBZO” and described in more detail hereinbelow) followed by one-octave up-scaling may be repeatedly applied to the watermarked RGB signal to smooth Z gradients within objects, while preserving and recreating the original edge discontinuities of the Z channel.
[0061] FIG. 4 is a block diagram illustrating exemplary steps of a reception and transformation method for stereoscopic displays, while FIG. 5 depicts the method of FIG. 4 modified for multi-view auto-stereoscopic displays, according to embodiments of the present invention. Referring now to FIGS. 4 and 5 , at the receiving end of a transmission channel, at step 402 , the decimated Z channel watermark is steganographically extracted from the received RGB data. At step 404 , the extracted Z watermark is subjected to a lossless decoding method. At step 406 , the decoded Z channel data is subjected to a 2 factor 5-sigma/bilateral filter employing the statistical domain of the RGB data to treat the Z channel data. In steps 408 , 410 , the Z channel data is repeatedly subjected to successive turns of one-octave bicubic up-scaling, followed by a run of the RGBZO operation, until one RGBZO operation has been run upon the 1 st octave up-scaled Z channel. The output of the last RGBZO constitutes a “restored” Z channel, which along with the extracted RGB data, are subjected to a depth-image-based rendering (DIBR) method 412 whereby the “restored” Z channel data is used in order to warp the current RGB image to construct one or more additional views suitable for stereoscopic ( FIG. 4 ) or auto-stereoscopic ( FIG. 5 ) 3D displays.
[0062] The RGBZO bilateral filter of the present invention differs from prior art bilateral filters in several significant ways. A normal bilateral filter as defined in Equations 1 and 2 below calculates filter weights adaptively by spatial distance constituting a range, and radiosity distance constituting a domain within an image under analysis to drive weighting. More particularly, for input image Z, output image Z′, and window of support Ω, a typical bilateral filter is defined as follows in Eq. 1:
[0000]
Z
x
′
=
∑
ξ
∈
Ω
g
(
ξ
-
x
)
r
(
Z
ξ
-
Z
x
)
Z
ξ
∑
ξ
∈
Ω
g
(
ξ
-
x
)
r
(
Z
ξ
-
Z
x
)
(
1
)
[0000] where g is a Gaussian spatial weighting function, and r is a radiosity weighting function. Typical values for radiosity include luminance or intensity of the constituent pixel samples. System input is typically supplied by constant factors σ s and σ r that modify the g and r functions as in Eq. 2 and 3:
[0000]
g
(
ξ
-
x
)
=
-
0.5
(
ξ
-
x
σ
s
)
2
(
2
)
r
(
ξ
-
x
)
=
-
0.5
(
Z
(
ξ
)
-
Z
(
x
)
σ
r
)
2
(
3
)
[0063] The radiosity function r for the Z domain is defined by Eq. 3 above. Eq. 2 defines spatial weighting in the function g. Radiosity weighting is defined by Eqs. 4-7 and its accompanying description hereinbelow.
[0064] Smaller values of factors σ s and σ r , increase the locality and similarity of spatial and radiosity weighting contributions, respectively. The L2 distance measure (i.e., the Euclidian distance) in the denominator of the exponential of radiosity function r is appropriate for images where only luminosity or intensity is enough to differentiate edges and boundary locality sufficiently.
[0065] In the preferred embodiment, a second image radiosity domain is provided by a second input of the RGB data, as function d in Eq. 4:
[0000]
Z
x
′
=
∑
ξ
∈
Ω
g
(
ξ
-
x
)
r
(
Z
ξ
-
Z
x
)
d
(
RGB
ξ
-
RGB
x
)
Z
ξ
∑
ξ
∈
Ω
g
(
ξ
-
x
)
r
(
Z
ξ
-
Z
x
)
d
(
RGB
ξ
-
RGB
x
)
(
4
)
[0000] where the new second domain radiosity function d is defined by Eq 5:
[0000]
d
(
ξ
-
x
)
=
-
0.5
(
δ
(
RGB
(
ξ
)
-
RGB
(
x
)
)
σ
d
)
2
(
5
)
[0000] and the function d measures not just luminosity difference, but a color difference measure in HSV color space. First, a hue value (as in HSV space) is calculated from the RGB color values as in Eq. 6:
[0000]
max
RGB
(
x
)
=
max
(
R
(
x
)
,
G
(
x
)
,
B
(
x
)
)
min
RGB
(
x
)
=
min
(
R
(
x
)
,
G
(
x
)
,
B
(
x
)
)
chroma
(
x
)
=
max
RGB
(
x
)
-
min
RGB
(
x
)
luma
(
x
)
=
RGB
T
·
[
0.3
,
0.59
,
0.1
]
Hue
(
x
)
=
{
NaN
,
if
chroma
=
0
(
G
(
x
)
-
B
(
x
)
)
chroma
mod
6
,
if
max
RGB
(
x
)
=
R
(
x
)
(
B
(
x
)
-
R
(
x
)
)
chroma
+
2
,
if
max
RGB
(
x
)
=
G
(
x
)
(
R
(
x
)
-
G
(
x
)
)
chroma
+
4
,
if
max
RGB
(
x
)
=
B
(
x
)
}
(
6
)
[0066] The function δ is defined as in Eq. 7:
[0000] δ( x −ξ)=min{abs[Hue( x )−Hue(ξ)],abs[Hue(ξ)−Hue( x )]}×(Luma(ξ)−Luma( x )) (7)
[0067] Similarly to the factors σ s and σ r , the new factor σ d affects the locality of the similarity measure against the RGB data. The radiosity weighting is not just provided by the Z channel, but the RGB channels as well. This combined, calculated radiosity weighting is in turn applied to the Z channel output. A repeated iteration of this type of filtering operation has the effect of regularizing the output of the up-scaled Z channel, minimizing an error functional comprising the difference between the edge gradient of the Z channel versus the color edge gradient of the RGB channels. Assuming that both the RGB channels and Z channel are ranged from 0.0 to 1.0, an exemplary set of parameters for such RGBZO filters are:
[0000] Ω={ 5 , 5 }
[0000] σ s =0.65000
[0000] σ r =0.06250
[0000] σ d =0.00825 (8)
[0068] This regularization step to “restore” the Z channel may be performed, according to an embodiment of the present invention, by means of a single up-scaling step from 4 th octave to 1 st octave, with a repeated iteration of the RGBZO operation upon the full resolution Z channel. This can be thought of as a gradient descent operation with repeated iterations until convergence. A result of the same quality with much less complexity may be achieved, according to an embodiment of the present invention, by successive turns of one-octave bicubic up-scaling, followed by a run of the RGBZO operation, until one RGBZO operation has been run upon the 1 st octave up-scaled Z channel as illustrated above in FIGS. 4 and 5 . The results of the application of this method may be seen in FIG. 12 , where the Z channel has been restored via the method described hereinabove. Clearly, the Z channel is now spatially correlated and a significant amount of the information lost in the decimation process at transmission has been restored.
[0069] According to an embodiment of the present invention, in the event that the above-described process does not result in a perfect restoration—wherein the combined transmission and reception methods can be likened to that of a lossy compression—the regenerated Z channel data produce stereoscopic reconstructions that mean observer scores suggest are largely indistinguishable from reconstructions using the original Z channel data. FIG. 15 shows such an exemplary restoration.
[0070] It will be appreciated by those skilled in the art that, according to embodiments of the method of the present invention, any estimation of depth maps may be performed at lower resolution and “treated” by the steps illustrated in FIG. 4 of the receiver 106 at any point of the transmission chain 101 , or the method of the receiver 104 taught in FIG. 4 may be utilized to generate a highly spatially correlated, object-coherent, full-resolution depth map from a lower resolution and lower-accuracy depth map given a correlated RGB image. This permits coarse approximations of depth maps to be calculated and to be used, no matter their ultimate source. An example of another preferred embodiment would use a low-complexity method such as those taught in an article by Tam et al., titled “ Depth Map Generation for 3- D TV: Importance of Edge and Boundary Information,” in: Three-Dimensional Imaging, Visualization, and Display, edited by B. Javidi et al. (Springer-Verlag, New York, 2008) pp. 153-182, to estimate depth from other cues such as motion or blur at the receiver at low resolution, and use the present method of FIG. 4 to treat such depth maps prior to utilizing them for depth-image-based rendering.
[0071] With a properly restored Z-channel in-hand to use as a depth map, what remains is to employ the Z channel to generate as many synthetic views as required by a display. In the case of a stereoscopic display, two views are necessary. An exemplary DIBR method is shown in FIG. 6 , according to an embodiment of the present invention. A primary issue any DIBR method needs to deal with is occlusions. When a foreground object is to be displaced to the left, or to the right, such displacement may reveal background pixel data for which there is no explicit replacement. The occluded data needs to be predicted, either spatially, temporally, or a combination of both.
[0072] With an accurate optical flow method (block 602 ) such as that taught in the co-pending U.S. patent application Ser. No. 12/555,472, filed Sep. 8, 2009, and titled “System and Method for Determination of Optical Flow,” which is incorporated herein by reference in its entirety, a probability table for each pixel comprising possible motion-compensated candidates (block 606 ) for filling in occluded pixels may be formed via motion-compensated image warping (block 604 ). Additionally, spatial prediction (block 608 ) utilizing the class of prediction algorithms known as “statistical in-painting” may be used if no suitable temporal predictions (block 610 ) are available. The term “in-painting” refers to a process for reconstructing lost or deteriorated parts of images and videos. Yet a third choice is to spatially blur the depth map itself (block 612 ), which has the effect of geometrically distorting foreground objects to cover such disocclusions.
[0073] In practice, the exemplary DIBR method uses geometric distortion for small-grade occlusions of less than 1% of image width, and chooses between temporal and spatial prediction based upon the availability and confidence measure of the temporal prediction probability table. In order to do this, an intermediate stage attempts to classify discocclusions (block 614 ) into one of four categories based on data manifest in the Z channel itself: left displacement, right displacement, full-Z-behind, full-Z-front. Additionally, the horizontal extent of the disocclusion is estimated. The horizontal extent is used to determine if local, directional blurring of the depth map covers the disocclusions without significant geometric distortion artifacts. Failing that, the presence of temporal prediction candidates is the second choice, and in the case no temporal prediction candidates are available, the classification of the disocclusion type (block 614 ) is used to inform the spatial prediction used by the in-paint procedure about which direction(s) to use when interpolating.
[0074] In blocks 618 and 620 , left and right eye views may be obtained via image warping based on the in-paint candidates mixture (block 616 ) previously obtained in blocks 608 , 610 and 612 .
[0075] A benefit of employing a DIBR method such as that illustrated in FIG. 6 is that varying display sizes may be accommodated by preset or user supplied parameters. In the exemplary system, both virtual views may be simulated by means of two virtual cameras. Three user input parameters may be specified—a simulated interaxial distance, a simulated focal length for each virtual camera, and a simulated convergence point.
[0076] While the exemplary DIBR method of FIG. 6 regenerates the left-eye view along with the right-eye view, it will be appreciated by those skilled in the art that economy may be achieved by utilizing the original RGB as the left-eye view, and only synthesizing the right-eye at a 1× focal length instead of +0.5× and −0.5× focal lengths for both eye views.
[0077] In a similar manner to FIG. 4 , FIG. 5 shows the same preferred embodiment with the same exemplary DIBR method used to generate an 8-view auto-stereoscopic output (blocks 412 ).
[0078] It is to be understood that the exemplary embodiments are merely illustrative of the invention and that many variations of the above-described embodiments may be devised by one skilled in the art without departing from the scope of the invention. It is therefore intended that all such variations be included within the scope of the following claims and their equivalents. | A digital image processing system takes color plus Z channel data as input, preprocesses, decimates, and codes the Z channel in-band as digital watermark data embedded within the color data prior to encoding and transmission. A second digital image processing system receives, decodes, and extracts the decimated Z channel data before applying statistical regularization to restore a full-resolution Z channel prior to depth-image-based rendering. | 7 |
[0001] This application is based on and claims priority from utility patent application Ser. No. 10/062,119, filed Jan. 31, 2002 which claims priority from provisional patent application Serial No. 60/299,225, filed Jun. 19, 2001.
FIELD OF THE INVENTION
[0002] Applicants' invention relates to a method for making road base using primarily waste material from oil and gas waste solids and non-hazardous industrial waste or natural occurring porous or semi-porous material to create a asphalt stabilized road base that is environmentally safe and meets industry standards for quality materials. More particularly, it relates to isolating oil and gas waste from the environment, treating the isolated oil and gas waste and combining, isolated, treated oil and gas waste material with aggregate to provide the major components for the roadbed base material.
BACKGROUND INFORMATION
[0003] Because of their importance in all aspects of both business and private life, the construction of roads has historically been of prime importance to a society. That importance remains today. However, it has also become more apparent in recent years that most resources are not infinite but rather, are depletable. Additionally, disposing of waste materials is becoming harder and harder due both to space limitations and liability resulting from waste materials entering the environment.
[0004] Thus, there is a need for developing methods and devices to recycle waste products into new, usable products. If the components of roadbeds can be obtained from the waste products of other products and processes, then both waste product production is decreased and new product consumption is decreased. Further, it is advantageous to recycle waste products due to the economic advantage of using recycling materials and thus compounding return on the original costs of the products.
[0005] While oil and gas waste material has been a component of roadbed material there has in the prior art not existed a method, or structures for practicing the method of combining oil and gas waste product into a road bed in a manner such that the oil and gas waste material is isolated, at each step of it's acquisition, transportation, delivery, storage, treatment and mixing at a remote production plant so as not to contaminate the environment. “On the ground mixing” of oil and gas waste material to make a road base may be environmentally harmful. Applicant's use of a man made impervious layer “MMIL” and other devices and methods, in order to isolate both the oil and gas waste material, and any harmful bi-products thereof, during a process of producing a roadbed, at a plant or site designed for such novel processes and devices will yield benefits in a clean environment and also benefits and recovery of harmless compositions in the treatment process which may be further treated in such a manner as to either become benign and/or be recycled.
[0006] Moreover, Applicant's providing of a managed, isolated site and treatment process may yield more efficiency then a “on the ground process.” Applicant's processes and devices for such processes used at a remote site would typically use less equipment then “on the ground mixing.” Further, Applicant's novel method of stacking and of mechanical separation of the proportion of liquids from a portion of solids of oil and gas yields benefit in both isolating harmful oil and gas waste material from the environment but allows the recycling of liquid portions of the oil and gas waste material apart from the oil and gas material as a whole. Applicant provides a cement slab operation, for example, the stacking oil and gas material to generate gravity induced separation. On the ground operation requires spreading to dry the material-by absorption with the ground material. Applicant's methods are believed to environmentally sound and yield treatment of liquid portions for, for example recycling.
SUMMARY OF THE INVENTION
[0007] The primary focus of the invention is the acquisition, transportation, storage and treatment of oil and gas waste as isolated from the environment at an environmentally safe facility, for use with other materials to make a suitable road base material. Treatment of isolated oil and gas waste is done to remove at least a portion of a liquid component, typically primarily oil and water to yield a treated oil and gas waste portion which is then combined, still isolated, with an aggregate and a binder and stabilizer to produce a suitable road base material. The treatment of the isolated oil and gas waste, while yielding a liquid portion may also yield other recyclable or useable products such as clean mud. Clean mud is a product often desired by oil and gas well drillers. Thus, it is the desired result of the present invention of using oil and gas waste material treated in isolation, such that it is converted into a material that is useable and, excepting perhaps “waste water” which may be reinjected, yields environmentally friendly, economically valuable components.
[0008] Turning to the separation of the liquid component from the oil and gas waste material it is anticipated by the present invention that there are a number of methods of liquid portion removal. Each such method will allow separation without contaminating the environment. One such method is a novel means of stacking of oil and gas waste in an impervious container, to yield gravity induced separation of some of the liquid portion from the solid portion. Another method is mechanical separation, such as by a centrifuge. A third method is mixing with a dry material, such, for example, as soil, overburden, or caliche limestone, on a man-made impervious layer (“MMIL”).
[0009] Such methods of treatment in isolation not only help keep the environment clean, but may yield, with further treatment, valuable material.
[0010] The present invention provides a novel method to produce road base material using waste products from one or both of two industries: oil and gas well drilling and from construction and/or demolition and manufacturing projects. The present invention also provides for a novel road base composition. The oilfield waste is typically comprised of hazardous and/or non-hazardous oilfield solid or liquid waste such as water based drilling fluid, drill cuttings, and waste material from produced water collecting pits, produced formation sand, oil based drilling mud and associated drill cuttings, soil impacted by crude oil, dehydrated drilling mud, waste oil, spill sites and other like waste materials tank bottoms, pipeline sediment and spillsite waste. Oilfield waste may include waste or recycled motor oil, petroleum based hazardous or non-hazardous materials, such oilfield waste materials are collectively referred to as “oil and gas waste material.” They typically have a solid component and a liquid component, the liquid component including quantities of oil and water. The solid components may be, in part, particulate, or cuttings.
[0011] An aggregate component of the road based material may include a non-hazardous industrial waste as defined in more detail below or any natural occurring stone aggregate such as limestone, rip rap, caliche, sand, overburden, or any other naturally occurring porous material. There may or may not be preparation of the aggregate material prior to combining with the treated oil and gas material to form the primary component of the road based material of Applicant's present invention.
[0012] The construction and/or demolition or manufacturing waste component of the aggregate material is typically comprised of non-hazardous industrial waste such as waste concrete, waste cement, waste brick material, gravel, sand, and other like materials obtained as waste from industrial construction, demolition sites, and/or manufacturing sites. Such materials are collectively referred to as “non-hazardous industrial waste.”
[0013] One application of the method of the present invention provides for recycling the oil and gas waste material and the non-hazardous industrial waste to combine to produce road base. Another application of the present invention provides for recycling the oil and gas waste material and an aggregate including limestone, rip rap, caliche, or any naturally occurring porous or semi-porous material to combine to produce road base. Hydration and mixing of the isolated, treated oil and gas waste material and aggregate along with a binder such as cement, fly ash, lime, kiln dust or the like, will achieve an irreversible pozzolanic chemical reaction necessary for a road base. An asphalt emulsifier may be included in the binder to manufacture asphalt stabilized road base. The ingredients are typically mixed in a cold batch process.
[0014] Solid waste from the oil and gas waste material typically contains naturally occurring aluminas and silicas found in soils and clays. The added pozzolan will typically contain either silica or calcium ions necessary to create calcium-silica-hydrates and calcium-aluminate-hydrates. A pozzolan is defined as a finally divided siliceous or aluminous material which, in the presence of water and calcium hydroxide will form a cemented product. The cemented products are calcium-silicate-hydrates and calcium-aluminate-hydrates. These are essentially the same hydrates that form during the hydration of Portland Cement. Clay is a pozzolan as it is a source of silica and alumina for the pozzolanic reaction. The aggregate including natural stone aggregate or non-hazardous industrial waste adds structure strength and bulk to the final mix.
[0015] The process of creating a stabilized road base using an aggregate including non-hazardous industrial waste and oil and gas waste material may incorporate a water based chemical agent such as waste cement, varying amounts of aggregate and waste to produce a cold mix, stabilized road base product. An aggregate crusher may process the inert material (typically aggregate including the non-hazardous industrial waste or natural stone aggregate), into the size and texture required (from, for example ½″ to 4″). The aggregate is added to the treated oil and gas waste material at a desired ratio in a manner that prevents contamination of the environment. It has been found that an approximate ratio of one-to-one treated oil and gas waste material to aggregate provides a good mix. This could vary depending upon the degree of contamination or the quality of the oil and gas waste. A chemical reagent may be added to congeal the mixture. An asphalt emulsifier is added to create an asphalt stabilized road base. The resulting product is a stabilized road base that not only is of a superior grade, but will not leach hydrocarbons, chlorides or RCRA metals in excess of constituent standards set forth in the Clean Water Act.
[0016] In order to further the environmental objectives of the present invention, it is desirable to isolate the oil and gas waste material from the source to the site and at the site from the environment prior to during and after mixing. Thus, while the aggregate may be stored on the ground, oil and gas waste material should be received, transferred and stored surrounded by a berm and/or placed on a cement pad, or otherwise isolated by a physical barrier that will prevent leaching of liquid contaminates into the soil. This also prevents storm water runoff. The manufactured road base typically is mixed, processed, and likewise stored surrounded by an earthen berm and on a cement pad and/or other physical barrier that will prevent leaching of liquid contaminates into the soil. Thus, the present invention provides a novel method that will produce an environmentally safe grade road base material.
[0017] Among the objectives of the present invention are to:
[0018] a. provide isolation of environmentally harmful oil and gas waste from acquisition through to treatment of and conversion to environmentally safe products;
[0019] b. combine treated oil and gas waste material with aggregate to produce a stabilized road bed composition;
[0020] c. reduce waste from oil drilling, and construction/demolition and manufacturing;
[0021] d. reduce the use of new materials for roadbeds;
[0022] e. provide a method for producing roadbed material at a lower cost than conventional methods;
[0023] f. provide methods and devices for treating oil and gas waste material isolated from the environment, to yield a material that can be used for preparing a stabilized roadbed and also yield clean mud and water,
[0024] g. combine treated oil and gas waste material with non-hazardous industrial waste or naturally occurring material to yield an environmentally safe, usable, stabilized road bed composition;
[0025] h. provide simple methods and devices of removing a liquid component from oil and gas waste material while the oil and gas waste and the resulting components remain isolated from the environment;
[0026] i. recycle aggregate waste from construction, demolition and manufacturing sites; and
[0027] j. provide for a single site or location to which oil and gas waste is transported, stored and at which it is treated and mixed, in isolation from the environment, to form a road base composition.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] [0028]FIG. 1 is an overview of a process of storage and treatment by dry mixing the oil and gas waste material.
[0029] [0029]FIG. 1A is a generalized view of a process of applicants present invention.
[0030] [0030]FIG. 2 is a flow chart illustrating an overview of a process of combining treated oil and gas waste material and aggregate to produce, typically in a pug mill, waste mix 14 , which cures to form a novel road base.
[0031] [0031]FIGS. 2A-2D illustrates applicants novel method and device for isolating stacking oil and gas waste material.
[0032] [0032]FIGS. 3 and 3A represent preferred alternate embodiments of a process of treating the oil and gas waste material in isolations to prepare it for combination with the aggregate waste material.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0033] [0033]FIG. 1A illustrates an overview of the steps of Applicant's present invention. Applicant provides for, in obtaining step 1 A, obtaining oil and gas waste from an oil and gas waste site as set forth in more detail below and transferring the waste to a treatment and mixing site. The second step, the obtaining step 1 B, is that of obtaining an aggregate, typically inert, from a natural source such as limestone rock, caliche, rip rap, sand, dirt or the like or, as waste material from a construction, manufacturing, or demolition site. Step 2 is the treatment of oil and gas waste to remove fluids and obtain water and recyclable material, which water and material may be further processed. The third step is some form of mixing (as described in more detail below) wherein treated oil and gas waste is combined with aggregate and other material while in isolation from the environment to provide an environmentally safe roadbed.
[0034] Turning back to the oil and gas waste, it is typically transported to the treatment site where applicant's novel treatment provides several methods of removing at least some of the fluids, from the oil and gas waste material to provide a treated oil and gas waste material road base component which then is mixed with the aggregate to form a road base. As is apparent from FIG. 1A, the treatment step, step 2 removes water and also provides for recyclable or reusable material, such as clean mud and oil in step 2 A. Further, it is seen that step 3 , a step of mixing, may include not only the mixing of the aggregate with the treated oil and gas waste, but also mixing in other material such as binder, emulsion, etc., as set forth in more detail below. The result of the novel process is to provide a novel road base composition which is made up of treated oil and gas waste material and an aggregate and to apply such composition to a road base location.
[0035] Turning to FIG. 1, it is seen that, what is received from the oilfield site ( 32 ) at mixing site ( 16 ) is either tank liquids ( 30 A) or truck solids ( 30 B) sometimes called “cuttings”. We will call these materials collectively oil and gas waste material ( 10 A). Upon arrival at mixing site ( 16 ), tank liquids ( 30 A) may be deposited into a leak proof liquid storage tank ( 11 ). Truck solids ( 30 B), which have a more solid like consistency than the tank liquids ( 30 A), may be deposited on an impervious layer ( 19 ) and contained, typically, in an impervious earthen storage berm ( 13 ). FIG. 1 shows that tank liquids ( 30 A) and truck solids ( 30 B), collectively referred to as oil and gas waste material ( 10 A) is obtained from an oilfield site ( 32 ) including but not limited to drilling sites, pit clean-up sites, spill clean-up sites, blow-out sites and oil and gas exploration, pipelines and refining industry or production sites. Typically the oil and gas waste material ( 10 A) will be either “liquids” transported away from the oilfield site ( 32 ) in vacuum trucks or waste of a more “solid” or “slurry” consistency and transported in dump trucks. In both cases the transportation keeps the oil and gas waste separated from the environment and the trucks deposit their loads in means to isolate the material from the ground at the site. The oil and gas waste material ( 10 A) is transported from the oilfield site ( 32 ) to a mixing site ( 16 ) by a first transport such as by a vacuum truck for liquids (“tank liquids”) ( 30 A) or a second transport such as a dump truck for the “slurries” (“truck solids”) 30 B.
[0036] [0036]FIG. 1 illustrates the dry mixing method of treatment; truck solids ( 30 B) may be combined with soil ( 15 ) or other dry, absorptive indigenous material to help dry them and then stored on an impervious layer ( 19 ) as dried truck solids ( 17 ) in a storage pile ( 19 A) on an impervious layer ( 19 ). The mixing and storage is typically done on an impervious layer. The impervious layers disclosed herein may be man-made, as from concrete, plastic, steel, the road base material described herein or the like. Indeed, all of the storage and treatment of the oil and gas waste material ( 10 A) may take place in an enlarged enclosure the bottom of which has an impervious layer ( 19 ) and optionally, sides of which include a storage beam ( 13 ) made of either concrete or same other suitable material.
[0037] The next step in handling the oil and gas waste material ( 10 A) is to treat it to at least remove some of the liquids therefrom (typically oil and water) so as to prepare a treated oil and gas waste/road base component material ( 29 ) for mixing in the pug mill ( 18 ) to produce road base ( 20 ). Applicant provides a number of processes to treat the oil and gas waste material ( 10 A). These processes include “dry mixing” as illustrated in FIG. 1, “stacking” as illustrated in FIG. 2B and “mechanical separation” as illustrated in FIGS. 3 and 3A. FIG. 1 illustrates a treatment of oil and gas waste material 10 A.
[0038] Turning to FIGS. 2A-2D, Applicant's treatment by stacking is illustrated. In this preferred embodiment of treatment of oil and gas waste by way of a draining/evaporation process, the draining induced by gravity and the weight of the waste material itself is used along with a unique apparatus including a drainage assembly ( 60 ) to help remove oil and other liquids from either the truck solids ( 30 B) or a mixture of truck solids ( 30 B) and tank liquids ( 30 A). It is pointed out here that it is preferable that the oil and gas waste material ( 10 A) be treated to remove some of the liquids as it then makes the mixing of the road bed composition more effective. Typically, when the treated oil and gas waste material ( 10 A) is paint filter dry or thereabout, it is sufficiently dry or damp to be processed in the pug mill. Moreover, it is not necessary for all the fluids to be removed from the oil and gas waste material ( 10 A) which may in fact, be somewhat damp after treatment.
[0039] Turning back to FIG. 2A it is seen that the stacking step ( 28 A) includes a step of providing a drainage assembly ( 60 ) which includes a screened enclosure ( 62 ) typically three-sided and contained within the an impervious enclosure ( 64 ). More specifically, drainage assembly ( 60 ) is designed to contain within impervious enclosure ( 64 ) the screen enclosure ( 62 ) which is usually constructed from rigid frame member ( 62 A) consisting of angle iron welded or bolted together, which frame members secure screened walls ( 62 B), which screened walls may be made from a suitable screening material or expanded metal, with holes, typically in the range of sixty mesh to 1 inch. The screened enclosure ( 62 ) is located in an impervious enclosure ( 64 ), which impervious enclosure includes a bottom wall ( 64 A) and a side wall portion ( 64 B). It is seen that the dimensions of the screen enclosure ( 62 ) are such that there is a gap created between screened wall ( 62 B) and side wall ( 64 B) of the impervious enclosure ( 64 ). It is in the gap ( 65 ) created by the dimensions of the screened enclosure ( 62 ) and impervious enclosure ( 64 ) respectively, that drainings ( 71 ), that is liquids comprising typically oil or some water, collect. Within screened enclosure ( 62 ) and typically piled such that its vertical height exceeds the length or width of the screened enclosure ( 62 ) is stacked oil and gas waste ( 59 ) which is comprised of either truck solids ( 30 B) or a combination of truck solids ( 30 B) and tank liquids ( 30 A). Stacking the stacked oil and gas waste ( 59 ) in a manner so that is has a substantial vertical dimension (height) helps to ensure that there is sufficient weight to squeeze out drainings ( 71 ), which may be then evacuated either continuously or periodically from gap ( 65 ) through the use of a pumping or vacuum system ( 66 ). The pumping system includes pump ( 66 A) and an engaging tube or hose ( 66 B) or a vacuum hose attached to a vacuum truck (not shown). Tube or hose ( 66 B) has a first end for immersion in the drainings ( 71 ) and a removed end outside impervious enclosure for transporting drainings to a desired site for isolation into the mud tank for further processing. Pump ( 66 A) may be electric or hydraulic or any other suitable means and may be float controlled for it to be activated when draining ( 71 ) reaches sufficient depth within impervious enclosure ( 64 ).
[0040] An alternate preferred embodiment of Applicant's drainage assembly ( 60 ) there may be troughs or grooves ( 65 ) provided in the bottom wall ( 64 A) of impervious enclosure ( 64 ) to assist in the draining of the stacked oil and gas waste ( 59 ) (See FIG. 2B).
[0041] The drainage assembly ( 60 ) may be any size, but is preferably designed to contain from 1 yard to 300,000 yards of stacked oil and gas waste ( 59 ) which may be dumped into the screened enclosure ( 62 ) using a front end loader or by dump truck or vacuum truck. They may be left to allow for the draining anywhere from a day to ten days or longer depending upon how saturated they are at the beginning of the treatment process. They are then removed from the screened enclosure ( 62 ) by any suitable method such as an excavator, to insure that they remain isolated from the ground and are then typically ready for transport to the crusher or the pug mill for mixing.
[0042] [0042]FIGS. 2C and 2D represent a top elevation and a cutaway side view of an alternate preferred embodiment of Applicant's drainage assembly ( 80 ). This embodiment differs from the embodiment illustrated in FIGS. 2A and 2B in several respects. First, the stacked oil and gas waste ( 59 ) is enclosed in a three-sided or walled mesh enclosure ( 82 ). That is, drainage assembly ( 80 ) includes a three-walled mesh enclosure ( 82 ) that consists of a side wall ( 82 A), a back wall ( 82 B) and a second side wall ( 82 C), opposite side wall ( 82 A). The three-walled mesh enclosure has an open front ( 82 D). The mesh enclosure ( 82 ) lies within concrete retainer shell ( 86 ) or impervious layer and slightly spaced apart therefor to create a gap ( 65 ). Retainer shell ( 86 ), typically made from concrete and about three feet high, has typically three walls: side wall ( 86 A), back wall ( 86 B), second side wall ( 86 C), the second side wall being opposite the first side wall. The retainer shell has an open front ( 86 D) to allow dump trucks to back in and dump their load of oil and gas waste. A floor ( 86 E), typically concrete, is provided.
[0043] The retainer shell is typically about 100 feet by 100 feet with the back and two side walls about three feet high. Further, the floor is typically slanted a few degrees from horizontal dipping towards the back wall to allow liquids to drain to the back rather than out the open front.
[0044] Mesh or screen sections ( 84 ) typically come in 4-foot by 8-foot sections and can be laid lengthwise inside the side and back walls of the impervious enclosure spaced apart therefrom by the use of steel braces ( 88 ) set vertically on the floor and typically having a length of about four feet (representing the height of the 4′×8′ sections) which lay on the concrete floor. The braces will prevent the mesh or screen ( 84 ) from collapsing from the weight of the oil and gas waste material stacked against them and the braces provide for a gap ( 65 ), usually about six inches or so, from which a pump or vacuum system and related plumbing may be provided to remove liquids accumulating therein. It is seen that across the top of the beams joining a top perimeter of the wire or mesh section may be a closed top ( 90 ) typically with an access door ( 90 A). The function of the closed top is to prevent any oil and gas waste material stacked too high from falling over the top perimeter of the mesh section into the gap between the mesh section and the concrete wall. The access door may be opened to periodically insert a hose or pipe to evacuate accumulated liquids from gap ( 65 ). It is noted with reference to FIG. 2D that mesh typically stands a bit higher than the top of the three walls of the retainer shell. The space between the top of the impervious layer and the closed top ( 90 ) may be left open or closed with a suitable member. Closing that area would of coarse prevent accidental spillage of material into gap ( 65 ).
[0045] The material that accumulates in the gap is typically oil with some water and may be sent via pipe or truck, to the mud tank or used to add to clean mud. It further may be separated, having an oil component and a water component with the water component disposed of, and the oil component used to add to the clean mud.
[0046] As is illustrated in FIG. 2, the oil and gas waste treatment ( 28 ) may also treat the oil and gas waste ( 10 A) to remove a clean mud component ( 23 ), and a water component ( 25 ), yielding treated oil and gas waste/road base component material ( 29 ). Such treated oil and gas waste/road base component material ( 29 ) may then be combined with stone ( 42 ), “sized” stone ( 44 ), non-hazardous industrial waste ( 12 ), or “sized” non-hazardous industrial waste ( 37 ) or a combination of the preceding. These may be combined directly with the treated oil and gas waste/road base component material ( 29 ) in a pug mill ( 18 ) or other suitable mixer or may be combined on an impervious pad to form a pre-mix ( 31 ), which is then deposited into a pug mill ( 18 ) for further combining the two components together and for adding other components, such as portland cement ( 22 ) and a binder such as asphalt emulsion ( 24 ) to yield, upon curing, the stabilized road base ( 20 ) (water may be added as necessary).
[0047] The second of the two primary components of the stabilized road base ( 20 ) is an aggregate component ( 61 ) which is collectively either stone ( 42 ) (naturally occurring) and/or non-hazardous industrial waste ( 12 ). This non-hazardous industrial waste ( 12 ) typically consists of inert aggregate material, like broken up brick or cinderblock, broken stone, concrete, cement, building blocks, road way, and the non-metallic and non-organic waste from construction and demolitions site.
[0048] Non-hazardous waste ( 12 ) can be obtained from many sources and have many compositions. It includes waste brick materials from manufacturers, waste cement or other aggregate solid debris of other aggregate from construction sites, and used cement and, cement and brick from building or highway demolition sites.
[0049] Aggregate sites ( 34 ) include construction sites, building and highway demolition sites and brick and cement block manufacturing plants quarries, sand, dirt, or overburden or caliche pits. The aggregate is transported by dump trucks or the like to mixing site ( 16 ) where it may be separated down to a smaller size, that is, into aggregate particles typically less than 1½″ in diameter by running them through a screen ( 33 ). Any material that is left on top of the screen may go to a crusher ( 35 ). That material may go back to the screen ( 33 ) until, falling through the bottom of the screen and measuring less than about 1½″ in size. This will result in what is referred to as “sized” aggregate ( 30 ). This sized aggregate ( 30 ) is the aggregate component of the stabilized road base ( 20 ). It may then be combined with the treated oil and gas waste/road base component material ( 29 ) in a pre-mix ( 31 ) as by using backhoes or loaders to scoop treated oil and gas waste/road base component material ( 29 ) to physically mix with sized aggregate ( 30 ) (or unsized aggregate) to create a pile or batch of pre-mix ( 31 ), which then can be added to the pug mill ( 18 ). Optionally, this premix ( 31 ), if it has sufficient dampness from residual oil and moisture, may be combined with sufficient portland cement ( 22 ) to coat the particles, before putting it into the pug mill ( 18 ). As set forth above, treated oil and gas waste/road base component material ( 29 ) may be deposited directly into the pug mill ( 18 ) and sized aggregate ( 30 ) can be separately dumped into the pug mill ( 18 ) and the material mixed directly without a pre-mix ( 31 ). Note that portland cement ( 22 ) and asphalt emulsion ( 24 ) may also be added to the pug mill ( 18 ) while the two primary components, treated oil and gas waste/road base component material ( 29 ) and aggregate are being mixed. Typically, the treated oil and gas waste/road base component material ( 29 ) and aggregate ( 30 ) are mixed in a ratio of about 50/50, but may be between 20/80 and 80/20. After the material is thoroughly mixed in the pug mill ( 18 ), it is deposited on the ground and may be contained by an impervious berm ( 13 ) on a impervious layer ( 19 ) for curing (typically for about 48 hours). At this point, leach testing ( 40 ) can also be performed to determine whether or not the ratios of any of the materials need to be adjusted. Leach testing is usually done at a lab to ensure that materials from the road base do not leach into the ground.
[0050] The oil and gas waste material ( 10 A) is comprised of hazardous and non-hazardous hydrocarbon based discarded material by oil and gas exploration production, transportation, and refining industries. Oil and gas waste material may include water base drilling fluid, drill cuttings, waste material from produced water collecting pits, produced formation sand, oil based drilling mud and associated drill cuttings, soil impacted by crude oil, dehydrated drilling mud, oil, pipelines and refining industries and like waste materials. It may be “dried” while isolated from the ground, by one or more of the novel drying processes disclosed herein. The term oil and gas waste material as used herein is not intended to be limited by definitions found in various codes or statutes.
[0051] Typically the oil and gas waste material ( 10 A) contains enough liquids such that the aggregate ( 61 ) will likely become saturated if a mix is prepared without removal of some liquids. Therefore, the oil and gas waste treatment ( 28 ) of the tank liquids ( 30 A) or truck solids ( 30 B) is usually required. Oil and gas waste treatment ( 28 ) may also be used when clean mud is desired, since clean mud is often readily saleable. The oil and gas waste treatment ( 28 ) results in the production of clean oil and gas waste/road base component material ( 29 ) from the oil and gas waste material ( 10 A).
[0052] The term “dry” is relative and means less liquid than before oil and gas waste treatment ( 28 ), typically, resulting in the loss of sufficient liquid such that mixing with the aggregate ( 61 ) will not result in saturation of the combination. If an oil and gas waste treatment ( 28 ) is used, then the treated oil and gas waste/road base component material ( 29 ) are mixed with the aggregate ( 61 ) and portland cement ( 22 ) and emulsion ( 24 ) in a ratio that results in a stabilized product. That ratio is determined by testing leachability of the roadbase for Benzene and RCRA metals; also for strength by testing for compressive strength and vheem stability, pH and chlorides. The ratio may be between 20/80 and 80/20, typically about 50/50. Whether oil and gas waste material ( 10 A) is mixed with aggregate ( 61 ) directly in a dry mix ( 17 ), or if oil and gas waste ( 10 A) is subjected to oil and gas waste mechanical or stacking treatment and treated oil and gas waste/road base component material ( 29 ) are mixed with aggregate ( 61 ), an oil/aggregate mix ( 14 ) results from by the combination.
[0053] Typically, aggregate ( 61 ) is optimally sized to ¾/inch to 1{fraction (1/2)} inch diameter pieces but may include a substantial portion smaller than ¾″. Therefore, a determination of desired size is made and, if the aggregate waste is in pieces that are determined to be too large, they may be crushed in a crushing process ( 35 ) such as by a jaw crusher, to obtain the desired size prior to being added to the treated oil and gas waste/road base component material ( 29 ).
[0054] It has been found that a pug mill ( 18 ) provides adequate characteristics for proper mixing. The characteristics of a good mixer are consistency, coatability and durability. An emulsion ( 24 ) is added to the oil/aggregate waste mix ( 14 ) in the pug mill ( 18 ). The emulsion ( 24 ) serves to hold or bind the treated oil and gas waste/road base component material ( 29 ) to the aggregate waste ( 12 ) when the components are mixed and cured. The stabilizer ( 22 ) is, typically, comprised of portland cement. A binder ( 24 ) is also provided, typically asphalt emulsion. While the portland cement and asphalt emulsion can be added in desired quantities, it has been found that portland cement added in range of ½-10% of the final product weight and asphalt emulsion added in range of ½-10% of the final product weight provides good characteristics for the finished product. The oil/aggregate waste mix ( 14 ), binder ( 24 ), and stabilizer ( 22 ) are mixed and cured and the final product, stabilized road base ( 20 ) as determined by compressive strength testing and leachate testing results. Portland cement and asphalt emulsion are added to the waste mix ( 14 ) and mixed into the pug mill ( 18 ) or may be added separately to the pug mill ( 18 ). Optionally, treated oil and gas waste/road base component material ( 29 ) which is sometimes damp, may be coated with portland cement before it goes into the pug mill ( 18 ). The pug mill mixing ( 18 ) is a cold batch process.
[0055] More details of Applicant's oil and gas waste material treatment ( 28 ) are provided for in FIGS. 3 and 3A. It will first be noted that one of the purposes of treating oil and gas waste material ( 10 A) may be to derive from it clean mud ( 23 ) which can be sold to oil and gas operators. Secondly, water is taken out of the oil and gas waste materials to be reinjected or otherwise disposed of Finally, the majority of the oil and gas waste material ( 10 A), upon treatment, will result in treated oil and gas waste/road base component material ( 29 ), that is, oil and gas waste material ( 10 A) from which at least some liquids have been removed.
[0056] Turning now to FIGS. 3 and 3A, it is seen that tank liquids ( 30 A) and tank solids ( 30 B) may be treated differently to achieve the removal of a liquid component and for the purposes of obtaining clean mud. Turning to FIG. 3A, it is seen that tank liquids ( 30 A) are typically stored in tank liquid storage ( 11 ) from which they may be piped to and deposited on the top of a fine shaker ( 41 ) which will typically remove off the top thereof a damp solids component ( 63 ). However, a substantial portion of the tank liquids ( 30 A) will work through the fine shaker ( 41 ) into a mud tank ( 43 ) typically located just below the fine shaker ( 41 ). From the mud tank, the fluid will enter a centrifuge ( 46 ) which will separate out another damp solids component ( 65 ) and send a fluid component to a 3 phase centrifuge ( 51 ). From the 3 phase centrifuge will come an additional damp solids component ( 67 ), clean mud ( 23 ) and water ( 25 ).
[0057] Turning now to the truck solids ( 30 B), they may be stored, isolated “unmixed” ( 16 ) or in a storage pile of dried truck solids ( 17 ) (see FIG. 1) on an impervious layer. Either way, truck solids ( 30 B) may be deposited, typically using a backhoe (or front loader) and a hopper and a conveyor belt onto a coarse shaker ( 45 ) off the top of which come particles which will be a coarse component ( 69 ). The coarse component is further treated by crushing. Much of the truck solids ( 30 B) will, however, fall through the coarse shaker ( 45 ) and these are transported or dropped into a centrifugal drier ( 47 ). The centrifugal drier ( 47 ) will yield a treated oil and gas waste/road base component material ( 29 C) and a liquid portion ( 49 ) which will be transported to mud tank ( 43 ) (see FIG. 3A for processing).
[0058] The coarse component ( 69 ) comes off the top of the shaker and typically includes large chucks of stone or rock which may be transported to the crusher. Occasionally, rags, wood, cans and other extraneous material may be found in this coarse component. This extraneous material may be isolated, transported and disposed of offsite in permitted landfills. It is noted that the crusher operation is typically isolated from the ground if it contains a portion of the coarse component to prevent contamination of the environment.
[0059] Thus it is seen that both tank liquids ( 30 A) and truck solids ( 30 B) coming from oil and gas waste material sites ( 32 ) will undergo some physical separation of some solids from liquids, the liquid portion of which will typically end up in mud tank ( 43 ). Following separation of liquids both resulting components remain isolated. The liquids in mud tank ( 43 ) will undergo a process that yields a treated oil and gas waste material/road base component material ( 29 ) and also clean mud ( 23 ) and water ( 25 ).
[0060] Novelty is achieved in taking oil and gas waste material including tank liquids and truck solids and making a road base that meets industry standards and is environmentally safe. However, treatment is done at a remote site while isolating the oil and gas waste before and during treatment From the solids a liquid is extracted by stacking, dry mixing or mechanical separation. From the tank liquids a solid portion and a clean mud portion and water is produced (see FIGS. 3 and 3A). Depending on weather, type of or source of waste material, extent of drying desired, economic consideration, environmental consideration may dictate which of the three separation types, or combination of the three types will be used.
[0061] The oil and gas waste material that is treated according to Applicant's present invention usually contains a solid phase and a liquid phase. It is Applicant's novel methods of treatment that help remove a part of the liquid phase. The following areas list of some of the oil and gas waste material that may be subject to Applicant's novel treatment and use and Applicant's novel roadbase:
[0062] Drilling fluids and cuttings from onshore operations
[0063] Basic sediment and water (BS&W) and tank bottoms;
[0064] Condensate;
[0065] Deposits removed from piping and equipment prior to transportation (i.e., pipe scale hydrocarbon solids, hydrates and other deposits);
[0066] Drilling fluids and cuttings from offshore operations disposed of onshore;
[0067] Liquid and sludge;
[0068] Liquid and solid wastes generated by crude oil and tank bottom reclaimers;
[0069] Weathered oil;
[0070] Pigging wastes from producer operated gathering lines;
[0071] Pit sledges and contaminated bottoms from storage or disposal of exempt wastes;
[0072] Produced sand;
[0073] Produced water constituents removed before disposal (injection or other disposal);
[0074] Slop oil (waste crude oil from primary field operations and production);
[0075] Crude oil contaminated soil;
[0076] Work over wastes (i.e., blowdown, swabbing and bailing wastes);
[0077] Waste in transportation pipeline related pits;
[0078] Cement slurry returns from the well and cement cuttings;
[0079] Produced water—contaminated soils.
[0080] Trucks solids or tank liquids or any other oil and gas waste material may be transported to Applicant's novel treatment site ( 21 ) via a boat or a barge, if the site is built next to water. If not, barges and boats that carry oil and gas waste material from offshore operations may be bring such material to a dock for offloading onto tanks or trucks for transportation to the treatment site ( 21 ). Boats typically transport oil and gas waste from an offshore drilling operations isolated and large containers. Barges typically carry the oil and gas waste material in bulk.
[0081] It is noted throughout the figures that at each point in the storage and treatment of the oil and gas waste material and the components derive from it, there is isolation, as by a man made or natural impervious layer ( 19 ). Indeed, treatment also occurs in isolation from the environment-as for example by mixing and/or curing on an imperious layer. Further, it is noted that Applicant's provide a novel treatment site ( 21 ) which itself may be surrounded by a berm ( 13 ) such an earthen berm or an impervious berm and may also include an impervious floor. The impervious floor may be natural material such as clay or packed dirt or compacted soil or may be a man made material, such a heavy plastic or concrete. The novel treatment site ( 21 ) is underlain by an impervious layer and bermed so that incoming oil and gas waste material, which often contains an environmentally unsafe compositions, will be treated and stored in isolation and will leave the treatment site in an nonhazardous and safe form-as environmentally safe roadbase, clean mud for use in further drilling operations and water, for injection offsite.
[0082] 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. | The present invention provides a novel method to produce grade road base material using recycled oilfield waste, called “oil and gas waste,” and aggregate waste and a novel road base material. Hydration and mixing of the waste materials along with a binder, will achieve an irreversible pozzolanic chemical reaction necessary for stabilization into a road base. An asphalt emulsifier may be included in the binder to manufacture asphalt stabilized road base. The entire method is a cold batch process. | 4 |
FIELD OF THE INVENTION
The present invention relates to an electrophotographic printer.
DESCRIPTION OF THE RELATED ART
FIG. 11 illustrates a conventional electrophotographic printer that performs the steps of charging, exposing, developing, transferring, and fixing. A charging unit 51 uniformly chargers a surface of a photoconductive drum 12. An exposing unit 55 illuminates the charged surface of the photoconductive drum 12 to form an electrostatic latent image. The electrostatic latent image is developed with toner by a developing roller 52 into a toner image. Then, the toner image is transferred to a recording medium. The toner image is subsequently fixed by a fixing unit 56. Arrows A show various, possible paths of the recording medium when it travels from the image forming unit 11 to the fixing unit 56.
The fixing unit 56 includes a heat roller 14 and a pressure roller 22. The heat roller 14 incorporates a halogen lamp 15 therein and rotates in pressure contact with the pressure roller 22. A separator tongue 17 is disposed downstream of the fixing unit 56 with respect to the direction of travel of the recording medium. The separator tongue 17 engages the surface of the heat roller 14 to separate the recording medium from the surface of the heat roller 22.
The pressure roller 22 is rotatably supported at longitudinal ends thereof by bearings 23. There is provided a spring 24 between the bearing 23 and the frame 21 and the spring 24 urges the pressure roller 22 against the heat roller 14. The recording medium having a toner image transferred thereto is pulled in between the heat roller 14 and the pressure roller 22. Then, the toner image is heated into a fixed image under a pressure applied by the pressure roller 22.
FIG. 12 illustrates the possible paths of a recording medium when printing on a curved recording medium.
When printing on an inwardly curved (i.e., toward the guide 21a) surface of a recording medium, the leading end of the recording medium will not slide on the guide 21a. As a result, the leading end of the recording medium will not be properly fed between the heat roller 14 and the pressure roller 22, but abuts, for example, the frame 21b. Such an improper feed of the recording medium causes the toner image on the recording medium to be scratched, and causes the recording medium to be folded or jammed.
Occasionally, a printing is performed on one side of a recording medium and subsequently on the other side. A recording medium is inwardly curved or outwardly (i.e., away from the guide 21a) curved after a toner image has been fixed thereto, depending on the type of the recording medium. If a subsequent printing is performed on an outwardly curved surface (i.e., a previously printed image is on an inwardly curved surface), the recording medium is allowed to travel with its leading end sliding on the guide 21a as depicted by arrow A of FIG. 11. However, if the subsequent printing is performed on an inwardly curved surface, the recording medium will turn up as shown by arrows C of FIG. 12, with the result that the recording medium is not allowed to travel with its leading end sliding on the guide 21a. As a result, the toner image before fixing may be rubbed by surroundings, resulting in deteriorated image quality, folded recording medium, or jamming of recording medium.
SUMMARY OF THE INVENTION
The present invention was made to solve the aforementioned drawbacks of the conventional medium-transporting device.
An object of the present invention is to provide an electrophotographic printer that is free from problems such as a poor image quality and the folding and jamming of recording medium.
A transferring section transfers a toner image from a photoconductive drum to a recording medium. The recording medium is guided by a guide member disposed between the transferring section and the fixing section. The recording medium is then fed to a fixing section which in turn fixes the toner image on the recording medium. The guide member having an upstream end and a downstream end with respect to a direction of travel of the recording medium. The guide member has opposed surfaces between which the recording medium is guided toward the fixing section.
The guide member has a plurality of ribs formed at intervals and aligned in a direction transverse to the direction of travel of the recording medium. The ribs extend substantially in a direction from the upstream end to the downstream end and are increasingly high from the surface of the guide as the downstream end is approached.
The ribs may extend progressively outwardly as the downstream end is approached.
The opposed surfaces include an upper surface and a lower surface that define a path therebetween in which the recording medium passes to the fixing section. The upper surface is supported so that the upper surface is allowed to pivot about an axis perpendicular to the direction of travel of the recording medium.
A voltage of the same polarity as the toner image may be applied to the guide member.
Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention, and wherein:
FIG. 1 illustrates the path of a recording medium according to a first embodiment;
FIG. 2 is an enlarged side view of a guide assembled to a frame;
FIG. 3 illustrates the guide surface of a guide according to a second embodiment;
FIG. 4 is a side view of the guide of FIG. 3 as seen in a direction shown by arrow S of FIG. 3;
FIG. 5 illustrates the guide surface of a guide according to a third embodiment;
FIG. 6 is a side view of the guide of FIG. 5 as seen in a direction shown by arrow S of FIG. 5;
FIG. 7 is a perspective view of a curved recording medium which is about to enter a fixing unit;
FIG. 8 illustrates a guide according to a fourth embodiment, the guide being at an operative position;
FIG. 9 illustrates the guide of FIG. 8 at a non-operative position;
FIG. 10 illustrates an electrophotographic printer according to a fifth embodiment.
FIG. 11 illustrates a conventional electrophotographic printer; and
FIG. 12 illustrates various, possible paths of a recording medium in the conventional electrophotographic printer when printing on a curved recording medium.
DESCRIPTION OF THE INVENTION
Preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Elements of the same construction have been given the same reference numerals throughout the embodiments and the description thereof is omitted.
First Embodiment
<Construction>
FIG. 1 illustrates the path of a recording medium according to a first embodiment.
Referring to FIGS. 1, an image forming unit 11 is detachably mounted on a frame 21 of an electrophotographic printer. The image forming unit 11 includes a photoconductive drum 12 rotatably mounted and driven in rotation by a drive source, not shown. A charging roller 51, developing roller 52 and cleaning roller 54 are disposed such that they rotate in contact with the photoconductive drum 12. The developing roller 52 is rotatably assembled in contact with a toner-supplying roller 53.
Rotatably disposed under the image forming unit 11 is a transfer roller 13 in contact with the photoconductive drum 12. The photoconductive drum 12 has a drum gear, not shown, mounted to one longitudinal end thereof. The drum gear is in mesh with a transfer roller gear, not shown, so that the photoconductive drum 12 operatively rotates together with the transfer roller 13. Disposed above the image forming unit 11 is an exposing unit 55 such as an LED head.
The charging roller 51 uniformly charges the surface of the photoconductive drum 12, and the exposing unit 55 illuminates the charged surface in accordance with print data to form an electrostatic latent image on the photoconductive drum 12. The latent image is developed into a toner image by the developing roller 52. The toner image is then transferred to a recording medium such as paper, not shown, by the transfer roller 13.
Arrows B show various, possible paths of the recording medium. The recording medium having the toner image transferred thereto is advanced to the fixing unit 56 which in turn fixes the toner image into a permanent print.
The fixing unit 56 will now be described.
The fixing unit 56 includes a heat roller 14 rotatably supported by a wall 16, and a pressure roller 22 rotatably supported in pressure contact with the heat roller 14. The heat roller 14 incorporates a halogen lamp 15 therein. The heat roller 14 and pressure roller 22 are accommodated in a fixing unit frame 21b. The fixing unit frame 21b is secured to a main frame, not shown, by bolts.
The pressure roller 22 is rotatably supported at both longitudinal ends thereof by bearings 23. Springs 24 are disposed between the bearings 23 and the frame 21 so as to urge the pressure roller 22 against the heat roller 14. The recording medium having the toner image transferred thereon is pulled in between the heat roller 14 and pressure roller 22. The toner is fused by the heat roller 14 and pressed by the pressure roller 22 against the recording medium.
The toner image transferred to the recording medium adheres to the recording medium only by the Coulomb force and the adhesion of the toner image is very weak. Therefore, the elements of the image forming unit 11 are carefully arranged not to scratch or rub the toner image on the recording medium. The recording medium, discharged from between the photoconductive drum 12 and transfer roller 13, is advanced with a leading end thereof rubbing a guide 21a that extends between the image forming unit 11 and the fixing unit 56.
FIG. 2 is an enlarged side view of a guide 25 assembled to the frame.
One side of the guide 25 is a flat surface S1 that faces the recording medium and the other side of the guide 25 has L shaped projections 25a (FIG. 2). The guide 25 is attached to an underside of the frame 21b with the flat surface S1 facing the guide 21a. The frame 21b is formed with holes 21c therein, through which the L shaped projections 25a of the frame 21b extend upon assembling the guide 25 to the frame 21b.
With the surface S1 facing the path R of the recording medium, the guide 25 is first placed on the frame 21b so that the projections 25a are inserted into the holes 21c. Then, the guide 25 is moved in a direction shown by arrow A till the projections 25a engage the edges defining the holes 21c, thereby firmly assembling the guide 25 to the frame 21b. The frame 21b is formed with a rib 21d thereon so that when the guide 25 is moved in the direction shown by arrow A, the rib 21d engages the end of the guide 25. In other words, the rib 21d serves to prevent pullout of the guide 25.
Once the guide 25 has been mounted to the frame 21b, the guide 25 extends horizontally between the image forming unit 11 and the fixing unit 56. Thus, even if the recording medium is curved upward after the toner image has been transferred to the upper surface of the recording medium, the leading end of the recording medium slides on the surface S1. The leading end of the recording medium is guided by the surface S1 and smoothly pulled in between the heat roller 14 and the pressure roller 22. Transporting the recording medium in this manner prevents the toner image on the recording medium from being scratched or rubbed by the surroundings, thereby preventing deterioration of image quality. Additional advantage is that the recording medium is prevented from being bent or being jammed.
In order to minimize the frictional resistance exerted on the leading end of the recording medium when the recording medium slides on the surface of the surface S1, the surface S1 is coated with a fluoroplastics. Alternatively, the entire guide 25 may be made of fluoroplastics.
Second embodiment
FIG. 3 illustrates the guide surface of a guide according to a second embodiment.
FIG. 4 is a side view of the guide of FIG. 3 as seen in a direction shown by arrow S.
The guide 25 is formed with a plurality of ribs 61 thereon which are aligned in a direction transverse to the direction (arrow B) of travel of the recording medium. Each of the ribs 61. extends in directions parallel to the direction of travel of the recording medium. The ribs extend from an upstream end 25c to a downstream end 25d. The ribs 61 are increasingly high from the surface of the guide 25 as the downstream end 25d of the guide 25 with respect to the direction shown by arrow B is approached.
Therefore, if the recording medium is curved upward after a toner image has been transferred to the upper surface of the recording medium, the ribs 61 guide the leading end of the recording medium with least frictional resistance. As a result, the recording medium can be smoothly fed to the fixing unit 56 (FIG. 1).
Third embodiment
FIG. 5 illustrates the guide surface of a guide according to a third embodiment.
FIG. 6 is a side view of the guide according to the third embodiment as seen in a direction shown by arrow T of FIG. 5.
FIG. 7 is a perspective view of a curved recording medium which is about to enter a fixing unit.
The guide 25 is provided with a plurality of ribs 62 formed thereon. The ribs 62 are aligned in a direction transverse to the direction (arrow B) of travel of the recording medium P. The ribs 62 extend substantially in the direction of travel of the recording medium. As the downstream end of the recording medium with respect to the direction of the recording medium P is approached, the ribs 62 are progressively close to lateral edges 25e of the guide 25 and are increasingly high from the surface of the guide 25.
As shown in FIG. 9, if the recording medium P is curved such that four corners P1-P4 of the recording medium P are warped upward after a toner image has been transferred to the upper surface of the recording medium P, the ribs 62 guide the leading end e1 of the recording medium P, straightening the widthwise curve of the recording medium P as well as minimizing the frictional resistance to which the recording medium is subjected. As a result, the recording medium P can be smoothly fed to the fixing unit 56.
Fourth embodiment
FIG. 8 illustrates a guide according to a fourth embodiment at an operative position.
FIG. 9 illustrates the guide at a non-operative position.
A guide 31 is pivotally mounted to a lower end of a frame 21b to oppose a guide 21a. The guide 31 is switched between an operative position and non-operative position. The guide 31 has posts 31a located at an upstream end of the guide 31 with respect to the direction of travel of the recording medium. The posts 31a are aligned in a direction transverse to the direction of travel of the recording medium and positioned at opposed lateral ends of the path of the recording medium. The posts 31a extend through holes, not shown, formed in the frame 21 so that the guide 31 is pivotally supported. A spring 32 is mounted between the frame 21.b and a substantial middle of the guide 31 and urges the guide 31 upwardly. The guide 31 has posts 31b formed at a downstream end thereof with respect to the direction of travel of the recording medium. The guide 31 is coupled through a solenoid lever 33 to a solenoid 34.
When the leading end of the recording medium passes between the photoconductive drum 12 and transfer roller 13, the solenoid 34 is energized so that the guide 31 pivots clockwise to the operative position as shown in FIG. 8. Subsequently, the leading end of the recording medium is guided by the guide 31 in a direction shown by arrow D. When the leading end of the recording medium enters between the heat roller 14 and the pressure roller 22, the solenoid 34 is deenergized. Then, the urging force of the spring 32 causes the guide 31 to pivot counterclockwise to the non-operative position as shown in FIG. 9.
When the guide 31 is at the operative position, the guide 31 smoothly guides the recording medium to the fixing unit 56. When the guide 31 is at the non-operative position, the gap between the guide 31 and the recording medium is wide open so that the toner image is not rubbed by the surroundings before the recording medium reaches the fixing unit. The recording medium travels in a direction shown by arrow E. In this manner, the image quality is maintained. The guide 31 is positioned at the non-operative position when an outwardly curved recording medium is printed, and at the operative position when an inwardly curved recording medium is printed.
Fifth embodiment
FIG. 10 illustrates an electrophotographic printer according to a fifth embodiment.
A guide 35 is formed of an electrically conductive material and has projections 35a that engage holes 21c just as in the first embodiment. The guide 35 is connected to a power supply 36 and receives from the power supply 36 a voltage of the same polarity as the charged toner image transferred to the recording medium, not shown. The recording medium travels in a direction shown by arrow F.
The power supply 36 continues to apply the voltage to the guide 35 from the time the leading end of the recording medium passes between the photoconductive drum 12 and the transfer roller 13 until the leading end of the recording medium enters between the heat roller 14 and the pressure roller 22. Since the toner image TN and the voltage applied to the guide 35 are of the same polarity, charges CR stored on the guide 35 repel those of the toner image. The repellent force between the guide 35 and the toner image TN suppresses the curving of the recording medium, facilitating feeding of the recording medium to the fixing unit 56 after transferring operation as well as preventing the toner image before fixing from being damaged.
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 as would be obvious to one skilled in the art intended to be included within the scope of the following claims. | A guide member is disposed between a transferring section and a fixing section. The guide member has an upstream end and a downstream end with respect to the direction of travel of the recording medium. First and second guide members define a path therebetween in which the recording medium passes to the fixing section. The first guide member is formed with a plurality of ribs formed at intervals and aligned in a direction either transverse or parallel to the direction of travel of the recording medium. The ribs extend substantially from the upstream end to the downstream end and increase in height from the surface of each guide as the downstream end is approached and guide a leading end of the recording medium. The ribs may extent progressively outwardly as the downstream end is approached. The first guide member is supported so that it is pivotal on an axis perpendicular to the direction of travel of the recording medium. The first guide member can be moved between an operative and a non-operative position. The first guide member can receive a voltage of the same polarity as the toner image. | 6 |
BACKGROUND OF THE INVENTION
This invention relates to a floor and bounded surface sweeper machine, in particular of the type usually employed to sweep indoor surfaces clean such as the floor areas of workshops and warehouses, as well as such outdoor surfaces as parking areas, courtyards, and no-traffic areas.
Such sweepers usually comprise, as is known, a wheel-mounted frame supporting at the top steering devices and drive members, and at the bottom a cylindrical brush having its axis parallel to the surface to be swept and at least one substantially upstanding frustoconical brush.
With the frame there is also engaged a container adapted to collect trash and dirt being swept, and located adjacent the cylindrical brush to which it presents a loading mouth. The container is also usually provided with a suction mouth facing a suction assembly of the machine which cooperates to deliver the swept trash to the container, and which filters out dust.
Whereas large size sweepers, designed for street sweeping, usually have said trash container lifted and shifted by specially provided hydraulic members operated directly from the driver's station, with the sweepers for floors and bounded surfaces, forming the subject matter of this patent, the subject container must be handled manually by an operator.
In particular, the container should be inserted in an empty state and then removed at least each time that it is substantially filled. For insertion it must be lifted by hand and then locked accurately and sealingly against a special seating provided below the frame. For removal the container must be taken off without sharp blows or sudden falls from the working level, to avoid spreading dust and trash.
Moreover, it is observed that if the container is located improperly on the machine, there may occur unacceptable spreading over the ground of the trash being conveyed by the cylindrical brush, as well as interference with the operation of the cited suction assembly, in communication with the container through a suction mouth of the latter.
This situation and the fact that the subject container is usually handled by unskilled personnel often wearing hand protecting gloves have in practice dictated in this type machines, heretofore, that said container be located at the forward end or the rear end of the sweeper. Selection of the forward or rear part of the machine depends on the path which the swept products are made to follow.
At these positions the container is in full view and easily accessed to, and hence easier to grip and handle by hand, as well as easier to check with respect to its location accuracy.
The state of the art provides, to enable manual insertion and withdrawal of the container, such first means as for example rigid chest-type guides, for positioning the container, and such second means as for example handles, handgrips, and the like for lifting the container up to the guides.
In any case the operator is required to operate at successive times means for lifting or lowering the container and means of inserting or withdrawing same, level with the working plane. The container locking and releasing operations are thus comparatively inconvenient and time-consuming, despite the cited accessibility to the container.
These drawbacks are of considerable practical moment, given that handling and precision positioning of the container is one of the most important tasks of an operator with this machine type. Positioning the container at the forward or rear ends of these machines not only fails to satisfactorily solve said problems of container handling but also gives rise to a serious drawback: the container interferes with the wheels, thus conditioning their location. Where the container is provided, moreover, it is impossible to provide a single central steering wheel.
SUMMARY OF THE INVENTION
The technical aim underlying this invention is therefore to provide a sweeper machine which can obviate said drawbacks and make the operation of inserting and withdrawing said containers easy to carry out, direct, and accurate, even where the containers are handled by unskilled operators.
Within said technical aim it is an object of the invention to provide a machine wherein said container can be handled in a convenient and accurate manner even when it is inserted at a distance from the forward and rear ends of the machine, so as not to interfere with the wheels.
Another object of the invention is to provide a sweeper machine of simple construction which is easily manufactured at low costs by the pertinent industry.
The outlined technical aim and the objects set forth are substantially achieved by a floor and bounded surface sweeper machine, of a type which comprises at least one supporting frame, rest wheels for said frame, a cylindrical brush having its axis substantially parallel to a surface to be swept and carried on said frame at a position across the longitudinal axis of the machine, and a storage container for swept trash engaged removably with said frame and having a loading mouth adjacent said cylindrical brush, characterized in that it comprises, for engaging said container with said frame, pivotally mounted guides located at a central region of said frame and extending lateral to the longitudinal axis of the machine, swivel members engaging pivotally said guides with said frame and defining a transverse pivot axis to said guides parallel to said longitudinal axis, hook-up elements provided between said frame and said guides, set apart from said swivel members and adapted to hold said guides at a raised position close against said frame, and pusher members projecting from said frame and acting by spring bias on said container in a substantially parallel direction to said guides, on said container being at least for a major part inserted on said guides and the same are at least close to said raised position.
BRIEF DESCRIPTION OF THE DRAWINGS
Further features and advantages will be apparent from the description of a preferred embodiment of the invention, as shown in the accompanying drawings, where:
FIG. 1 is a schematical side view of the sweeper machine;
FIG. 2 is a fragmentary view of FIG. 1 which shows, to an enlarged scale, that machine area which is engaged by the collecting container, with the latter in the raised position;
FIG. 3 is a view similar to the previous one but with the container in the lowered position; and
FIGS. 4 and 5 bring out the sections IV--IV and V--V respectively of FIG. 2 and FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENT
With reference to the cited figures, the sweeper machine comprises a wheel-mounted frame 1: in particular mounted on two rear drive wheels 2 and on a central forward steering wheel 3.
Above the frame 1 there are provided steering devices 4 and control devices 5, known per se. The control devices 5 are housed inside a shroud which extends from the frame 1 and comprise a suction assembly 5a.
The frame 1 supports a plurality of rotatable brushes. In particular on the right-hand side forward part of the frame 1, relatively to an operator at the driver's station, there is provided a conical brush 6 having its axis set obliquely relatively close to the vertical direction, adjustable in height over the ground and power driven. Below the middle part of the frame 1 there is provided a cylindrical brush 7 lying across the forward travel direction and the machine longitudinal axis and having its axis substantially parallel to the surface 8 to be swept. The cylindrical brush 7 is also adjustable in height and power driven, and is rotated in the opposite direction to the direction of rotation of the wheels.
In practice this brush 7 picks up dirt from the surface 8 and throws it toward a loading mouth 9a.
Forwardly of the cylindrical brush 7 there is provided a container or bin 9 for collecting the swept trash which comprises, inter alia, the cited loading mouth 9a, a flexible band 10 attached to the bottom edge of the loading mouth 9a, and a suction mouth 9b provided on the top end of the container 9 itself and being adapted to communicate with a suction and filtering chamber being part of the cited suction assembly 5a (FIGS. 4 and 5).
FIG. 5 shows that the container 9 is equipped with four small idler wheels 11 and a big handle 12 for handling and inserting or removing the container 9 into/from a small supporting frame 13.
On the side engaged with the handle 12, the container 9 has a height extension 9c forming a lip along one side of container 9.
The handle 12 is extended above the suction mouth 9b and the frame 13 is configured like a picture frame having the shape of the suction mouth 9b.
The frame 13 comprises two pivotally mounted guides 14 extending across the direction of forward travel of the machine and being fashioned channel-like with parallel facing grooves. There are closed ends 14a and open ends 14b, opposite the closed ones, in the guides 14. Through the open ends 14b, two brackets, with substantially horizontal extending surfaces 17, projecting from the top of the container 9 are inserted and withdrawn.
The guides 14 are connected by first and second dihedral members 15 and 16 of substantially squared shape. The first member 15 connects between the closed ends 14a and the second member 16 connects between the open ends 14b and is on the side where the handle 12 is located.
The first member 15 is engaged by swivel members embodied by at least one hinge 18 connected by a swivel member to the frame 1. The hinge 18 defines a pivot axis transverse to the pivotally mounted guides 14 and parallel to the longitudinal axis of the machine, and allows the guides 14 to pivot between a raised position close against the frame 1 (FIG. 4) and a lowered position toward said surface 8. The hinge 18 includes limiting elements adapted to fix the maximum possible pivoting movement of the frame 13.
Furthermore, the first member 15 has its dihedral angle facing downwards and facing inward toward the middle longitudinal portion of the frame 1, thereby its depending side functions as an end closure for the guides 14 and as a stop to the slipping in of the container 9.
The second member 16 is oriented in the opposite direction to member 15 and secured above the guides 14, purposely to permit slipping in and withdrawing the brackets with extending surfaces 17 through the open ends 14b of the guides themselves.
The second member 16 abuts on the extension 9c of the container 9, when the opposite side of container 9 pushes against the first member 15, and member 16 is engaged with hook-up elements connecting it to the frame 1 and adapted to support the guides 14 in the raised position. These hook-up elements are advantageously embodied, in the embodiment form shown, by a snap-action mechanism.
The upward extending side of the second member 16 is affixed centrally to a resilient blade 19 which has portions bent relative to each other and is provided with a release handle 20 attached to its top portion. On the inside face of the blade 19 there is secured a hook-up element 21 having its active profile facing downwards and conforming with a detent dog 22 connected on the frame 1.
In another embodiment form, the hook-up elements are embodied by a link and a second class lever. The link is swivel mounted at its ends and extends between the second member 16 and an intermediate portion of said lever, whilst the lever itself extends between a pin of engagement with the frame 1 and a free handgrip. The lever is movable toward and away from the frame 1 and when the same is close against the latter said link locates between the frame 1 and said pin.
On the same lateral side of the machine on which said snap-action mechanism is pre-arranged, there engage pusher members embodied by spring members 23 which project from the frame 1 to engage the container 9 by spring bias, forcing same to take an appropriate position when raised.
The spring members 23 are embodied by leaf springs in the shape of an ordinary stylized "omega" which extend downwards beyond the lower side of the second member 16 with the pivoting small frame 13 raised (FIGS. 2 and 4).
In practice the spring members 23 have a top end attached to the frame 1, and intermediate portion of saddle-like shape extending to contact the container 1, in the working position, level with the small frame 13, and a terminating portion 24 diverging from the frame 13 and the guides 14.
Lastly, it is observed that on the upper peripheral edge of the frame 13 there is provided a gasket 25 adapted to provide a seal with the frame 13 raised. The gasket 25 makes a seal above the frame 13, whilst the seal between the small frame 13 and the container 9 is due to the structure itself of the small frame, that is to say to the shape and position of the guides 14 and members 15 and 16, as already specified.
The invention operates as follows.
To release the small frame 13, it will be sufficient to force the handle 20 away from the frame 1 and deform the blade 19 inwards, thus causing release of the hook-up element 21 from the retaining dog 22. The frame 13 can thus turn downwards to bring a part of the wheels 11 of the container 9 to rest on the surface 8. At this position the spring members 23 are disengaged from the container 9 and the latter can therefore be slid off along the pivotally mounted guides 14, by pulling on the handle 12. Resting of container 9 on the ground occurs gradually and without shocks.
For reverse operation the frame 13 is inserted into the guides 14 which are pivoted downwardly and is then raised, again by means of the handle 12 alone. On completion of the lifting step, the hook-on element 21 and detent dog 22 will engage together automatically. At this position the spring members 23 contact the container 9 and prevent the latter from slipping off.
During the lifting operation, the spring members 23 will push the container 9, by means of their terminating portions 24, into the proper position against the tops of closed ends 14a in the guides 14, until this position has been reached.
The invention achieves the important advantage of making the container loading and unloading, simple and direct operations, to be carried out even by unskilled personnel. Neither serious lifting efforts nor special attention to the positioning of the container are required, and insertion and withdrawal can be effected with a single pull or push movement. And this can be accomplished with the container advantageously located away from the wheels. | The invention relates to a sweeper machine for floors and bounded surfaces, e.g. the floors of workshops and warehouses, courtyards, having engaged with the machine frame, a removable container for collecting the swept trash supported by pivotally-mounted guides engaged by swivel members extending in a crosswise direction to the machine's longitudinal axis and cooperating to define a small frame intervening sealingly between a suction assembly in the frame and a suction mouth of the container, and with snap-action hook-up elements provided between the frame and the pivotally-mounted guides and spring members projecting from the frame and acting by spring contact on the container. | 0 |
DESCRIPTION
BACKGROUND OF THE INVENTION
Leveling devices in the past have been employed for adjustably supporting loads of varying sizes and weights. The level conditions of machine tools, production equipment, and, more recently, nuclear reactors, have presented a critical need for preciseness. Although several levelers are usually used to obtain this precise condition, full compensation for uneven or non-level supporting planes has been difficult, if possible, to attain. The result of a non-level condition will result in load shifting and an accompanying impairment of operation or other serious and costly consequences.
Previous attempts to compensate for supporting plane unevenness and slope have included the combination of wedges and spherical surfaces, as taught in U.S. Pat. No. 3,306,562, but these earlier devices had a limited range of adjustability and stability. Usually the supporting plane upon which the leveling device was to rest required substantial preparation to approach near levelness.
SUMMARY OF THE INVENTION
An important object of this invention is to provide an improved leveling device designed and constructed so that true level alignment is achieved and maintained while avoiding severe stresses without considerable preparation of the load supporting plane.
Another important object of the invention is to provide an improved leveling device which is self-aligning in any direction for automatically compensating for surface slope.
A further object of the invention is to provide an improved leveling device for carrying heavy loads which is designed in a novel manner to compensate for support plane unevenness or slope without concern for the direction of such unevenness or slope.
Another important object of the invention is to provide an improved leveling device for heavy loads which distributes the load weight over the whole supporting area and minimizes shifting tendencies of the load usually caused by vibration.
To achieve these objectives, the leveling device herein described combines a containing base member, a mechanical means for adjustment of relative position between two wedges and the base, an automatically adjusting third wedge, and a self-aligning load support. While the mechanical shifting of the two wedges accomplishes vertical adjustment, the automatic and self-aligning features of the device are designed to maintain structural strength and stability while compensating for unevenness and lack of level in the support plane.
Other objects and advantages of this invention will be apparent from the following specifications, appended claims, and accompanying drawings.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a vertical cross-section of a leveling device embodying the invention;
FIG. 2 is a cross-sectional view taken on the line 2--2 of FIG. 1;
FIG. 3 is a cross-sectional view taken on the line 3--3 of FIG. 1;
FIG. 4 is a horizontal cross-sectional view taken on the line 4--4 of FIG. 1;
FIG. 5 is a horizontal cross-sectional view taken on the line 5--5 of FIG. 1;
FIG. 6 is a schematic view similar to FIG. 1 showing the relative position of its various parts when the device is at its maximum vertical adjustment;
FIG. 7 is similar to FIG. 6 but showing the position of the various parts at the alternative midpoint of vertical adjustment;
FIG. 8 is similar to FIG. 6 but showing the position of the various parts at the lowest vertical adjustment; and
FIG. 9 is a schematic view similar to FIG. 6 showing the position of the various parts at the preferred midpoint of vertical adjustment.
DESCRIPTION OF PREFERRED EMBODIMENT
With particular reference to FIGS. 1 to 3, the preferred embodiment of the invention disclosed therein comprises a base member 10 of general U-shape formation, including a bottom portion 12 and two opposite end wall portions 14 and 16; end wall 14 being an integral part of base 10 and end wall 16 being a separate piece bolted to base 10 by bolts 13, only one of which is shown. The cradle-like appearance of base member 10 forms a partial housing for a pair of superimposed wedge-shaped members, the upper one being indicated at 20, the lower one being indicated at 18. The lower wedge 18 is seated in the cradle of base 10 on the upwardly facing inclined surface 15. The lower wedge has a downwardly facing inclined surface 17 which slidably engages the surface 15. The lower wedge has a generally horizontally extending upwardly facing surface 19 which slidably engages the complementary horizontal surface 23 of the upper wedge. Both wedges are permitted relative longitudinal sliding movement in the direction of one or the other of the end walls 14 and 16. The two wedges are of equal size and of a length less than the distance between the confronting surfaces of the end walls, and both serve to function as sliding and lifting wedges.
A third wedge, load supporting member 22, is a portion of the load engaging means and rests upon the upper wedge 20. This third wedge has an inclined downwardly facing surface 25 which is slidably supported on a complementary upwardly facing inclined surface 27 of the upper wedge 20. The third wedge 22 functions as a lifting wedge. The three wedges are designed to nest within the end walls of the base 10.
Torque means is provided for slidably adjusting the wedges. Such means comprises an adjusting screw 24 operatively engaging the lower and upper wedges 18 and 20, and having polygonally shaped head 26 which is engageable by a tool for turning purposes. To prevent sidewise movement, each wedge has downwardly extending tongues 18a, 20a, and 22a which overlap the member below as shown in FIGS. 2 and 3. For this purpose, wedges 18 and 20 are provided with grooves 18b and 20b into which the complementary tongues are received.
The wedges 18, 20 and 22 have relatively wide dimensions, as shown in the FIGS. 2 and 3, and the engagement of their respective interfaces, as well as the engagement of the interface of wedge 18 and base 10, is maintained against lateral movement as above described. The action of raising and lowering a load to a desired level line is achieved by converting horizontal motion into vertical motion and particularly by the interaction of the inclined planes of wedge members 18, 20 and 22. More specifically, the shank of screw 24 is slidably received in an upwardly opening slot 11 of frame wall 14. Torque applied to screw head 26 causes rotation of screw 24 within the operatively engaged portions of wedges 18 and 20. This rotation is converted into longitudinal forces acting upon the wedges and a resultant relative longitudinal shift occurs. The load supporting member 22 adjusts itself on the upwardly inclined surface 27 of upper wedge 20 so as to maintain contact with the end wall 14, thus, as the lower and upper wedges are moved longitudinally relative to each other by the rotation of the adjusting screw in either direction, the load supporting member is moved vertically by the interaction of the inclined wedging surfaces.
Relative longitudinal movement of the upper and lower wedges is accomplished by an idler coupling 30 connected to the lower wedge 18 and an adjusting nut 32 connected to the upper wedge 20. The idler coupling comprises a pair of U-shaped internally radially grooved members 30a and 30b encircling and meshing with a similarly radially grooved portion of screw 24, said U-shaped members joined to each other and attached to lower wedge 18 by bolts 34, FIG. 2. Although the meshed radial grooves of said screw and U-shaped members are designed without pitch to allow rotation of said screw in said coupling and not cause longitudinal movement of these members relative to each other, a longitudinal movement of said screw or wedge will force concurrent longitudinal movement in the coupled members.
The adjusting nut 32 is attached to upper wedge 20 by bolts 33, FIG. 3. The nut has a thread pitch which, when the nut is threadedly engaged with a similarly pitched portion of screw 24 and the screw is rotated, will cause a longitudinal movement of nut and screw relative to each other. The idler coupling 30 is attached to a longitudinally extending channel 36 in lower wedge 18, FIG. 2, and, similarly, the adjusting nut 32 is attached to a longitudinally extending channel 38 in upper wedge 20, FIG. 3. FIGS. 2 through 5 illustrate that channels 36 and 38 provide clearance for fore and aft movement of idler 30 and nut 32. Thus, with the connection of screw 24 to nut 32 and idler 30 as described, rotation of said screw will cause longitudinal relative movement between wedges 18 and 20.
Reference to FIGS. 6 through 9 will illustrate the novel combination which converts rotational movement of the adjusting screw 24 into longitudinal movement of the lower and upper wedges 18 and 20 with the ultimate vertical movement of the load supporting member 22. FIG. 6 depicts the leveling device at its maximum vertical extension with upper wedge 20 in contact with base end wall 14 and lower wedge 18 in contact with the opposite base end wall 16. Rotation of adjusting screw 24 will cause nut 32 and its attached upper wedge 20 to move away from base end wall 14. The force of the load support member 22 on inclined interface of surfaces 25 and 27 will cause the load support member 22 to continuously adjust itself to maintain contact with end wall 14 as wedge 20 moves toward end wall 16. Idler coupling 30 allows the rotation of screw 24 without disturbance of wedge 18. As wedge 20 moves to contact wall 16, the retreat of its wedge shape from beneath support member 22 allows member 22 to lower until the device reaches the status depicted by FIG. 7. At this point, wedge 20 is restrained by wall 16. Since continued rotation of screw 24 forces continued relative longitudinal movement between adjusting nut 32 and said screw, and since said nut is attached to wedge 20 and wedge 20 is now constrained by end wall 16, further rotation of said screw will cause the screw to retreat from the now stationary nut and attached wedge 20. The retreat of screw 24 is evident by the retreat of screw head 26 from end wall 14, FIG. 8. As said screw retreats, it draws the idler 30 and its attached lower wedge 18 towards wall 14. The effect of the retreat of wedge 18 down the interface of surfaces 15 and 17 is to cause a lowering of upper wedge 20 and the resultant decrease in height of the load support member 22 until the status of FIG. 8 is attained. This is the lowest vertical height of the device. Because surfaces 15 and 27 are parallel, it is obvious that a reverse direction of rotation of screw 24 will cause the wedges to retreat from wall 16 by the principles discussed above and effect the status depicted by FIG. 9.
The invention provides compensation for an unevenness or slant of the supporting surface or floor upon which the leveling device is set. This is achieved by "floatingly" supporting the load for universal movement in any direction. For accomplishing this purpose, the device is provided with an alignment compensating means having mated relatively shiftable spherical surfaces. More specifically, and with particular reference to FIGS. 1 and 2, the aligning means comprises a load engaging member 28 having a downwardly directed convex spherical surface 44 and the top side of the load supporting member 22 is provided with a mating concave spherical recess 46 of the same radius of curvature as the surface 44.
In plan view the load engaging or alignment compensating member 28, is of circular outline. It is provided with a central upwardly projecting boss 48 for engagement with the supporting structure of the load which the leveler will support. When laid on a floor, the load leveling base member 10 will assume whatever inclination the floor has. The alignment compensating member 28 is free to slide over the spherical surface 46 of the load supporting member 22 in any direction as the heavy load carried thereby is vertically adjusted and leveled. Any slant in the floor within the capability of the leveling assembly can be readily compensated for in this manner.
A leveling device constructed in accordance with this invention, in carrying out its function of supporting heavy loads, will spread or distribute the forces of the load equally over the wide surface of the spherical portions 44 and 46, and thereby avoid load concentrations at any low spot or line which might easily cause a fracture of one of the parts of the leveler. No care need be exercised about the direction of floor slant and the disposition of the parts of the leveler with respect thereto. During the operation of vertically adjusting and leveling the load, the base 10 and the wedging members contained therein may be slid and swiveled under the spherical protuberance 44 of the alignment compensating means regardless of the floor slant. Final adjustments of previous levelers could cause the entire leveling device to move to the extreme limits of its self-aligning capability and thus move the load stress to the outer limits of the device. The embodiment of the present invention provides the alignment capabilities of the spherical surfaces 44 and 46 while presenting the novel design feature that allows the load supporting member 22 to maintain its position against end wall 14, thus maintaining the load forces at the center of mass and structural strength of the assembled device. Although the embodiment herein presented places the alignment compensating means on top of the leveling device, it would be obvious to one skilled in the art that such alignment means might also be placed under the base 10 without adverse effect on the other basic features of the device.
In the described embodiment of this invention, horizontal surfaces 12 and 19 are parallel and the angles of the inclined surfaces are equal, making surface 15 parallel to surface 27. This relationship between said surfaces is not necessary for successful employment of the device and other combinations of surface relationships may be employed. However, it has been found that variations of slope in the surfaces will affect the torque requirements necessary for adjustment as well as vary the range of vertical adjustment available to the user. The preferred embodiment of said surface relationships provides a "locking angle" which gives stability to the final adjustment of the device.
While the preferred embodiment of the invention has been described and illustrated, it is to be understood that it is capable of variation and modification without departing from the spirit and scope of the invention. | A leveling device for mounting and leveling heavy loads independent of the inclination of the floor upon which the device is supported utilizes a plurality of wedges disposed between a base member and a load supporting member in combination with mated spherical surfaces to provide two self-adjusting features which obviate concern for non-level mounting surfaces or misaligned loads. | 5 |
This invention was made with United States government support awarded by USDA Biopulping Consortium II. The United States Government has certain rights in this invention.
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of Ser. No. 08/289,479 filed Aug. 11, 1994 now U.S. Pat. No. 5,620,564.
BACKGROUND OF THE INVENTION
In general, the field of the present invention is the biopulping of wood. In particular, the field of the present invention is biopulping of wood with a white rot fungi and a nutrient adjuvant.
In the manufacture of paper from wood, the wood is first reduced to an intermediate stage in which wood fibers are separated from their natural environment and transformed into pulp, a viscous liquid suspension. Several techniques are used to produce pulp from various types of wood. The simplest of these techniques is the refiner mechanical pulping (RMP) method, in which the input wood is simply ground or abraded in water through a mechanical milling operation until the fibers are of a defined desired state of freeness from each other. Other pulping methodologies include thermo-mechanical pulping (TMP), chemical treatment with thermo-mechanical pulping (CTMP), chemi-mechanical pulping (CMP) and the chemical pulping, sulfate (kraft) or sulfite processes for pulping wood. The general concept in all of these processes for creating pulp from wood is to separate the wood fibers to a desired level of freeness from the complex matrix in which they are embedded in the native wood.
Of the various components of wood, cellulose polymers are the most abundant and are the predominate molecule desired for retention in pulp for paper production. The second most abundant polymer in wood, which is the least desirable component in the pulp, is lignin. Lignin is a complex macromolecule of aromatic units with several different types of interunit linkages. In the native wood, lignin physically protects the cellulose polysaccharides in complexes known as lignocellulosics. In chemical pulping processes, lignin is removed. In chemi-mechanical processes, lignin is disrupted to free the cellulose or to make it easier to mechanically free the cellulose.
Biological systems can be utilized to assist wood pulping. A desirable biological system would liberate cellulose fibers from the lignin matrix by taking advantage of the natural abilities of an organism. Research in this area has focused on white-rot fungi, so named because the characteristic appearance of infected wood is a pale color. This color is the result of the depletion of lignin in the wood, the lignin having been degraded or modified by the fungi. Because white-rot fungi appear to preferentially degrade or modify lignin, it is a logical choice for biological treatment to pulp wood. Pulping by this method is referred to as "biopulping."
Several attempts to create biopulping systems using white-rot fungi on a variety of wood fibers have been reported. The most commonly utilized fungus is the white-rot fungus Phanerochaete chrysosporium, also referred to as Sporotrichum pulverulentum. Other fungi which have been previously used in such procedures include fungi of the genera Polyporus and Phlebia. The prior art is generally cognizant of the fact that attempts have been made to use microorganisms, such as white-rot fungi, as part of a process of treating wood in combination with a step of either mechanical or thermo-mechanical pulping of cellulose fiber.
Another example is U.S. Pat. No. 3,962,033, directed to the biopulping of cellulose using white-rot fungi. The fungi used included both naturally occurring wild-type strain cultures and mutant strains produced which lacked cellulase, so as to reduce the amount of cellulose degraded by the organisms. Various types of wood were degraded with the fungi. This wood was then used as input materials for a thermo-chemical or thermo-mechanical pulping procedure. This patent discloses various techniques for making a cellulose pulp by depleting lignin while reducing the cellulose-decomposing action of the enzymes produced by these organisms in order to preserve the cellulose yield. Groups working with the inventor of this patent have several publications regarding use of fungi for biomechanical pulping, e.g. Anders and Erikkson, Svensk Papperstidning, 18:641-2 (1975), Erikkson and Vallander, Svensk Papperstidning, 6:85:33-38 (1982).
U.S. Pat. No. 5,055,159 discloses biopulping with Ceriporiopsis subvermispora. Biomechanical pulping of both hardwood and softwood chips with this white-rot fungus has been demonstrated. During this process at a laboratory scale, fungal pretreatment of both hardwood and softwood species saves substantial amounts of the electrical energy during refining, improve paper strength, and reduce the environmental impact of pulping (Akhtar, et al., "Biomechanical pulping of loblolly pine with different strains of the white-rot fungus Ceriporiopsis subvermispora," Tappi J. 75:105-109, 1992; Akhtar, et al., "Biomechanical pulping of loblolly pine chips with selected white-rot fungi," Holzforschung 47:36-40, 1993; Akhtar, et al., "Biomechanical pulping of aspen wood chips with three strains of Ceriporiopsis subvermispora," Holzforschung 48:199-202, 1994; Kirk et al., "Biopulping: A Glimpse of the Future?", Res. Rep. FPL-RP-523, Madison, Wis., pp. 74, 1993). These results show the technical feasibility of biopulping.
One of the key factors determining the commercial and economic feasibility of biopulping is the cost of the fungal inoculum and the related question of culture time of the organism in the wood. Commercial considerations impose a particular time frame on the amount of time, referred to as the dwell time, that can be dedicated to permitting the biopulping fungus to propagate in the wood. One solution to the problem of obtaining sufficient fungal action prior to pulping is to simply add more fungal inoculum. However, the process soon becomes cost prohibitive, if an excessive amount of fungal biomass is needed. Therefore, the art needs a method to reduce the quantity of fungal inoculum needed for successful biopulping in a time scale suitable for commercial application.
BRIEF SUMMARY OF THE INVENTION
The present invention is a method of making a wood pulp. The method comprises inoculating wood chips with an inoculum of white rot fungi and a nutrient adjuvant. The nutrient adjuvant is sterilized or unsterilized corn steep liquor. The wood chips are introduced into a bioreactor either before or after inoculation and incubated under conditions favoring the propagation of the fungus. After a sufficient amount of time the fungus modifies a significant amount of lignin naturally present in the wood chips. The chips are then pulped.
In another embodiment of the present invention, paper is made from the pulped chips. In yet another embodiment, the invention is the inoculated wood chips.
In a preferred embodiment of the present invention, between 0.5% and 3% nutrient adjuvant (on a weight basis as a proportion of the wood chip mixture) is used. In another preferred form of the invention, the nutrient adjuvant is corn steep liquor.
It is an advantage of the present invention that wood is biopulped using a smaller amount of fungal inoculant. Preferably, the amount of inoculant is less than 0.3% on a dry weight basis of the total inoculated wood chip mixture. More preferably the amount of the inoculant is less than 0.1% on a dry weight basis. Most preferably, the amount of inoculant is less than 0.0005% on a dry weight basis.
It is an advantage of the present invention that corn steep liquor, molasses or yeast extract may be used as a nutrient adjuvant in a biopulping process.
It is a feature of the present invention that a dramatic reduction in amount of inoculum needed to successfully biopulp wood is enabled.
Other features, advantages and objects will become apparent upon review of the specification, claims and drawing.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
FIG. 1 illustrates the laboratory scale bioreactor used in the illustrative Examples of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is a method of biopulping using a combination of a white rot fungi and corn step liquor as a nutrient adjuvail. Use of this nutrient adjuvant, as described below, enables one to dramatically decrease the amount of fungal inoculum (calculated on a dry weight basis as a proportion of the amount of wood chips) from 0.3% to 0.0005% while achieving comparable efficacy. This 600-fold reduction in the amount of inoculum is important in making biopulping technology economically feasible.
1. Wood Preparation
The process begins with wood chips. The process of the present invention was developed with and is particularly useful for the biopulping of softwoods, such as U.S. southern pine species. A preferred species for use in the biopulping process of the present invention is Loblolly pine, Pinus taeda, which is a major pulpwood species. The Examples below focus on the use of Loblolly pine. The method is also useful with hardwood species. The Examples below disclose the success of the present invention with both pine and aspen chips. Example 5, below, discloses the success of aspen chips in the present invention. The present invention has utility for other softwood species and hardwood species as well. The efficacy of biopulping with both softwood and hardwood has been demonstrated in the art.
The wood is converted to chips through a conventional technology to a preferable chip size of anywhere between 1/8 and 3/4 of an inch.
Because conditions of high humidity during the fermentation process will be desired, a relatively high moisture content of the chips prior to fermentation with the biopulping fungus is most desirable. Therefore, the chip moisture content prior to inoculation is preferably at the fiber saturation point or greater. A preferred moisture content would be approximately 55-65% of the total wood. This measurement indicates that of the total weight of the moist wood, approximately 55-65% of that weight is moisture.
2. Fungi Application
Separately from the chips, a seed inoculum must be maintained of a white rot fungal culture to be utilized during the biopulping process. The preferred culture is any useful strain of the fungal species Ceriporiopsis subvermispora, with one preferred strain being strain CZ-3 available from the Center for Forest Mycology Research of the Forest Products Laboratory, U.S. Department of Agriculture. Almost all other strains of Ceriporiopsis subvermispora are suitable for the present invention. Other preferred strains are the haploid Ceriporiopsis subvermispora strains FP-105752 SS-4, L-14807 SS-1, L-14807 SS-3, L-14807 SS-S, and L-14807 SS-10 which are also obtainable from the Center for Forest Mycology Research, USDA Forest Products Laboratory, Madison, Wis. (Our experiments below demonstrate that two of the haploid strains gave more energy savings and strength improvements than the diploid CZ-3 strain.) Ceriporiopsis subvermispora strains are common in the environment and can readily be isolated from the wild.
A second preferred culture is any useful strain of the fungal species Phlebia subserialis. The preferred strain of Phlebia subserialis for use within the present invention is known as HHB7099. Under many biopulping processes and conditions, Phlebia subserialis offers results in terms of energy savings and improvement in wood quality that rival, in many cases, those which can be achieved with Ceriporiopsis subvermispora. Other strains of Phlebia subserialis are believed useful as well.
It is also believed that the present invention is useful with other white rot fungal species which can be used in biopulping methods. Other white rot fungal species from which strains have been isolated that have useful biopulping characteristics include Phlebia brevispora, Dichomitus squalens, Phlebia tremellosa, Perenniporia medulla-panis, and Hyphodontia setulosa. It is further believed that the method of the present invention will be equally applicable when used with any other lignin-degrading white rot fungi in a biopulping process.
Strains of the white rot fungi can be maintained by conventional fungal culture techniques, most conveniently by growing on potato dextrose agar (PDA) slants. Stock slants may routinely be prepared from an original culture for routine use and may be refrigerated until used.
The fungal culture may be applied to the wood in several ways. For example, to inoculate significant volumes of wood chips, a starter inoculum may be prepared. The starter inoculum can be simply a smaller volume of chips carrying the fungal mycelium throughout, so that the starter inoculum may be conveniently mixed into a larger volume of chips for the inoculation of the larger quantity of chips. In the starter inoculum culture, a relatively high moisture content in the wood, at least 55%-65% is maintained to ensure better colonization of the chips with the fungal mycelia.
In the laboratory-scale procedures described below, a liquid inoculum is prepared and mixed with the wood chips. The liquid inoculum is prepared by combining potato dextrose broth and yeast extract with distilled water and sterilizing the combined mixture. After cooling to room temperature, the flasks are inoculated with plugs cut from a ten day old potato dextrose agar plate prepared from a working culture of the fungus. These potato dextrose agar plates had been incubated at 27° C. and 65% relative humidity for ten days. The inoculated flasks are then incubated at 27° C. at 65% relative humidity for ten more days.
The flasks are decanted and washed with sterile distilled water to remove the excess medium from the fungal biomass. The fungal biomass is then placed in distilled water and blended in an electric blender twice for 15 seconds at high speed. More distilled water is added to the suspension. An amount of the suspension is dried to determine the dry weight per ml. Different dilutions of the fungal inoculum can then be made from this fungal stock culture to obtain inoculants of different strengths.
The chips are mixed with the liquid inoculum and the mixture is incubated for a time period, preferably between 2 weeks and 4 weeks. Of course, if a commercial scale inoculation is planned, the incubation period may have to be adjusted to meet commercial concerns.
Alternatively, the fungal inoculum may be applied to the wood chips in other ways, such as a liquid spray or a solid inocula.
When the rate of application of the fungal inoculants are discussed here, the inoculum is measured on a dry weight basis. This measurement indicates the percentage of total dry mass of the inoculated wood chips that is represented by the fungal inoculum. For example, a 0.3% inoculum on a dry weight basis means that in 100 g of dry weight of wood chips plus inoculum, 0.3% (0.3 g) of the dry mass is fungus.
Preferably, the fungal inoculant of the present invention is less than 0.3% on a dry weight basis. More preferably, the inoculant is less than 0.1% on a dry weight basis. It has also been found that the fungal inoculant of the present invention can be equal to or even less than 0.0005% on a dry weight basis.
3. Addition of a Nutrient Adjutant
The present invention requires the addition of a nutrient adjuvant to the biopulping procedure described above. Preferably, an amount of the nutrient adjuvant is added to the fungal inoculum prior to the addition of the inoculum to the wood chips. In the Examples below, nutrient adjuvant is added to the inoculum and both inoculum and nutrient are immediately added to the wood chips. However, the nutrient adjuvant could be added separately to the wood chips, before or after the fungal inoculum. Additionally, it is envisioned that it might be advantageous to incubate the nutrient adjuvant and fungal inoculum for a period of time before application to the wood chips.
The nutrient adjuvant of the present invention possesses the capabilities of fostering growth of the fungal biomass in a manner that allows successful biopulping with a limited amount of fungal inoculum. Specifically, the nutrient adjuvant of the present invention will allow at least 100-fold less fungal inoculant to be used for equivalent dwell times to achieve equivalent results. This requirement means that the nutrient adjuvant must possess the appropriate chemical composition to allow the fungal biomass to significantly and dramatically increase its mass relative to a culture growing without a nutrient adjuvant.
Preferably, the nutrient adjuvant of the present invention allows a fungal inoculum of less than 0.1% on a dry weight basis to be used. Most preferably, the nutrient adjuvant of the present invention allows a fungal inoculum of less than or equal to 0.0005% to be used.
As a comparison of Examples 1 and 2 below will demonstrate, a 0.3% fungal inoculum (on a dry weight basis) without a nutrient adjuvant is required for an energy savings of 19% after a 2 week incubation or dwell time. When a 0.001% inoculum (on a dry weight basis) is combined with 1% corn steep liquor (measured as weight of semi-solid liquid as a percentage of dry weight of the wood chips), an identical energy savings of 19% is realized after a 2 week incubation. Therefore, the amount of fungal inocula needed to achieve equivalent energy savings is reduced by at least 300-fold through the use of the adjuvant. Table 2, below at Example 2, indicates that inocula levels of 0.0005% (on a dry weight basis) can be used, thus achieving a significant economic savings.
Nutrient adjuvants are expressed as percentages on a liquid to dry weight basis. Therefore, a 1% adjuvant solution represents the addition of 1 gram of viscous liquid corn steep liquor to 100 grams of dry weight of the wood. Since the corn steep liquor is about 50% solids, the additive levels could be reduced by about 50% to obtain dry weight levels for this additive.
Most preferably, the nutrient adjuvant of the present invention is corn steep liquor. The nutrient adjuvant may be sterilized or autoclaved corn steep liquor, but sterilization is specifically not required.
Corn steep liquor is a by-product of the production of corn starch and, as a by-product, is relatively economical. Corn steep liquor is selected because it is relatively cheap ($55/ton of semi-solid liquid in 1994) and is commercially available from Corn Products, a Unit of CPC International Inc., Summit-Argo, Ill.
Corn steep liquor is a condensed fermented corn extractive which is produced in the corn wet milling process when the dry corn is soaked (steeped) in a warm sulfurous acid solution. Corn steep liquor is sold commercially by several companies as a viscous light brown liquid. During the process, the grain solubles are released and undergo a mild lactic acid fermentation from naturally occurring microorganisms. Currently corn steep liquor is used as a liquid supplement for ruminants, unidentified nutrient source for poultry and protein source and biding agent for cattle range blocks.
The composition of corn steep liquor varies slightly. A typical composition is about as follows:
______________________________________Dry substance (%) 50.7pH 3.9Protein (% dry basis) 40.8Lactic acid (% dry basis) 16.0Reducing sugars (% dry basis) 12.8______________________________________
The Examples below demonstrate the use of a corn steep liquor obtained from Corn Products division of CPC International with the above-identified composition. However, in other experiments, we have used corn steep liquors obtained from other batches, and our results were similar to those obtained with the batch identified above. In general, in a preferred corn steep liquor, the dry substance will vary from about 50%-55%, the pH will vary from about 3.9-4.2, the protein percent will vary from about 20%-50%, the lactic acid percent will vary from about 15%-20% and the reducing sugars will vary from about 5%-15%.
Preferably, between 0.5% and 3.0% (on a weight to weight basis) corn steep liquor nutrient adjuvant is used. On a cost basis, it is advantageous to use as little nutrient as possible. However, this savings has to be weighed against an increase in fungal biomass when increased amount of nutrient adjuvant is used. We envision that nutrient adjuvant of about 0.0005% or less, on a weight to weight basis, will be successful.
4. Incubation of Wood Chips
The actual incubation of the wood chips for fungal degradation may now proceed. Wood chips combined with both the fungal inoculant and nutrient adjuvant are placed in the fermentation reactor (bioreactor). The bioreactor may be any of a number of styles capable of containing solid media fermentation cultures. Though it has been found that rotating drum bioreactors host the fermentation reaction to a sufficient degree, it has also been advantageously found that stationary or static reactors work sufficiently well within the present invention to be preferred. It is merely required that the stationary or solid phase reactor have sufficient aeration so as to ensure adequate oxygen flow to the fungus and significant removal of carbon dioxide therefrom. In fact, it is an advantage of the process described herein that a stationary, and even rudimentary, reactor will suffice. Since what is required is simply some level of aeration, humidity, and temperature control, it is envisioned that simple pits or piles of chips on the ground may be utilized if aeration is provided, as by inserted tubing, and humidity is controlled, if necessary, either by containment or by moisture application.
A particularly suitable laboratory scale reactor is described in FIG. 1. This bioreactor, referred to as the air-lift bioreactor, was fabricated using a polypropylene bucket 20 as the fermentation or reactor vessel. The top of the vessel 20 was sealed with a lid 22 which was vented to the atmosphere through an exit air tube 24. Placed suspended above the bottom of the reactor 20 was a polypropylene perf board, which was a solid disk of polypropylene material vented with air holes. The perf board 26 was suspended in place by a stand 28.
An air filter 30 was provided connected by air tubing 32 to the base of the bioreactor 20. The air filter 30 received its input air supply from a manifold 35 which was supplied, in turn, through an air line 36 connected to the output of a rotameter 38. The rotameter 38 received air from an air line 40 connected to a humidifier 42, which passed incoming air through deionized water in a flask to adjust relevant humidity. Input air was supplied through piping 44 from a regulated air supply.
The air lift reactor 20 thus provided a constant temperature reactor through which constant aeration was provided in a sterile environment. The sterile, humidified air constantly passed through the chip mass. To maintain constant temperature water could be heated to increase the humidity and additional stages of humidification could be added as needed. Air was disbursed to individual reactors from the manifold and passed through a 0.20 micron filter prior to entering the reactor to avoid contamination of other microbial agents.
After mixing the inoculum with the wood chips, the chips were then fermented in the bioreactors at 27° C. plus or minus 1° C. and at 65 plus or minus 5° relative humidity for 2 weeks. Parallel batches were treated both with the solid-phase and liquid-phase starter inoculum along with an untreated control. After harvest both sets of chips were refined in a 300 mm diameter mechanical single disk refiner and paper was made from the pulp thus created.
Prior to making the pulp, the weight loss of the wood chips was measured to provide an indication of the relative digestion of the wood chips by the fungal mycelia from each of the experimental preparations.
The inoculation with the starter inoculant culture and nutrient adjuvant is made to the wood chips to be treated. As discussed above, the amount of inoculum starter culture added to the chips can vary. The inoculant fungal culture can be in liquid or dry form. The inoculum and chips are then mixed and the bioreactors set up as in FIG. 1. The bioreactors are preferably incubated for 4 weeks at 27°±1° C. at 65±5% moisture content with constant aeration with moisture-saturated air.
The inoculated chips will then be incubated during a time period in which the fungal mycelia will penetrate throughout the wood chips. The temperature range most desired depends on the fungal strains. It has been found that a bioreactor kept in the range of 22°-32° C. with a moisture content in the wood of 55%-65% plus or minus 5% achieves a degree of mycelia penetration of the wood chips that results in significant and useful degradation of the chips for paper pulping purposes. The wood chips are preferably aerated continually during the incubation period with moisture-saturated air such that the wood maintains the constant moisture content of about 55%-65%. It is most desired that the pH of the chip incubation culture be specifically monitored so that the pH stays within the broad range of between 3.0 and 6.0. Thus it is not required that pH be specifically controlled, but only monitored on occasion so that it remains within the physiological limits necessary for the growth of the fungal culture.
5. Processing the Inoculated Chips
The biologically degraded wood is then pulped. Many pulping methods are suitable for the present invention although mechanical pulping is preferred.
In its simplest form, a mechanical refining process is utilized. Dilution water is added to the chips and the chips are run through a mechanical refiner in a number of sequential passes. The number of passes of the chips/pulp mixture will depend upon the freeness desired for the particular paper application to be made. Freeness is an arbitrary measure of water drainage. The chip/pulp mixture is repeatedly fed through the refiner until the desired level of freeness is achieved. Thus freeness may be periodically monitored to determine the progress of the pulps toward the freeness level which is desired for the paper. The wood pulp may be dewatered as necessary between passes. Loblolly pine, which has been incubated for a time period of four weeks with the procedures described above, requires between ten and fifteen passes to obtain the value of 100 ml Canadian standard freeness in a single disk mechanical refiner with an initial setting of 18 mils.
The overall energy efficiency of the process can be compared with that of a straight mechanical process by pulping in the same apparatus either untreated chips or treated chips while at the same time monitoring the energy consumption of the refining mill itself. The treated chips require significantly less energy input through the refiner to achieve the same level of freeness in the resulting pulps.
The biomechanical pulps made through this procedure may then be made into paper using standard papermaking techniques. Standard techniques (as described by the Technical Association of the Pulp and Paper Industry, TAPPI), which are known to work with mechanically refined pulps, work equally well with biomechanically refined pulps of the type created by the process described herein. Accordingly, the paper may be formed by conventional methods.
Paper made from the biomechanically created pulp can be compared in quality, strength and texture to that created through simple mechanical pulping. The biomechanically created pulp has significantly increased strength property. Thus, it is apparent that the process of the present invention does not sacrifice the quality or strength of the paper in order to achieve the highly desirable energy savings, but, in fact, results in a unique combination of both significant reduction in energy utilization in the process and an increase in the strength properties of the resulting paper.
The details of the process of the present invention will become more apparent from the following Examples which describe the laboratory-scale utilization of the present process and the results achieved thereby. It is understood that the scale-up from a laboratory-scale to a plant-scale process of the pulping operation described below may involve some alteration of the parameters or details of the process steps described herein. It is to be understood that the Examples described below, while they demonstrate the efficacy and practicability of the process of the present invention, have not been optimized for a commercial scale.
Nevertheless, the experimental evidence presented makes it clear that the procedure is efficacious and efficient and enables the creation of commercial scale-procedures for implementing the general process described herein.
EXAMPLES
Example 1
Objective: To determine the optimal fungal inoculum level for saving electrical energy and improving paper strength properties.
Wood chips: Freshly cut Loblolly pine (Pinus taeda L.) pulpwood-size logs were obtained from the Talladega National Forest in Talladega, Ala. The logs were debarked and chipped to an average size of 16-mm. The chips were bagged in plastic bags and frozen until used to prevent the growth of contaminating microorganisms.
Fungus: The biopulping fungus Ceriporiopsis subvermispora strain CZ-3 was used. This culture was obtained from the Center for Forest Mycology Research of the USDA Forest Products Laboratory, Madison, Wis. The culture was continuously maintained in cereal culture and potato dextrose agar slants. Working cultures were prepared from the stock cultures as needed and refrigerated until used. Potato dextrose agar plate culture was inoculated from a working culture and incubated at 27° C. and 65% relative humidity for 10 days.
In preparing liquid inoculum, potato dextrose broth (50.4 g) and yeast extract (15.28 g) were added to 2100 ml of distilled water and mixed well. 300 ml of this medium was poured into seven 2800 ml flasks. Each flask was autoclaved for 20 min. at 121° C. After cooling to room temperature, each flask was inoculated with 30 plugs cut with a number 9 size cork bore from a 10-day old potato dextrose agar plate of the fungal culture. The flasks were then incubated at 270° C. at 65% relative humidity for 10 days. Prior to use, the flasks containing the fungal biomass were decanted and washed with sterile distilled water to remove excess medium from the fungal biomass. The fungal biomass was then placed in distilled water and blended in a Waring blender (VWR scientific) twice for 15 seconds each time at high speed, following which distilled water was added to the suspension to make the total volume 700 ml.
About 100 grams of this suspension produced 1.50 g dry weight of the fungus. Different dilutions of fungal inoculum were made from the fungal stock solution to obtain 0.01%, 0.05%, 0.10%, 0.15%, and 0.30% inoculum on a dry weight basis, and the appropriate amount of fungal inoculum was diluted to a 100 ml suspension with sterilized water.
Chips preparation and bioreactor inoculation: Frozen loblolly pine chips were thawed and thoroughly mixed to obtain uniform samples. Six static-bed bioreactors (FIG. 1) each containing 1500 g of chips (on a dry weight basis) were autoclaved for 90 min. at 121° C. and then cooled to room temperature.
These bioreactors were inoculated with different levels of inoculum as mentioned above. The full 100 ml of fungal culture was used as the inoculant. One non-inoculated bioreactor served as control. About 55% moisture (wet weight basis) in wood chips was maintained during fermentation. After receiving inocula, the bioreactors were shaken vigorously for uniform mixing.
Each bioreactor was sealed and placed in an incubator at 27° C. for 2 weeks and aerated with a specific aeration rate of 0.0227 liter/liter/min. At harvest, fungus-treated chips and control chips were refined in a 300 mm diameter mechanical atmospheric disk refiner to measure energy consumption during refining and the resulting pulp was made into paper and tested for strength properties.
Results: Table 1 describes the results. The lowest amount of inoculum (0.01% on a dry weight basis) only saved 4% of electrical energy during refining and did not improve paper strength compared to the control. The highest amount of inoculum (0.30% on a dry weight basis) saved 19% of electrical energy and improved only tear index significantly (28%) compared to the control.
TABLE 1______________________________________Energy savings and strength properties duringbiomechanical pulping of loblolly pine chips withCeriporiopsis subvermispora CZ-3 (2-week incubation).Treatments Strength properties(% inoculum on Energy Burst index Tear indexdry weight basis) Savings (%).sup.a (kN/g) (mNm.sup.2 /g)______________________________________Control -- .62 ± .05.sup.b 1.67 ± .13.01 4 .63 ± .04 1.89 ± .09.05 11 .71 ± .04 2.16 ± .20.10 12 .74 ± .03 2.13 ± .14.15 12 .70 ± .06 2.04 ± .15.30 19 .70 ± .05 2.14 ± .15______________________________________ .sup.a Energy savings are calculated based on the untreated control values .sup.b Standard Deviation
Example 2
The above results are acceptable, but the amount of inoculum (0.3% on a dry weight basis) needed to achieve the results is quite high. Therefore, we attempted to reduce the amount of fungal inoculum to the level of commercial application (0.0005% on a dry weight basis) with the use of specific nutrient adjuvants without sacrificing energy savings or strength improvements.
Objective: To reduce the amount of fungal inoculum.
Wood: As in Example 1
Fungus: The inoculum was prepared as in Example 1. Three different levels of inoculum were used (0.002%, 0.001%, and 0.0005% on a dry weight basis). 210 g of semi-solid corn steep liquor was autoclaved in a beaker for 20 min. at 121° C. 15 or 45 g of semi-solid corn steep liquor was added to different levels of inoculum. These inocula containing corn steep liquor were used to inoculate wood chips contained in the bioreactors. Therefore, 1% or 3% corn steep liquor on a dry wood basis was added to each bioreactor.
Chips preparation and bioreactor inoculation: Same as in Example 1. In this experiment, bioreactors each containing 1500 g of chips (dry weight basis) were steam sterilized for approximately 10 min. instead of autoclaving because this method of sterilization using atmospheric steaming seems practical and is economically feasible. Two bioreactors without the biopulping fungus, one without the corn steep liquor and the other with 1% corn steep liquor, served as controls to see whether corn steep liquor alone has any beneficial or detrimental effect. Similarly another bioreactor was added in the experiment with the reduced amount of inoculum (0.0005% on a dry weight basis), but without the corn steep liquor, to see whether reduced level of inoculum itself can do biopulping.
Results: Table 2 reports the results. The addition of 1% corn steep liquor to the control bioreactor did not save any energy or improve paper strength compared to the control bioreactor without the corn steep liquor. Addition of 1% or 3% corn steep liquor to all the inocula saved 1-19% or 25-30% of electrical energy, respectively, compared to the control. However, overall strength properties due to these treatments were not significantly improved. The reduced amount of inoculum (0.0005% on a dry weight basis) without 1% corn steep did not show any colonization of wood chips. The following conclusions can be drawn from this experiment:
1. Corn steep liquor itself is inert.
2. Reduced amount of inoculum (0.0005% on a dry weight basis) without the corn steep liquor was not successful.
3. Addition of 1% corn steep liquor to 0.0005% inoculum gave about the same amount of energy savings as did the 0.3% inoculum without nutrient adjuvant (Table 1). However, the reduced inoculant plus adjuvant did not improve tear index as did the 0.3% inoculum in the previous experiment (Example 1).
4. 3% corn steep liquor gave more energy savings than 1% corn steep liquor.
Therefore, another experiment (Example 3) was conducted to determine whether high concentration of corn steep liquor (3%) produced more fungal biomass during fermentation and resulted in better biopulping performance of the fungus.
TABLE 2______________________________________Energy savings and strength properties duringbiomechanical pulping of loblolly pine chips with three levelsof inoculum of Ceriporiopsis subvermispora CZ-3 in thepresence of two levels of corn steep liquor (CSL) from CornProducts (batch E802) (2-week incubation). Strength propertiesTreatments Energy Burst Tear(% inoculum or CSL savings index indexon dry weight basis) (%).sup.a (kN/g) (mNm.sup.2 /g)______________________________________Control - CSL -- .65 ± .03.sup.b 2.12 ± .20Control + 1% CSL -- .67 ± .02 2.07 ± .10.002% inoculum + 1% CSL 18 .72 ± .05 2.17 ± .12.001% inoculum + 1% CSL 19 .71 ± .05 2.35 ± .17.0005% inoculum + 1% CSL 8 .74 ± .04 2.15 ± .11.0005% inoculum - 1% CSL.sup.c.002% inoculum + 3% CSL 30 .76 ± .04 2.37 ± .13.001% inoculum + 3% CSL 25 .74 ± .04 2.18 ± .12.0005% inoculum + 3% CSL 25 .82 ± .06 2.27 ± .15______________________________________ .sup.a Energy savings are calculated based on the untreated control values .sup.b Standard Deviation .sup.c Fungus did not grow
Example 3
Objective: To study the effect of two levels of corn steep liquor on fungal biomass in liquid medium.
Dry weight determination: We maintained 55% moisture in wood on a wet weight basis during fermentation. For example, the 1500 g wood chips (dry weight basis) in a bioreactor have 1833 g of water added. Therefore, to duplicate the bioreactor's moisture content in a flask, 1833 g of water was added to each 2800 ml flask (total of six flasks). 15 or 45 gram of semi-solid corn steep liquor was added to each flask. Therefore, there were three replicates per treatment.
Each flask was covered with the aluminum foil. These flasks were autoclaved for 20 min. at 121° C. Inoculum was prepared as described in Example 1. The 0.0005% inoculum as used in the bioreactor was added to each flask. These flasks were incubated for 14 days at 27° C.
At harvest, the flasks containing the fungal biomass were decanted and washed with sterile distilled water to remove excess medium from the fungal biomass. Replicates were mixed and fungal biomass was dried overnight in an oven set at 105° C. 15 g corn steep liquor (1%) produced 410 mg dry weight of fungus/flask at harvest, whereas 45 g corn steep liquor (3%) at harvest produced 1060 mg dry weight of fungus/flask (Table 3). These results suggest that a high amount of corn steep liquor increased fungal biomass during fermentation and, therefore, resulted in increased biopulping efficacy of the fungus.
TABLE 3______________________________________Dry weight of CZ-3 strain of Ceriporiopsissubvermispora on sterilized corn steep liquor (CSL) (2-weekincubation). Dry Weight ofTreatments Fungus (mg/flask)______________________________________1% CSL (dry wt. basis) 4103% CSL (dry wt. basis) 1050______________________________________
Because 1% sterilized corn steep liquor and reduced amount of fungal inoculum (0.0005% on a dry weight basis) gave good results, we decided to use this combination in the following experiments. Because the addition of corn steep liquor to control wood chips did not affect our results, no corn steep liquor was added to the control in the subsequent experiments.
Example 4
Objective: To compare haploid strains with that of the best diploid strain of Ceriporiopsis subvermispora (CZ-3).
Wood: As in Example 1
Fungus: Strain CZ-3 of Ceriporiopsis subvermispora gave us good energy savings, but no strength improvements with the use of 1% corn steep liquor and 0.0005% inoculum. This strain was a diploid. In order to save energy and improve paper strength, we started screening haploid strains (single basidiospore isolates) of Ceriporiopsis subvermispora. Five different haploid strains (FP-105752 SS-4, L-14807 SS-1, L-14807 SS-3, L-14807 SS-S, L-14807 SS-10) were obtained from the Center for Forest Mycology Research, USDA Forest Products Laboratory, Madison, Wis. Inoculum was prepared the same way as described in Example 1. The biopulping performance of these haploid strains was compared with that of diploid CZ-3 strain.
Chips preparation and bioreactor inoculation: Same as in Example 1, except that the bioreactors containing wood chips were sterilized with atmospheric steaming for 10 min. or so.
Results: Table 4 reports the results. Diploid strain of Ceriporiopsis subvermispora (CZ-3) saved 15% of electrical energy and improved tear index by 14% compared to the control. All haploid strains performed better than the diploid strain. Two haploid strains L14807 SS-3 and L-14807 SS-5 saved 28-29% electrical energy and increased tear index by 21-22% compared to the control.
TABLE 4______________________________________Energy savings and strength properties duringbiomechanical pulping of loblolly pine chips using .0005%inoculum (dry weight basis) of diploid (CZ-3) and haploidstrains of Ceriporiopsis subvermispora in the presence of 1%corn steep liquor from Corn Products (batch E802) (2-weekincubation). Strength properties Energy Burst Tear savings index indexTreatments (%).sup.a (kN/g) (mNm.sup.2 /g______________________________________Control -- .69 ± .05.sup.b 2.07 ± .13CZ-3 15 .67 ± .05 2.37 ± .09FP-105752 SS-4 22 .68 ± .07 2.36 ± .13L-14807-SS-1 18 .65 ± .05 2.35 ± .13L-14807-SS-3 29 .67 ± .06 2.50 ± .17L-14807-SS-5 28 .63 ± .04 2.53 ± .12L-14807-SS-10 22 .68 ± .05 2.29 ± .13______________________________________ .sup.a Energy savings are calculated based on the untreated control values .sup.b Standard Deviation
These results demonstrate the following:
1. With the use of corn steep liquor and a reduced amount of fungal inoculum, both diploid and haploid strains saved energy and improved paper strength.
2. Two haploid strains gave more energy savings and strength improvement than the diploid strain.
Example 5
Objective: To evaluate the biopulping performance of haploid strain of Ceriporiopsis subvermispora (L-14807 SS-3) on aspen wood chips in the presence of sterilized and unsterilized corn steep liquor.
Wood chips: The aspen wood chips were obtained from aspen logs harvested in the Nicolet National Forest of Wisconsin. Other details are the same as described in Example 1.
Fungus: The details about inoculum preparation have been described in Example 1. A 0.0005% inoculum (dry weight basis) with 1% (dry wood basis) sterilized or unsterilized corn steep liquor was used.
Chips preparation and bioreactor inoculation: In this experiment wood chips were steamed for 10 min. or so for sterilization. One set of bioreactors was incubated for 2 weeks while the other was incubated for 4 weeks at 27° C. Other details have been described in Example 1.
Results: Table 5 reports our results. In the absence of corn steep liquor, fungus did not grow well enough during this dwell time to achieve significant energy savings, as a result consistent with the previous experiment (Example 2). The difference between the addition of sterilized or unsterilized corn steep liquor, compared to the control chips, did not affect the values for energy and strength properties. Fungal pretreatment in the presence of sterilized or unsterilized corn steep liquor saved the same amount of energy in two weeks (13-15%) and in 4 weeks (35-37%) compared to the control. In two weeks, strength properties were not improved regardless of the type of corn steep liquor used. However, in 4 weeks, sterilized and unsterilized corn steep liquor improved burst index by 21-23%, and tear index by 46-48% compared to the control. These results clearly show that unsterilized corn steep liquor can be used during commercial application and, therefore, biopulping process becomes more cost-effective since sterilization is not required.
TABLE 5______________________________________Energy savings and strength properties duringbiomechanical pulping of aspen wood chips using .0005%inoculum (dry weight basis) of L-14803 SS-3 haploid strain ofCeriporiopsis subvermispora (Treatment) in the presence ofsterilized and unsterilized 1% corn steep liquor (CSL) fromCorn Products (batch E802) (2- and 4-week incubation). Strength properties Energy Burst Tear savings index indexTreatments (%).sup.a (kN/g) (mNm.sup.2 /g)______________________________________2-week incubationControl -- 1.01 ± .05.sup.b 2.16 ± .20Treatment (sterilized CSL) 15 1.11 ± .07 2.49 ± .16Treatment (unsterilized CSL) 13 1.11 ± .04 2.37 ± .234-week incubationControl -- 1.08 ± .04 2.14 ± .12Treatment (sterilized CSL) 35 1.33 ± .05 3.13 ± .20Treatment (unsterilized CSL) 37 1.31 ± .07 3.16 ± .14______________________________________ .sup.a Energy savings are calculated based on the untreated control values .sup.b Standard Deviation
Example 6
Objective: To evaluate the biopulping performance of haploid strain of Ceriporiopsis subvermispora (L-14807 SS-3) on loblolly pine chips in the presence of unsterilized corn steep liquor.
Wood chips: Details same as in Example 1
Fungus: The details about inoculum preparation have been described in Example 1. A 0.0005% inoculum (dry weight basis) with 1% (dry wood basis) unsterilized corn steep liquor was used.
Chips preparation and bioreactor inoculation: In this experiment wood chips were steamed for 10 min. or so for sterilization. Control and the inoculated bioreactors were incubated for 2 weeks at 27° C. Other details have been described in Example 1.
Results: Table 6 reports the results. Fungal pretreatment saved a substantial amount of energy (38%) and improved tear index by 51% compared to the control. Addition of sterilized 1% corn steep liquor saved 29% electrical energy and improved tear index by 21% compared to the control (Table 4). These results show that the use of unsterilized corn steep liquor compared to the sterilized corn steep liquor (Example 4) enhanced the biopulping efficacy of haploid strain of the fungus. In a previous experiment (Example 3), enhanced biopulping efficacy was attributed to more fungal biomass in the liquid medium due to increased quantity of corn steep liquor (3% on a dry wood basis). To establish the same relationship between the fungal biomass in the liquid medium and the biopulping efficacy of the fungus in a bioreactor, we determined the effect of unsterilized and sterilized corn steep liquor on the fungal biomass in the liquid medium.
TABLE 6______________________________________Energy savings and strength properties duringbiomechanical pulping of loblolly pine chips using .0005%inoculum (dry weight basis) of L-14803 SS-3 haploid strain ofCeriporiopsis subvermispora (Treatment) in the presence ofunsterilized 1% corn steep liquor from Corn Products (batchE802) (2-week incubation). Strength properties Burst Tear Energy index indexTreatments savings (%).sup.a (kN/g) (mNm.sup.2 /g)______________________________________Control -- .61 ± .05.sup.b 1.81 ± .12Treatment 38 .70 ± .04 2.73 ± .14______________________________________ .sup.a Energy savings are calculated based on the untreated control values .sup.b Standard Deviation
Example 7
Objective: To compare the effect of sterilized corn steep liquor with that of unsterilized corn steep liquor on fungal biomass in liquid medium.
Dry weight determination: 1833 g of water was added to each 2800 ml flask (total flasks four). 30 g of corn steep liquor was added to two of these flasks each containing 15 g of corn steep liquor. Each flask was covered with the aluminum foil. All of these flasks were autoclaved for 20 min. at 121° C. 30 g of unsterilized corn steep liquor was added to the remaining two flasks each containing 1833 g of sterilized water. Inoculum was prepared as described in Example 1. A 0.0005% inoculum as used in the bioreactor was added to each flask.
These flasks were incubated for 14 days at 27° C. At harvest, the flasks containing the fungal biomass were decanted and washed with sterile distilled water to remove excess medium from the fungal biomass. Replicates were mixed and fungal biomass was dried overnight in an oven set at 105° C.
Results: Table 7 records the results. Sterilized corn steep liquor at harvest produced 425 mg dry weight of fungus/flask, whereas unsterilized corn steep liquor at harvest produced only 190 mg dry weight of fungus/flask. These results indicate that a combination of unsterilized corn steep liquor and steamed wood might be responsible for the enhanced biopulping efficacy of the haploid strain of the fungus. Since in the above experiment, unsterilized corn steep liquor produced substantially less fungal biomass than the sterilized corn steep liquor in the liquid medium, we decided to study the effect of other chemicals (sterilized and unsterilized) on fungal biomass in liquid culture first and subsequently on the biopulping performance of the haploid strain (L-14807 SS-3) of the fungus using unsterilized chemicals.
TABLE 7______________________________________Dry weight of L-14807 SS-3 haploid strain ofCeriporiopsis subvermispora on sterilized and unsterilizedcorn steep liquor (CSL) (2-week incubation). Dry weight ofTreatments fungus (mg/flask)______________________________________Sterilized CSL 425Unsterilized CSL 190______________________________________
Example 8
Objective: To study the effect of the use of corn steep liquor on biopulping with other species of white rot fungi on a softwood.
The experiments were performed on loblolly pine chips in accordance with the methods of Example 6 above with utilizing of fungal inoculants of the species Phlebia brevispora (Pb), Phlebia subserialis (Ps), Dichomitus squalens (Ds), Phlebia tremellosa (Pt) and Perenniporia medulla-panis (Pm-p). Five grams per ton of inoculum (dry weight basis) was applied to the loblolly pine chips in the absence and the presence of unsterilized 0.5% corn steep liquor during a two week incubation. Paper was made from the cultured wood chips and the energy savings, burst index, and tear index of the resulting paper was compared to parallel experiments with and without corn steep liquor added as the adjuvant. The results are summarized in the following Table 8. The results demonstrate increased energy savings with use of corn steep liquor.
TABLE 8______________________________________Energy savings and strength properties duringbiomechanical pulping of loblolly pine chips using 5 g perton of inoculum (dry weight basis) of several lignin-degrading fungi in the absence and presence of unsterilized0.5% corn steep liquor (± CSL) (2-week incubation). % savings or improvements over controlFungi CSL Energy Burst Index Tear Index______________________________________Pb HHB 7099 - 12 0 5Pb HHB 7099 + 16 0 13Ps RLG 6074-sp - 25 0 36Ps RLG 6074-sp + 33 37 44Ds MMB 10963-sp - 0 0 0Ds MMB 10963-sp + 18 13 41Pm-p HHB 12172 - 10 0 16Pm-p HHB 12172 + 19 24 34Pt FP 102557-sp - 17 Not determinedPt FP 102557-sp + 21 Not determined______________________________________ Pb: Phlebia brevispora; Ps: Phlebia subserialis; Ds: Dichomitus squalens; Pt: Phlebia tremellosa; Pmp: Perenniporia medullapanis
Example 9
Objective: To study the effect of the use of corn steep liquor on biopulping with other species of white rot fungi on a hardwood.
The experiments were performed on aspen chips in accordance with the methods of Example 6 above with utilizing of fungal inoculants of the species Phlebia brevispora (Pb), Phlebia subserialis (Ps), Hyphodontia setulosa (Hs), and Phlebia tremellosa (Pt). Five grams per ton of inoculum (dry weight basis) was applied to the aspen chips in the absence and the presence of unsterilized 0.5% corn steep liquor during a two week incubation. Paper was made from the cultured wood chips and the energy savings, burst index, and care index of the resulting paper was compared to parallel experiments with and without corn steep liquor added as the adjuvant. The results are summarized in the following Table 9.
TABLE 9______________________________________Energy savings and strength properties duringbiomechanical pulping of aspen chips using 5 g per ton ofinoculum (dry weight basis) of several lignin-degradingfungi in the absence and presence of unsterilized 0.5% cornsteep liquor (± CSL) (2-week incubation). % savings or improvements over controlFungi CSL Energy Burst index Tear Index______________________________________Ps RLG 6074-sp - 0 0 0Ps RLG 6074-sp + 40 0 0Hs FP 106976 - 0 0 0Hs FP 106976 + 36 0 0Pb HHB 7099 - 0 0 0Pb HHB 7099 + 38 0 19Pt FP 102557-sp - 0 0 0Pt FP 102557-sp + 27 0 24______________________________________ Ps: Phlebia subserialis; Hs: Hyphodontia setulosa; Pb: Phlebia brevispora; Pt: Phlebia tremellosa | A method of making a wood pulp is disclosed. The method includes chipping wood into wood chips and then inoculating the wood chips with an inoculum of a white rot fungi and a nutrient adjuvant selected from the group consisting of corn steep liquor, molasses and yeast extract. The wood chips are introduced into a bioreactor and incubated. The incubated wood chips are then pulped. A method of pretreating wood including chipping the wood into wood chips and inoculating the wood chips with an inoculant of the white rot fungi and a nutrient adjuvant selected from the group consisting of corn steep liquor, molasses and yeast extract is also disclosed. A method for producing paper from the treated wood chips is also disclosed. The addition of the nutrient adjuvant dramatically reduces the amount of fungal inoculant needed (by multiple orders of magnitude), to achieve similar results. | 3 |
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This is a Divisional application of U.S. Ser. No. 13/394,605 filed Mar. 7, 2012 which was a 371 of PCT/EP/2010/061748 and claiming priority to DE 10 2009 041 089.9 filed Sep. 10, 2009.
BACKGROUND OF THE INVENTION
[0002] The invention relates to methods for producing cement clinker, having the following steps: preheating calcium carbonate-containing raw meal in a preheating stage which is heated by exhaust gases from a sintering stage which follows in the gas flow direction, deacidifying the preheated raw meal, sintering the deacidified raw meal into cement clinker in a sintering stage, cooling the cement clinker from the sintering stage in a cooling stage which cools the cement clinker by means of a gas.
[0003] In the methods for producing cement which are carried out most often throughout the world, a calcium carbonate-containing initial material in the form of limestone is freed of CO2 formally by the supply of heat and is thereby converted into unslaked lime, calcium oxide, and is subsequently sintered by the supply of even more heat, in the presence of silicate-containing rock, into cement clinker which is composed of various calcium silicate phases and constitutes the principal fraction of customary cement. In this case, heat energy of between 2850 and 3350 kJ is used per kg of cement clinker. The heat quantity required for this purpose is usually generated from the combustion of carbon-containing fuel. Combustion, on the one hand, and the formal freeing of CO2 from the limestone, on the other hand, together form an intensive CO2 source, the released CO2 hitherto being introduced into the free earth's atmosphere. The CO2 emission thereby generated makes an appreciable contribution to the overall anthropogenic CO2 emission on earth. It is known since then that CO2 is the main cause of an anticipated greenhouse effect which leads to the undesirable warming of the earth's atmosphere. The endeavor, therefore, is to reduce the CO2 emission substantially.
[0004] In order to reduce the introduction of CO2 into the earth's atmosphere due to the production of cement, it is necessary to rely on preventing the released CO2 from escaping into the earth's atmosphere by storing it in underground caverns. Such caverns are, for example, natural gas or petroleum deposits which have for the most part been emptied. Since, in the conventional method for producing cement, very large quantities of CO2 occur, which are mixed with even much larger quantities of nitrogen from atmospheric air, storage, along with compressing the exhaust gas and transferring it to the deposit, is scarcely possible in economic terms.
[0005] In the hitherto known method for producing cement, it is customary to fine-grind the calcium carbonate-containing initial material into what is known as raw meal and then first to heat it in a preheater. In the preheater, the raw meal falls in countercurrent to the gas flow direction through the hot exhaust gases of a cylindrical rotary kiln, in order first to heat by the waste heat the large quantities of limestone to be burnt. Depending on the configuration of the plant, there is then provision for deacidifying the raw meal in a cylindrical rotary kiln and sintering it into limestone in one step or for carrying out deacidification and sintering in separate plant parts. The gases which heat the raw meal and are composed of nitrogen, CO2, small quantities of CO, nitrous gases and further combustion gases are then, in many plants, conducted through a heat exchanger to separate the heat still remaining in the exhaust gases and are then released into the free earth's atmosphere.
[0006] Since the exhaust gas quantities occurring in order to prevent CO2 emission are very large, European patent application EP 1 923 367 A1 proposes to modify the hitherto known method for producing cement. According to the proposal of the last-mentioned patent application, preheating and deacidification are to be carried out in spatially separate regions of the plant, the exhaust gases from deacidification being circulated, along with a high degree of enrichment of CO2, so that deacidification is carried out in a CO2 atmosphere. The chemical balance lies in this case on the side of unslaked lime due to the heat introduced. By contrast, as is known, the exhaust gases from a cylindrical rotary kiln are used to preheat the raw meal and are then discarded by being released. In order to utilize the residual heat from the cylindrical rotary kiln exhaust gases after heat exchange with the raw meal, the last-mentioned patent application proposes to cool down the exhaust gas with the aid of a heat exchanger in favor of heating water for energy generation, during which steam occurs in the second circuit of the heat exchanger and is to be used for driving steam turbines.
[0007] The method referred to in the last-mentioned patent application therefore still causes the CO2 occurring during the combustion of carbon-containing fuels to escape into the atmosphere, approximately 40% of the entire fuel burnt in the plant usually being converted in the cylindrical rotary kiln. It would be ideal if the CO2 escaping here could also be captured and stored.
SUMMARY OF THE INVENTION
[0008] The object of the invention, therefore, is to increase further the degree of separation of the CO2 emissions occurring in the overall process, in order thereby to reduce the CO2 emission further.
[0009] The object according to the invention is achieved by combining the exhaust gases from the sintering stage with the exhaust gases from deacidification and by routing the combined exhaust gases in the open gas circuit.
[0010] Since both CO2 gas sources are routed in the open gas circuit, to be precise the occurrence of CO2 during deacidification, together with the occurrence of CO2 from heat generation necessary for this purpose, on the one hand, and the occurrence of CO2 from heat generation for sintering, on the other hand, it is possible to separate and store the entire CO2 emission of a plant for producing cement. Besides, including the exhaust gases from the cylindrical rotary kiln, too, has a further advantage, to be precise that nitrous gases called nitrogen oxides or else NOx, which occur during the upgrading of CO2 in the circuit necessarily reduce the concentration of atmospheric nitrogen in the circuit gas. Since less atmospheric nitrogen is present in the cylindrical rotary kiln during the generation of heat, much less atmospheric nitrogen is also burnt into nitrous gases during combustion. The occurrence of nitrous gases is much more pronounced in the cylindrical rotary kiln than during combustion in the deacidification stage, because oxidative conditions are necessary in the cylindrical rotary kiln for the desired formation of various desired calcium silicate phases as cement clinker, and under these conditions nitrogen is unavoidably oxidized into nitrous gases in the great heat of the cylindrical rotary burner.
[0011] However, combining the exhaust gases from the deacidification stage and the sintering stage is not possible without further changes to the known method. An apparently obvious solution, to be precise simply to include the exhaust gases from the cylindrical rotary kiln additionally into the circuit, is not readily possible for further plant-related reasons, since the exhaust gases from the preheater are used as lifting and drying air in a raw meal mill preceding the plant for producing cement clinker from raw meal. The initial material from which raw meal for producing cement clinker is generated is usually moist, for example because it comes from open cast mining, but also contains hydration water. In order, during preheating, to avoid the energy-intensive heating of entrained water, and also to facilitate the grinding process, using sifters, even during grinding care is taken to ensure that the raw meal is dry by using the preheater exhaust air in the grinding process. The grinding process is not a closed process, which means that there are many places in the grinding process where the initial material is in free contact with the earth's atmosphere during crushing. If, therefore, the exhaust gases from the cylindrical rotary kiln were included in the circuit, these would be absent during the required grinding. As a solution, it would therefore be necessary to seal off the grinding process with respect to infiltrated air, thus demanding a high outlay in terms of very complicated apparatus, or use is made here of a special variation, according to the invention, of the hitherto known method for producing cement.
[0012] So that the heat coming from the preheater for preheating the raw meal can be utilized for drying the initial material, it is proposed, according to the invention, to use an at least two-stage cooler for the ready-burnt cement clinker which cooler has between the two stages, for example, a middle crusher, by means of which gas separation of the two gas circuits is possible. The first stage of the cooler is included in the open gas circuit in which a highly CO2-enriched gas atmosphere is present. However, the second stage of the cooler operates with atmospheric air, as in known plants, the cooler exhaust air of this part being used for lifting and drying the initial material in the grinding stage. However, since the cooler exhaust air of the second grinding stage does not carry sufficient heat with it to dry the entire initial material, the heat from the preheater is used to reheat the cooler exhaust air conducted as grinding circulation air into the grinding circuit, after this cooler exhaust air from the grinding stage is cooled, with moisture from the initial material at the same time being absorbed. The invention therefore makes use of the fact that, on the one hand, in the method according to the invention and in the corresponding plant, heated atmospheric air from the second cooler stage is available, which is not laden with exhaust gases, in particular with CO2, and, on the other hand, the invention utilizes the heat from the preheating stage, which cannot readily be supplied to the grinding stage by being included in a dedicated open circuit, along with the enrichment of the CO2 concentration, because an undesirable introduction of infiltrated air would take place there and would reduce the effectiveness of the method with separation of CO2.
[0013] A particular feature of the method according to the invention is that it is suitable both for the conversion of those plants in which deacidification and sintering take place in a single stage, a longer cylindrical rotary kiln, and for plants in which sintering and deacidification take place is spatially separated plant parts.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The invention is explained in more detail by means of the following figures in which:
[0015] FIG. 1 shows a sketch of a plant according to the invention for carrying out the method according to the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0016] FIG. 1 illustrates a sketch of a flow diagram of a plant 1 according to the invention for producing cement clinker from calcium carbonate-containing initial material, which plant has two essential open gas circuits 5 and 10 separate from one another. The calcium carbonate-containing initial material for producing cement clinker runs through these two separate open gas circuits 5 and 10 , at the same time traveling in the gas flow direction in the first open gas circuit 5 and for the most part flowing through the plant part in counter current in the second open gas circuit 10 , the material flow of the calcium carbonate-containing initial material in the gas circuit 10 therefore being for the most part opposite to the gas flow direction.
[0017] A gas stream for drying the calcium of carbonate-containing initial material and for crushing it into raw meal in a grinding stage 15 preceding a preheating stage 35 flows in the first open gas circuit 5 which is separated from the second open gas circuit 10 , the preheating stage 35 following the grinding stage 15 in the material flow direction of the plant 1 .
[0018] By contrast, a gas stream, in which the calcium carbonate-containing raw meal from the first open gas circuit 5 is converted into cement clinker, flows in the second open gas circuit 10 of the plant 1 .
[0019] In the overall plant 1 , to produce cement clinker from calcium carbonate-containing raw meal, the calcium carbonate-containing initial material, usually a mixture, still moist from open cast mining, of limestone and of silicate-containing rock, is first fed to a grinding stage 15 at the feed point 20 a. The sketch illustrates a vertical meal as a grinding stage 15 , but, depending on the material properties of the calcium carbonate-containing initial material, roller presses for high-pressure crushing, or circulatory grinding plants with various grinding and sifting stages are also suitable as a grinding stage 15 . In the grinding stage 15 , the calcium carbonate-containing initial material is simultaneously crushed into calcium carbonate-containing raw meal to an extent such that it has a meal-like consistency and is dried by the dry cooler exhaust air 23 coming from the right at the point 22 of the grinding stage 15 in the sketch. In this case, the calcium carbonate-containing initial material to be crushed is lifted in the grinding stage 15 by the dry cooler exhaust air 23 introduced as grinding circulation air 23 ′, sifters, not depicted here, also being present within the grinding stage 15 and discharging the calcium carbonate-containing raw meal out of a grinding circuit only beyond a specific degree of fineness. After the calcium carbonate-containing raw meal has left the grinding stage 15 at the point 25 with the aid of the partially dry cooler exhaust air 23 and partially moist grinding circulation air 23 ′, it is separated from the then cooled and moist grinding circulation air 23 ′ in a cascade 26 of dust separators. At this point, the path of the calcium carbonate-containing raw meal separates from the cooled and moist grinding circulation air 23 ′ located in the open gas circuit 5 .
[0020] The largely dust-free moist grinding circulation air 23 ′ leaves the cascade 26 of dust separators in an upward direction and is compressed by a compressor 27 in order to compensate for the pressure drop in the following gas/gas heat exchanger 30 and the part gas outlet 28 . Since part of the moist grinding circulation air 23 ′ is extracted at the point 28 b between the compressor 27 and gas/gas heat exchanger 30 , in order to discard the moisture from the calcium carbonate-containing initial material together with the extracted moist grinding circulation air 23 ′, and also to keep constant the gas quantity which is located in the first gas circuit 5 and which is replaced continually by new atmospheric air from the cooler air supply 28 a. However, gas loss and gas introduction in the first gas circuit 5 not only take place as a result of the extraction of the moist grinding circulation air 23 ′ at the point 28 b and the cooler air supply 28 a, but also by means of the introduction and discharge of infiltrated air in the grinding stage 15 . Since infiltrated air is introduced into the first gas circuit 5 in the grinding stage 15 , but also moist grinding circulation air 23 ′ escapes from the first gas circuit 5 , only as much moist grinding circulation air 23 ′ is extracted between the compressor 27 and gas/gas heat exchanger 30 , as mentioned above, as is necessary for the gas quantity located in the gas circuit 5 to remain constant, since it is constantly replaced by warm and still dry cooler exhaust air 23 at the point 22 , the dry cooler exhaust air 23 coming from the second stage 45 b of the two-stage cooler 45 in which the almost ready cement clinker is cooled by means of atmospheric air. This atmospheric air is introduced into the plant at the point 28 a. The open gas circuit 5 described here is open, which means that new gas, cooler exhaust air 23 , is introduced into the open gas circuit 5 and gas, moist grinding circulation air 23 ′, leaves the open gas circuit 5 . In this case, in the context of this disclosure, an “open gas circuit” is understood to mean a gas circuit which is continuously fed with gas and freed of gas, and also a gas circuit which is fed with gas and freed of gas batchwise or interruptedly.
[0021] In the gas/gas heat exchanger 30 , the remaining fraction of the cooled and moist grinding circulation air 23 ′ is heated by the heat which, together with the combined exhaust gases 32 from the preheating stage 35 , escapes from the preheating stage 35 in the second open gas circuit 10 . In this case, the combined exhaust gases 32 are freed in a dust separator 33 of raw meal and of cement clinker particles from the right-hand plant part which have possibly passed into the dust separator 33 , and the combined exhaust gases 32 run in the second open gas circuit 10 through the gas/gas heat exchanger 30 where they discharge the heat transported by them to the cooled grinding circulation air 23 ′ into the first gas circuit 5 .
[0022] The combined exhaust gases 32 and the cooled moist grinding circulation air 23 ′ which flow through the gas/gas heat exchanger 30 differ greatly from one another in their composition, because the moist grinding circulation air 23 ′ largely has the composition of atmospheric air, with the exception of the moisture absorbed from the calcium carbonate-containing initial material. By contrast, the combined exhaust gases 32 have a very high CO2 fraction which comes, on the one hand, from the gas fraction of the deacidification gas CO2 32 a for the deacidifying reaction of the limestone according to CaCO3⇄CaO+CO2 and, on the other hand, from the gas fraction of the combustion gas 32 b which comes from the combustion of carbon-containing fuel according to C+O2⇄CO2 in the burner 56 of the sintering stage, here a cylindrical rotary kiln 40 , and finally from the gas fraction of the combustion gases 32 c from the combustion of carbon-containing fuel according to the above equation in the burner 60 of the calciner 55 .
[0023] After the reheated moist grinding circulation air 23 ″ has left the gas/gas heat exchanger 30 , it flows to the point 41 where it is combined with the fresh dry cooler exhaust air 23 , of virtually the same temperature, which flows in from the right out of the second stage 45 b of the two-stage cooler 45 , after the dry cooler exhaust air 23 has been freed by the dust separator 46 of cement clinker dust from the two-stage cooler 45 , since the cement clinker dust coming from the two-stage cooler 45 is highly abrasive and would prematurely wear the grinding stage 15 by abrasion. The heated moist grinding circulation air 23 ″ and the fresh cooler exhaust air 23 are then compressed by a compressor 47 , and the gas circuit 5 of the dry cooler exhaust air 23 , of the moist grinding circulation air 23 ′ and of the grinding circulation air 23 ″ having virtually the same composition as atmospheric air is closed at this point.
[0024] The above-described calcium carbonate-containing raw meal which has been separated by the dust separator 26 from the grinding circulation air 23 ′ used as drying and lifting gas is fed by a suitable transport device, not shown here, to the preheating stage 35 , the calcium carbonate-containing raw meal running through the preheating stage 35 from the top downward in countercurrent, at the same time running through the cyclone stages 48 , 49 and 50 and at the same time being heated to near the temperature of the combined exhaust gases 32 which the combined exhaust gases 32 have in the second lowest cyclone stage 50 of the preheating stage 35 . The heated calcium carbonate-containing raw meal falls from the second lowest cyclone stage 50 into the lower part of the calciner 55 and is lifted by the exhaust gases from the cylindrical rotary kiln 40 , since in the cylindrical rotary kiln 40 , a burner 56 heats the cylindrical rotary kiln 40 by combusting a mixture 57 of primary fuel with primary air, the primary air ideally being oxygen-enriched and correspondingly nitrogen-depleted air. In addition to the exhaust gases from the combustion of the mixture 57 , secondary air 58 from the first stage 45 a of the two-stage cooler 45 is forced into the cylindrical rotary kiln 40 and leaves the cylindrical rotary kiln 40 via the calciner 55 together with the exhaust gases 32 b from combustion.
[0025] In addition to the exhaust gases 32 b and the secondary air 58 from the cylindrical rotary kiln 40 , the tertiary air 59 which likewise comes from the first stage 45 a of the two-stage cooler 45 , also lifts the heated calcium carbonate-containing raw meal out of the second lowest cyclone stage 50 in the calciner 55 . There, the calcium carbonate-containing raw meal is deacidified in an endothermic reaction in the additional heat from the burner 60 which burns a mixture 61 of secondary fuel and of an oxygen-enriched and correspondingly nitrogen-depleted air, gaseous CO2 being released and CaO remaining as a solid suspended in the combined exhaust gases 32 . The combined exhaust gases 32 are therefore composed of the exhaust gases 32 b and of the secondary air 58 from the cylindrical rotary kiln 40 , of the tertiary air 59 , of exhaust gases 32 c from the combustion of the mixture 61 and of released deacidification exhaust gas CO2 32 a from the deacidifying reaction. For the complete burnout of the mixture 61 , which ideally oxidizes flamelessly in the calciner 55 , the suspension composed of the combined exhaust gases 32 and of the deacidified raw meal is intimately mixed in a swirl chamber 62 before it is conducted into the lowest cyclone stage 63 . In this lowest cyclone stage 63 , the combined exhaust gases 32 are separated from the largely deacidified raw meal from the calciner 55 .
[0026] The largely deacidified raw meal subsequently leaves the lowest cyclone stage 63 and falls from there into the cylindrical rotary kiln entry chamber 65 where it passes, protected from the rising exhaust gases of the cylindrical rotary kiln 40 , into the cylindrical rotary kiln 40 , is sintered there into cement clinker and then leaves the cylindrical rotary kiln 40 and falls into the first stage 45 a of the two-stage cooler 45 . In the first stage 45 a of the two-stage cooler 45 , the here coarse-grained sintered cement clinker is cooled by the combined exhaust gases 32 recirculated in the gas circuit 10 and cooled in the heat exchanger 30 , the combined exhaust gases 32 heating up sharply and passing, on the one hand, as secondary air 58 into the cylindrical rotary kiln 40 and, on the other hand, as tertiary air 59 into the calciner 55 and thus leaving the first stage 45 a of the two-stage cooler 45 again. In this case, the two-stage cooler 45 separates the gases located in the first stage 45 a from the gases in the second stage 45 b of the two-stage cooler 45 . Such separation is possible, for example, by means of what is known as a middle crusher, as a gas separation stage, in which the still coarse-grained clinker has to pass through a clinker crusher 45 c, the open gas circuits 5 and 10 being largely separated by a partition. A minimal gas slip, which occurs due to gas entrained by the coarse cement clinker to be crushed, has in this case to be taken into account.
[0027] The combined exhaust gases 32 which are separated from the largely deacidified raw meal in the lowest cyclone stage 63 run subsequently through the cyclone stage 50 , thereafter the cyclone stage 49 and finally the cyclone stage 48 . After the cyclone stages 50 , 49 and 48 , the combined exhaust gases run through the dust separator 33 , and from there from the gas/gas heat exchanger 30 which, as described above, transfers the heat from the combined exhaust gases 32 to the moist and cooled grinding circulation air 23 ′, and the combined exhaust gases 32 are compressed in a compressor 70 to compensate the pressure loss hitherto experienced and from their pass via a part gas outlet 75 back into the first stage 45 a of the two-stage cooler 45 where the gas circuit 10 is closed.
[0028] The highly CO2-enriched gas located in the gas circuit 10 leaves the plant 1 at the point 57 b / 61 b through the part gas outlet 75 , this gas being delivered constantly by the exhaust gases 32 , 32 a, 32 b, 32 c from the combustion of the mixtures 57 and 61 in the burners 56 and 60 and by the deacidifying reaction of the carbonate-containing raw meal.
[0029] Only as much highly CO2-enriched combined exhaust gases 32 is taken off from the part gas outlet 75 as is introduced into the open gas circuit 10 as a result of the introduction of combustion and deacidification gases, in order to keep the gas quantity in the gas circuit 10 constant. In this case, in the context of this disclosure, as regards the gas circuit 10 too, an “open gas circuit” is understood to mean a gas circuit which is continuously fed with gas and freed of gas, and also a gas circuit which is fed with gas and freed of gas batchwise or interruptedly. The gases taken off in the part gas outlet 75 are then discarded by storage, instead of being released into the atmosphere.
[0030] A particular feature of the plant described here and of the corresponding method is that, instead of the exhaust gases from the preheater being used to dry the initial material in a preceding grinding stage, exhaust air from a clinker cooler is used for the almost ready cement clinker, the heat from the preheater being discharged to this cooler exhaust air not laden with harmful exhaust gases. The exhaust gases coming from the preheater are routed in the circuit of the plant, with the result that the degree of separation of the overall CO2 occurring in the process is greatly increased, as compared with known plants for producing cement clinker with separation of the CO2 occurring.
[0031] As is apparent from the foregoing specification, the invention is susceptible of being embodied with various alterations and modifications which may differ particularly from those that have been described in the preceding specification and description. It should be understood that I wish to embody within the scope of the patent warranted hereon all such modifications as reasonably and properly come within the scope of my contribution to the art.
[0000]
LIST OF REFERENCE SYMBOLS
1
Plant
5
Open gas circuit
10
Open gas circuit
15
Grinding stage
20a
Feed point
22
Point, incoming cooler exhaust
air
23
Cooler exhaust air, dry
23′
Grinding circulation air, moist
23″
Grinding circulation air, moist,
heated
25
Point, outgoing raw meal
26
Cascade, dust separator
27
Compressor
28
Part gas outlet
28a
Cooler air supply
28b
Point, outgoing cooler exhaust
air
30
Gas/gas heat exchanger
32
Combined exhaust gases
32a
Deacidification gas CO 2
32b
Combustion exhaust gas
32c
Combustion exhaust gas
33
Dust separator
Preheating stage
Cylindrical rotary kiln
41
Point, combination of cooler
exhaust gases 23, 23′
45
Two-stage cooler
45a
First stage
45b
Second stage
45c
Clinker crusher, gas
separation stage
46
Dust separator
47
Compressor
48
Cyclone stage
49
Cyclone stage
50
Cyclone state
55
Calcinor
56
Burner
57
Mixture, fuel
57b
Point, outgoing gas
58
Secondary air
60
Burner
61
Mixture, fuel
61b
Point, outgoing gas
62
Swirl chamber
63
Cyclone stage
65
Cylindrical rotary kiln entry
chamber
70
Compressor
Part gas outlet | A plant for producing cement clinker from calcium carbonate-containing raw meal. A preheating stage preheats the raw meal, which preheating stage is heated by exhaust gases from a following sintering stage. A stage is provided for deacidification and sintering of the raw meal. A cooling stage for the sintered meal is of at least two-stage design and has a gas separation stage for separating exhaust gases from the deacidification and sintering stage which is routed in a first gas circuit from the cement clinker cooling gas. A gas/gas heat exchanger is arranged downstream of the preheating stage in the gas flow direction, through which heat exchanger heat from the combined exhaust gases which leave the preheating stage is transferred into a gas, extracted from the gas for cooling the cement clinker, routed in a second gas circuit, for drying the raw meal in a preceding grinding stage. | 8 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims priority from U.S. Provisional Application Serial No. 60/345,864 filed Nov. 7, 2001.
BACKGROUND OF THE INVENTION
[0002] The present invention generally relates to a method and apparatus for producing identification (ID) cards using a photosensitive imaging system employing microcapsules. In accordance with one aspect of the invention, ID cards are produced by translating an image containing identifying indicia into a latent image on an appropriate photosensitive donor sheet, pressure developing the latent image, forming a full color print of the image on a developer sheet, laminating an ID card substrate in registration with the image to the developer sheet and die cutting the laminated article to produce an ID card. The image preferably includes unique information useful in identifying the card holder such as a photograph, fingerprint, signature, description, name, etc. The identifying indicia may be combined with non-variable information including background printing, card issuer data, logos, security features, etc. An ID card produced in accordance with certain embodiments of the present invention provides a secure identification card which is inherently more durable and less susceptible to delamination and tampering because the image is directly laminated to the ID card substrate.
[0003] The photosensitive imaging system useful in accordance with the present invention employs microcapsules containing a photosensitive composition in the internal phase. Photosensitive imaging systems employing microencapsulated radiation sensitive compositions are the subject of U.S. Pat. Nos. 4,399,209; 4,416,966 and 4,440,846. These imaging systems are characterized in that an imaging sheet including a layer of microcapsules containing a photosensitive composition in the internal phase is image-wise exposed to actinic radiation. In the most typical embodiments, the photosensitive composition is a photopolymerizable composition including a polyethylenically unsaturated compound and a photoinitiator and is encapsulated with a color former. The exposure image-wise hardens the internal phase of the microcapsules. Following exposure, the imaging sheet is subjected to a uniform rupturing force by passing the sheet through the nip between a pair of pressure rollers. U.S. Pat. No. 4,399,209 discloses a transfer system in which the imaging sheet is assembled with a developer sheet prior to being subjected to the rupturing force. Upon passing through the pressure rollers in contact with the developer sheet, the microcapsules image-wise rupture and release the internal phase whereupon the color former migrates to the developer sheet where it reacts with a developer and forms a color image. The imaging system can be designed to reproduce monochromatic, polychromatic or full color images.
[0004] Identifying information for the ID card may be collected by using a scanner, camera, video camera, digital camera, personal computer including a keyboard, mouse or other image or data input device. Imaging systems for recording an image from a video signal are well known and described, for example, in U.S. Pat. Nos. 5,140,428 and 5,223,960 to Goldstar, U.S. Pat. Nos. 5,128,773 and 5,189,468 to Fuji, U.S. Pat. No. 4,935,820 to 3M and U.S. Pat. No. 4,816,846 to AT&T. Such patents generally teach the use of a liquid crystal display (LCD) and/or a cathode ray tube (CRT) to produce a latent image on a photosensitive medium.
SUMMARY OF THE INVENTION
[0005] The present invention relates to a method and apparatus for producing identification (ID) cards using a photosensitive imaging system employing microcapsules. In accordance with one aspect of the invention, identification cards are produced by a method comprising the steps of:
[0006] (a) providing a photosensitive imaging media comprising a developer material and a plurality of microcapsules encapsulating a photohardenable composition and a color former;
[0007] (b) image-wise exposing the plurality of microcapsules to actinic radiation to form a latent image;
[0008] (c) developing the image; and
[0009] (d) laminating an ID card substrate to the image to form an identification card comprising an image, wherein the image contains identifying information.
[0010] In accordance with another embodiment of the present invention, an image containing identifying indicia is translated into actinic radiation capable of image-wise exposing a suitable photosensitive donor imaging sheet, the exposed donor sheet is developed to provide a full color print of the image on the developer sheet, an ID card substrate in registration with the image is laminated to the developer sheet and the laminated article is die cut to produce an ID card. The present invention is particularly advantageous where a photosensitive layer comprising microcapsules containing a photosensitive composition in the internal phase is image-wise exposed to actinic radiation and subjected to a uniform rupturing force whereupon the microcapsules rupture and image-wise release the internal phase which reacts with a developer material to produce an image therein. The image, containing identifying information, is preferably protected by laminating an ID card substrate to the image bearing surface of the developer sheet. Finished ID cards are produced by die cutting the laminated article to the desired dimensions.
[0011] According to yet another embodiment of the invention, there is described a method for producing identification cards using a photosensitive imaging system containing microcapsules, the method comprising the steps of image-wise exposing a photosensitive pressure-sensitive donor sheet to actinic radiation to form a latent image thereon, juxtaposing the donor sheet to a developer sheet, subjecting the juxtaposed sheets to pressure to develop the latent image, thereby forming a full color print of the image on the developer sheet, laminating an ID card substrate in registration with the image to the developer sheet and die cutting the laminated article to produce a finished ID card comprising a full color image containing identifying information regarding the cardholder.
[0012] In accordance with another embodiment of the invention, an apparatus for producing ID cards is described. The apparatus comprises: an exposure means for image-wise exposing a photosensitive donor sheet to actinic radiation to form a latent image thereon, the image comprising personalized information; a pressure developer means for pressure developing the latent image on the exposed donor sheet and forming an image on a developer sheet; lamination means for laminating an ID card substrate in registration with the image to the developer sheet; and a die for die cutting the laminated article to produce a finished ID card.
[0013] Particular aspects of the invention will become apparent from the following description and the accompanying drawing.
BRIEF DESCRIPTION OF THE DRAWING
[0014] The FIGURE is a schematic diagram of an apparatus for making an ID card according to one embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0015] All documents cited are, in relevant part, incorporated herein by reference; the citation of any document is not to be construed as an admission that it is prior art with respect to the present invention.
[0016] The ID system of the present invention utilizes an apparatus that has a small footprint and can be used to generate photograph-like quality ID cards quickly and on-site. Typical examples of ID card applications include bank cards (e.g., credit cards, debit cards, etc), driving licenses, national ID cards, student ID cards, passports, clearance cards, smart cards, etc. ID cards prepared in accordance with certain embodiments of the present invention are advantageous in that the image is directly laminated to the ID card substrate. Any attempt at tampering or alteration would destroy the personalized information as well as the background information that identifies the cardholder. Since the personalized information is a part of the laminate structure, the photographic image cannot be removed and replaced without destroying the card because the image on the developer sheet is directly laminated to the ID card substrate.
[0017] Referring to the accompanying drawing, a detailed description will be given for an apparatus and method for producing a secure ID card using a photosensitive media.
[0018] The FIGURE is a diagrammatic side view of an apparatus 10 for making an ID card in accordance with the present invention. The apparatus 10 includes a donor unwind 12 and a donor rewind 14 , wherein a photosensitive donor sheet 16 , in the form of a continuous web, rolled around the donor unwind 12 is unrolled and is conveyed along a path and is rewound on donor rewind 14 .
[0019] An exposure unit 18 is disposed downstream of the donor unwind 12 with respect to the direction in which the donor sheet 16 is conveyed, wherein the donor sheet 16 is image-wise exposed to actinic radiation preferably corresponding to a digitized image containing personalized information. The exposure unit 18 in the FIGURE includes a light source 18 a and a source image 18 b wherein light emitted from the light source 18 a passes through the source image 18 b to illuminate the photosensitive donor sheet 16 . In accordance with other embodiments, the exposure unit may include various devices for directly image-wise exposing the donor sheet to actinic radiation. Examples of actinic radiation sources include, but are not limited to, LED's, liquid crystal arrays, electroluminescent lamps, light emitting plasma and laser devices and other light emitting elements.
[0020] Apparatus 10 also includes a developer unwind 20 and a developer rewind 22 , wherein a developer sheet 24 , in the form of a continuous web, rolled around the developer unwind 20 is unrolled and is conveyed along a path and is rewound on developer rewind 22 . Disposed downstream of the exposure unit 18 is a pressure developing unit 26 comprising a pair of developer rollers 28 , 30 . The developer rollers 28 , 30 bring the donor sheet 16 into facial contact with the developer sheet 24 and subject the donor sheet 16 and developer sheet 24 to a uniform rupturing force whereupon the photosensitive microcapsules in the donor sheet rupture and image-wise release the internal phase which reacts with the developer material to produce an image on the developer sheet 24 . The donor sheet 16 is conveyed along a path around developer roller 28 and is rewound on donor rewind 14 .
[0021] The developer sheet 24 with a visible image therein is conveyed along a path around developer roller 30 in a direction toward the developer rewind 22 . In the conveying path of the developer sheet 24 , an ID card substrate feed system 32 is disposed for feeding ID card substrate 34 to the imaged surface of the developer sheet 24 in registration with the visible image. Downstream of the ID card substrate feed system 32 is a lamination unit 36 for laminating ID card substrate 34 on the image formed surface of the developer sheet 24 to produce a laminated article. The lamination unit 36 comprises a pair of laminating rollers 38 , 40 having a nip therebetween allowing passage of the ID card substrate 34 and the developer sheet 24 therethrough when the rollers 38 , 40 are rotated. The laminating rollers 38 , 40 may be heated to facilitate lamination or, in the case of thermosetting or thermoplastic adhesives, cause activation of the adhesive. Alternatively, a preheat unit may be provided before the lamination unit to heat the ID card substrate and developer sheet to the desired temperature. Heating of the media with a preheat unit can be accomplished using an oven, heated forced air, IR, thermal head, heating strip or plate, etc. In cases where the imaging media is heated during lamination to activate a thermally activated adhesive, the media is typically laminated at a temperature of from about 70° C. to 125° or higher, preferably around 100° C.
[0022] Disposed downstream of the lamination unit 36 is a die cutter 42 for die cutting the laminated article comprising the ID card substrate 34 and the imaged developer sheet 24 to produce finished ID cards 44 of the desired dimensions which are separated from the developer matrix 46 which is rewound on developer rewind 22 . Preferably, the ID card substrate 34 as supplied to the ID card feed system 32 , is precut to the appropriate dimensions for the finished ID card such that the die cut operation is limited to precision cutting of the developer sheet 24 to the same dimensions as the ID card substrate 34 . In accordance with a preferred embodiment of the present invention, the developer sheet comprises a clear coating of developer material on a transparent substrate, preferably light-transmissive polyester or polyolefin such as polypropylene, polyethylene, etc. Accordingly, the image on the ID card can be viewed through the developer sheet against the ID card substrate backing. The image is sandwiched between the ID card substrate and the developer sheet thereby providing protection for the image against elements which could damage the image as well as producing a secure ID card which is resistant to tampering and alteration.
[0023] The exposure producing elements useful in this invention are any elements or other sources of radiation which are capable of producing modulated light in an array of colors or the light from the exposure producing elements such as light emitting diodes, liquid crystal display panels or projectors, cathode ray tubes, fiber optics, lasers, light bulbs, etc. may pass through a color producing element, e.g., lenses, crystals, LCD's, etc. The light from the exposure producing elements may be time modulated, intensity modulated, etc. to produce any number or variety of colors. Preferably, the light producing elements are time modulated LED's and, most preferably, colored LED's. Satisfactory colored prints have been obtained using red, green and blue LED's.
[0024] The imaging system described above is especially suitable for use in the present invention for exposure using a liquid crystal array or light emitting diodes driven by an electronic signal for the reproduction of images from a computer, digital camera, camera, scanner, video cassette recorder, camcorder, or the like. Personalized or identifying information and background information may be captured and processed using a variety of techniques. A Charge Couple Device (CCD) scanner may be used to capture signatures, logos, fingerprints, etc., a video camera may be used to capture a photograph and a keyboard, mouse or other input device may be used to enter related data such as date of birth, age, height, etc. The information from all of the devices may be captured and converted into one or more digital images for output to the photosensitive imaging system.
[0025] The ID card substrate may comprise any material typically used for construction of ID cards. The substrate may be transparent or reflective. Examples of ID card substrates useful in the present invention include polycarbonate, polyvinyl chloride, polyethylene, polystyrene, polyester, synthetic papers, etc. Preferably, the ID card substrate is precoated with a laminating adhesive which bonds to the developer sheet under heat and/or pressure to produce the laminated card of the invention. In a preferred embodiment, the adhesive is applied over substantially the entire face of the ID card substrate to securely adhere the substrate to the developer sheet. Preferred adhesives include pressure sensitive and thermally activated (thermosetting or thermoplastic adhesives). Specific examples of pressure sensitive adhesives include hot melts, water borne, solvent borne, etc. Preferred examples of pressure sensitive adhesives include acrylics such as 300 adhesive from 3M Company, S2001 from Avery Dennison. Examples of commercially available thermally activated adhesives include Waytek W60 and W35 and Dow Chemical Integral 801 and DAF-709. These thermally activated adhesives are advantageous because they are non-tacky at room temperatures and become tacky at or above the activation temperature typically from about 70° C. to 125° or higher, preferably around 100° C. Accordingly, ID card substrates with a thermally activated adhesive can be stacked without blocking or sticking together, thereby facilitating processing and handling. UW and EB curable adhesives may also be useful. A preferred example of a UV curable hot melt pressure sensitive adhesive is RC 21151 from Novamelt Company.
[0026] The photosensitive imaging system useful in accordance with one aspect of the present invention employs a transfer imaging system comprising a donor sheet and a developer sheet. The donor sheet is coated with a composition including microcapsules containing a photosensitive composition in the internal phase. These imaging systems are characterized in that an imaging sheet including a layer of microcapsules containing a photosensitive composition in the internal phase is image-wise exposed to actinic radiation. In the most typical embodiments, the photosensitive composition is a photopolymerizable composition including a polyethylenically unsaturated compound and a photoinitiator and is encapsulated with a color former. The exposure image-wise hardens the internal phase of the microcapsules. Following exposure, the donor sheet, in contact with a developer sheet, is subjected to a uniform rupturing force by passing the sheets in facing relationship through the nip between a pair of pressure rollers. Upon passing through the pressure rollers in contact with the developer sheet, the microcapsules image-wise rupture and release the internal phase whereupon the color former migrates to the developer sheet where it reacts with a dry developer and forms a color image. The imaging system can be designed to reproduce monochromatic, polychromatic or full color images.
[0027] The photosensitive imaging system in accordance with another embodiment of the present invention may be a self-contained imaging system comprising a support and an imaging layer containing photosensitive microcapsules and a developer material. In accordance with this embodiment, the photosensitive imaging media may be embodied in a self-contained copy sheet in which the encapsulated chromogenic material and the developer material are co-deposited on one surface of a single support as one layer or as two interactive layers or they are deposited on two supports in layers which can interact when the supports are juxtaposed. The self-contained sheet may have a protective coating on the surface of the imaging layer as described in U.S. patent application Ser. No. 09/761,014 filed Jan. 16, 2001. In the case of a self-contained sheet, the self-contained sheet is imagewise exposed to actinic radiation and the image developed by passing the self-contained sheet through the pressure developing unit 26 comprising a pair of developing rollers 28 , 30 . The image develops on the self-contained sheet. Since a separate developer sheet is not required, the self-contained sheet basically follows the path of the donor sheet in the FIGURE.
[0028] Lamination of the self-contained image to the ID card substrate may be effected by providing the ID card substrate with a laminating adhesive or by providing an adhesive layer on the surface of the self-contained sheet. In accordance with one embodiment, the self-contained sheet includes a thermally activated (thermosetting or thermoplastic) adhesive layer overlying the imaging layer. The thermosetting or thermoplastic adhesive layer is not tacky until heated to the activation temperature for the adhesive and may function as a protective coating for the imaging layer prior to activation.
[0029] The imaging systems of the present invention utilize microcapsules to carry the image forming components. The operational center of the imaging system is the encapsulate or internal phase of the coating composition. The internal phase comprises a chromogenic material and a photohardenable composition.
[0030] The internal phase preferably includes a diisocyanate or polyisocyanate compound which functions as a pre-wall reactant. As is known in the art, the polyisocyanate compound is capable of reacting with the water from the aqueous phase by polycondensation to form a thin layer of a polyurea polymer around the internal phase. A particularly preferred polyisocyanate is Desmodur N-100, a biuret of hexamethylene diisocyanate and water available from Mobay Chemical Company. Other isocyanates, such as SF-50, manufactured by Union Carbide may be used in this invention. The polyisocyanate is typically added in an amount of about 2 to 15 parts per 100 parts of internal phase.
[0031] Typically, the photosensitive composition includes a photoinitiator and a substance which undergoes a change in viscosity upon exposure to light in the presence of the photoinitiator. That substance may be a monomer, dimer, oligomer or mixture thereof which is polymerized to a higher molecular weight compound or it may be a polymer which becomes cross-linked.
[0032] Typically, the substance which undergoes a change in viscosity is a free radical addition polymerizable or crosslinkable compound. The most typical example of a free radical addition polymerizable or crosslinkable compound useful in the present invention is an ethylenically unsaturated compound and, more specifically, a polyethylenically unsaturated compound. These compounds include both monomers having one or more ethylenically unsaturated groups, such as vinyl or allyl groups, and polymers having terminal or pendant ethylenic unsaturation. Such compounds are well known in the art and include acrylic and methacrylic esters of polyhydric alcohols such as trimethylolpropane, pentaerythritol, and the like; and acrylate or methacrylate terminated epoxy resins, acrylate or methacrylate terminated polyesters, etc. Representative examples include ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate (TMPTA), pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hydroxypentacrylate (DPHPA), hexanediol-1,6-dimethacrylate, and diethylene glycol dimethacrylate.
[0033] The radiation curable or depolymerizable material usually makes up the majority of the internal phase. A radiation curable material must be present in an amount sufficient to immobilize the chromogenic material upon exposure. Typically these materials constitute 40 to 99 wt % of the internal phase (based on the weight of the oil solution containing the chromogen, the photosensitive composition and the carrier oil when present).
[0034] In some embodiments, it has been found desirable to dilute the photosensitive composition with a carrier oil to improve half-tone gradation. In these cases a carrier oil is present in the amounts disclosed below and the aforesaid materials make up to 40 wt % of the internal phase.
[0035] The chromogenic materials used in the present invention are those chromogenic materials conventionally used in carbonless paper. In general, these materials are colorless electron donating type color formers which react with a developer compound to generate a dye. Representative examples of such color formers include substantially colorless compounds having in their partial skeleton a lactone, a lactam, a sultone, a spiropyran, an ester or an amido structure. Specifically, there are triarylmethane compounds, bisphenylmethane compounds, xanthene compounds, thiazine compounds, spiropyran compounds and the like. Typical examples of useful color formers include Crystal Violet lactone (CVL), benzoyl leuco methylene blue (BLMB), Malachite Green Lactone, p-nitrobenzoyl leuco methylene blue, 3-dialkylamino-7-dialkylamino-fluoran, 3-methyl-2,2′-spirobi(benzo-f-chrome), 3,3-bis(p-dimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2dimethylindole-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-methylindole-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-phenylindole-3-yl)phthalide,3,3-bis(1,2-dimethylindole-3-yl)-5-dimethylaminophthalide, 3,3-bis-(1,2-dimethylindole-3-yl)6-dimethylaminophthalide, 3,3-bis-(9-ethylcarbazole-3-yl)-5-dimethylaminophthalide, 3,3-bis(2-phenylindole-3-yl)-5-dimethylaminophthalide, 3-p-dimethylaminophenyl-3-(1-methyl pyrrole-2-yl)-6-dimethylaminophthalide, 4,4′-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl leuco Auramine, N-2,4,5-trichlorophenyl leuco Auramine, Rhodamine-B-anilinolactam, Thodamine(p-nitroanilino)lactam, Rhodamine-B-(p-chloroanilino)lactam, 3-dimethylamino-6-methoxyfluoran, 3-diethylamino-7-methoxyfluoran, 3-diethylamino-7-chloro-6-methylfluoroan, 3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-7-(acetylmethylamino)fluoran, 3-diethylamino-7-(dibenzylamino)fluoran, 3-diethylamino-7-(methylbenzylamino)fluoran, 3-diethylamino-7-(chloroethylmethylamino)fluoran, 3-diethylamino-7-(diethylamino)fluoran, 3-methyl-spiro-dinaphthopyran, 3,3′-dichloro-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho-(3-methoxybenzo)-spiropyran, 3-propyl-spirodibenzoidipyran, etc. Mixtures of these color precursors can be used if desired. Also useful in the present invention are the fluoran color formers disclosed in U.S. Pat. No. 3,920,510, which is incorporated by reference. In addition to the foregoing dye precursors, fluoran compounds such as disclosed in U.S. Pat. No. 3,920,510 can be used. In addition, organic compounds capable of reacting with heavy metal salts to give colored metal complexes, chelates or salts can be adapted for use in the present invention.
[0036] In accordance with the invention, the chromogenic material is incorporated in the internal phase in an amount sufficient to produce a visible image of the desired density upon reaction with the developer. In general, these amounts range from approximately 0.5 to about 20.0 percent based on the weight of the internal phase solution (e.g., monomer or monomer and oil) containing the chromogen. A preferred range is from about 2 percent to about 10 percent. The amount of the chromogenic material required to obtain suitable images depends on the nature of the chromogen, the nature of the internal phase, and the type of imaging system. Typically less chromogenic material is used in the internal phase of a self-contained imaging system in comparison to a transfer system. This is because the developer material is co-deposited on a common substrate with the chromogenic encapsulate and there is a tendency for the chromogenic material to diffuse through the capsule wall and react with the developer material during storage and because there is no inherent loss in transfer.
[0037] In addition to the chromogenic material and the photosensitive material, the internal phase of the present invention may also include a carrier oil to affect and control the tonal quality of the images obtained. While tonal quality (half-tone gradation) is not critical when copying printed documents, it is an important factor in faithfully reproducing pictorial images. In some cases where trimethylolpropane triacrylate is used in the radiation curable material, 20% of a carrier oil such as brominated paraffin improves tonal qualities. Preferred carrier oils are weakly polar solvents having boiling points above 170° C. and preferably in the range of 180° C. to 300° C. The carrier oils used in the present invention are typically those conventionally used in carbonless paper manufacture. These oils are generally characterized by their ability to dissolve Crystal Violet Lactone in a concentration of 0.5 wt % or more. However, a carrier oil is not always necessary. Whether a carrier oil should be used will depend on the solubility of the chromogenic material in the photosensitive composition before exposure, the nature of the chromogenic material and the viscosity of the characteristics of the internal phase. When present, examples of carrier oils are alkylated biphenyls (e.g., monoisopropylbiphenyl), polychlorinated biphenyls, castor oil, mineral oil, deodorized kerosene, naphthenic mineral oils, dibutyl phthalate, dibutyl fumerate, brominated paraffin and mixtures thereof. Alkylated biphenyls are generally preferred.
[0038] Various photoinitiators can be selected for use in the present invention. These compounds absorb the exposure radiation and generate a free radical alone or in conjunction with a sensitizer. Conventionally, there are homolytic photoinitiators which cleave to form two radicals and initiators which radiation converts to an active species which generates a radical by abstracting a hydrogen from a hydrogen donor. There are also initiators which complex with a sensitizer to produce a free radical generating species and initiators which otherwise generate radicals in the presence of a sensitizer. Both types can be used in the present invention. If the system relies upon ionic polymerization to tie up the chromogen, the initiator may be the anion or cation generating type depending on the nature of the polymerization. Where, for example, ultraviolet sensitivity is desired, as in the case of direct transmission imaging using ultraviolet light, suitable photoinitiators are described in the aforementioned patents. The sensitivity among these compounds can be shifted by adding substituents such that the compounds generate radicals when exposed to the desired radiation wavelength.
[0039] The photoinitiator is present in the internal phase in an amount sufficient to initiate polymerization or cross-linking within a short exposure time. Using benzoin methyl ether as an example, this photoinitiator is typically present in an amount of up to 10% based on an amount of radiation curable material in the internal phase. Naturally, the amount varies depending on the nature of the other components of the photosensitive composition.
[0040] Particularly useful as photoinitiators in the present invention are cationic dye-borate anion complexes as disclosed in commonly assigned U.S. Pat. Nos. 5,112,752; 5,100,755; 5,057,393; 4,865,942; 4,842,980; 4,800,149; 4,772,530 and 4,772,541 which are incorporated herein by reference. When employed as a photoinitiator in the present invention, the cationic dye-borate anion complex is usually used in an amount up to about 1% by weight based on the weight of the photopolymerizable or crosslinkable species in the photohardenable composition. More typically, the cationic dye-borate anion complex is used in an amount of about 0.2% to 0.5% by weight. While the cationic dye-borate anion complex can be used alone as the initiator, film speeds tend to be quite low and oxygen inhibition is observed.
[0041] The photosensitive composition may include a photoinitiator containing a thiol as described in commonly assigned U.S. Pat. No. 4,874,685 which is incorporated herein by reference. Representative examples of thiols useful in the present invention are mercaptobenzoxazole, ethoxymercaptobenzothiazole, mercaptobenzothiazole and 1-phenyl-5-mercaptotetrazole.
[0042] In accordance with one embodiment of the invention, a full color imaging system is provided in which the microcapsules are in three sets respectively containing cyan, magenta and yellow color formers sensitive to red, green, and blue light respectively. For good color balance, the visible-sensitive microcapsules are sensitive (λ max) at about 450 nm, 540 nm, and 650 nm, respectively. Such a system is useful with visible light sources in direct transmission or reflection imaging. They are useful in electronic imaging using digital printers, lasers or pencil light sources of appropriate wavelengths. Because digital imaging systems do not require the use of visible light, sensitivity can be extended into the UV and IR. Accordingly, the sensitivity can be extended into the IR and/or UV to spread the absorption spectra of the photoinitiators and avoid cross-sensitization.
[0043] The developer materials employed in carbonless paper technology are useful in the present invention. Illustrative examples are clay minerals such as acid clay, active clay, attapulgite, etc.; organic acids such as tannic acid, gallic acid, propyl gallate, etc.; acid polymers such as phenol-formaldehyde resins, phenol acetylene condensation resins, condensates between an organic carboxylic acid having at least one hydroxy group and formaldehyde, etc.; metal salts of aromatic carboxylic acids or derivatives thereof such as zinc salicylate, tin salicylate, zinc 2-hydroxy napththoate, zinc 3,5 di-tert butyl salicylate, zinc 3,5-di-(α-methylbenzyl) salicylate, oil soluble metals salts or phenol-formaldehyde novolak resins (e.g., see U.S. Pat. Nos. 3,672,935 and 3,732,120) such as zinc modified oil soluble phenol-formaldehyde resin as disclosed in U.S. Pat. No. 3,732,120, zinc carbonate etc. and mixtures thereof. The particle size of the developer material is important to obtain a high quality image. The developer particles should be in the range of about 0.2 to 3 microns and, preferably in the range of about 0.5 to 1.5 microns.
[0044] A suitable binder such as polyethylene oxide, polyvinyl alcohol, polyacrylamide, acrylic latices, neoprene emulsions, polystyrene emulsions, and nitrile emulsions, etc. may be mixed with the developer and the microcapsules, typically in an amount of about 1 to 8% by weight, to prepare a coating composition.
[0045] A preferred developer material is one which has excellent compatibility with the microcapsule slurry solution. Specific examples of useful developers, which have good stability include phenolic resins from Schenectady International, such as HRJ-4250 and HRJ-4542 and OR-1 developer from Sanko.
[0046] The microcapsules used in the present invention can be produced using known encapsulation techniques including coacervation, interfacial polymerization, polymerization of one or more monomers in an oil, as well as various melting, dispersing and cooling methods. The capsule forming material used in a given imaging system is selected based on the photosensitive composition present in the encapsulate. Thus, the formed capsule wall must be transmissive to the exposure radiation. Melamine-formaldehyde capsules are preferred.
[0047] The mean size of the capsules used in the present invention may vary over a broad range but generally ranges from approximately 1 to 10 microns. As a general rule, image resolution improves as the capsule size decreases with the caveat that if the capsule size is too small, the capsule may sit within incongruities in the support and the support may screen the capsules from exposure. Very small capsules may also fail to rupture upon the application of pressure. In view of the foregoing, it has been found that a preferred mean capsule size range is approximately 1 to 10 microns and particularly approximately 1 to 5 microns.
[0048] The photosensitive imaging media is then exposed to actinic radiation such that the microcapsules are image-wise exposed to form a latent image. As used herein, the term “actinic radiation” encompasses wavelengths in the ultraviolet spectral region, visible region and infrared spectral region. Typically, the actinic radiation source will be ultraviolet or visible wavelengths. The exposure to actinic radiation causes the encapsulated radiation curable composition to polymerize thereby preventing release of the image-forming chromogenic composition.
[0049] Typically, capsule rupture is effected by the application of pressure to the imaging sheet using pressure rollers. Although the present system has been described with reference to pressure development, alternative means of capsule rupture can also be used. For example, systems are envisioned in which the capsules are ruptured ultrasonically, by vibration, thermally, or by solvent.
[0050] Media stability may be improved by conditioning the components of the photosensitive imaging system (either the donor sheet or donor sheet and developer sheet or self-contained media) at a temperature of from about 15° C. to 40° C., preferably from about 30° C. to 40° C., most preferably around 35° C. The imaging media is typically stored at a relative humidity of from about 50-90% RH.
[0051] In accordance with another aspect of the present invention, the imaging media is developed at a temperature of from about 15° C. to 40° C., preferably from about 30° C. to 40° C., most preferably around 35° C., by providing a means for heating the imaging media to the desired temperature. Typically, this is achieved by providing a means for heating the imaging media before and/or during pressure developing. Means for heating the imaging media include conductive, convective and radiant heat. Specific means for heating the imaging media include use of an oven, heated developer rollers, heated forced air, IR, thermal head, heating strip or plate, etc.
[0052] In accordance with yet another aspect of the present invention, the imaging media is subjected to an elevated temperature after development to improve image development and increase density. Post development heat can be applied at any stage after development. For example, the imaging media can be heated to a temperature of from about 60° C. to 120° C. either before, during or after laminating the ID card substrate to the image by providing a means for heating the imaging media. Means for heating the imaging media include conductive, convective and radiant heat. Specific means for heating the imaging media include use of an oven, heated laminating rollers, heated forced air, IR, thermal head, heating strip or plate, etc. If a pressure sensitive adhesive is utilized as a laminating adhesive the post heating step is typically conducted after lamination. If the lamination adhesive is a thermally activated adhesive, then the lamination step will typically involve the application of heat to the imaging media during the lamination step to activate the adhesive, typically from about 70° C. to 125° or higher, preferably around 100° C. The heat applied to the media during lamination can also improve image development. Production of ID cards in accordance with the present invention may include more than one post development heating step.
[0053] Although the present invention has been described with reference to imaging materials in roll form, cut sheet imaging materials are also within the scope of the present invention. For example, precut developer sheets or precut self-contained sheets could be used. Furthermore, the die cut step could be eliminated if the cut sheets were of the appropriate size for the ID card or perforated to provide multiple cards per sheet which could subsequently be separated into individual ID cards.
[0054] The ID cards of the present invention may also incorporate other security features as is well known in the art. Examples of other security features that can be incorporated into the ID cards of the present invention include magnetic stripes, holograms, bar codes, fingerprints, microprinting, signatures, etc. | A method and apparatus for producing identification (ID) cards using a photosensitive imaging system employing microcapsules is described. In accordance with one aspect of the invention, ID cards are produced by translating an image containing identifying indicia into a latent image on an appropriate photosensitive donor sheet, pressure developing the latent image, forming a full color print of the image on a developer sheet, laminating an ID card substrate in registration with the image to the developer sheet and die cutting the laminated article to produce an ID card. Self-contained imaging systems can also be used to produce identification cards. The image preferably includes unique information useful in identifying the card holder such as a photograph, fingerprint, signature, description, name, etc. The identifying indicia may be combined with non-variable information including background printing, card issuer data, logos, security features, etc. An ID card produced in accordance with certain embodiments of the present invention provides a secure identification card which is inherently more durable and less susceptible to delamination and tampering because the image is directly laminated to the ID card substrate. | 6 |
BACKGROUND OF THE INVENTION
This invention relates to an endoscope whose illumination optical system has been improved.
In recent years, the number of foreground subjects to be observed by an endoscope has grown in the fields of medical treatment and manufacturing industries, and has assumed extremely diversified forms. Sometimes a wide angle is preferred, depending on the type of foreground subject to be examined. As a result, the range of the illumination carried out by the endoscope illumination apparatus has to be widened. To meet this requirement, various attempts, including the use of a wide angle lens, have been made. However, none of the proposals advanced to date have been able to realize a sufficiently wide illumination angle. Moreover, the illumination by the conventional illumination apparatus is brightest at its center and grows progressively darker toward its periphery. When, therefore, observation was made of the inner walls of, for example, the alimentary canal or intestines which are located at the peripheral portions of the illumination range of the apparatus, it was difficult to distinctly observe the subject due to the great darkness prevailing over the peripheral portions. In such a case, the light at the center of the illumination range of the illumination apparatus made no contribution to the observation of the above-mentioned inner walls and was simply wasted. Therefore, the conventional illumination apparatus is accompanied with the drawback that its illumination efficiency was considerably unsatisfactory.
SUMMARY OF THE INVENTION
This invention has been accomplished in view of the above-mentioned circumstances and is intended to provide an illumination apparatus for an endoscope which enables its illumination range to be widened and also the peripheral portions of the illumination range to be supplied with a sufficient amount of light, thereby ensuring the efficient illumination of the inner wall of a tubular foreground subject.
To attain the above-mentioned object, this invention provides an illumination apparatus for an endoscope which comprises:
an optical element whose light-receiving surface faces the light-issuing end of a light guide of an endoscope;
a lens arranged opposite to a light-issuing surface of the optical element,
and wherein a depression is formed at the center of the light-issuing surface of the optical element.
An illumination apparatus according to one aspect of this invention which is arranged as described above offers the advantages that the range of illumination is widened; light beams emitted from the optical element and conducted through the lens can be so distributed that the central part of the illumination range grows darker, whereas the peripheral portions of the illumination range conversely become brighter.
An illumination apparatus according to another aspect of the invention is characterized in that the light-issuing surface of the optical element is separated by a distance g determined by the following equation from a point conjugate with that plane which is assumed to face a foreground subject. The illumination range can be widened, thereby enabling a uniform amount of light to be distributed through the illumination range.
|g|≧D/2 tan α
α: Emission angle (degrees) of a light beam
D: Diameter (mm) of the depression measured in the plane of the light-issuing surface.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the whole endoscope;
FIG. 2 is a side view of an optical system involved in an illumination apparatus according to one embodiment of this invention;
FIG. 3 shows the distribution of light emitted from the subject illumination apparatus;
FIG. 4 illustrates the manner in which the illumination apparatus sheds light beams over the inner wall of one of the canals lying in the celiac cavity of, for example, a human body taken as a foreground subject;
FIG. 5 shows the course taken by a light beams emitted from one point on the subject illumination apparatus;
FIG. 6 is a side view of an illumination apparatus according to a first modification of the invention;
FIG. 7 illustrates the arrangement of said first modification showing its operation;
FIG. 8 is a partly cut-out side view of an illumination apparatus according to a second embodiment of the invention;
FIG. 9 indicates the distribution of light beams issued from the illumination apparatus according to the second embodiment;
FIG. 10 shows the course taken by the light beams emitted from one point on the illumination apparatus of FIG. 8;
FIG. 11 sets forth the arrangement of an illumination apparatus according to the second modification of the invention;
FIG. 12 is a partly cut-out side view of an illumination apparatus according to a third embodiment of the invention;
FIG. 13 indicates the distribution of light beams emitted from the illumination apparatus according to the third embodiment;
FIG. 14 set forth the arrangement of an illumination apparatus according to a third modification of the invention;
FIG. 15 illustrates the operation of the third modification;
FIG. 16 is a partly cut-out side view of an illumination apparatus according to a fourth modification;
FIG. 17 shows the distribution of light beams emitted from the fourth modification;
FIG. 18 is a partly cut-out side view of an illumination apparatus according to a fifth modification; and
FIG. 19 shows the distribution of light beams issued from the fifth modification.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A description may now be made of the preferred embodiments of this invention with reference to the accompanying drawings. FIG. 1 shows the whole endoscope. The endoscope 10 comprises an operation section 14 fitted with an eyepiece 12, an insertion section 20 which extends from the operation section and has an illumination window 18 formed at the distal end 16, and a flexible tube 24 which extends from the operation section 14 and is connected to a light source device (not shown) through a connector 22. A light guide 26 (FIG. 2) extends from the connector 22 to the proximity of the illumination window 18 through the flexible tube 24, operation section 14 and insertion section 20. When the connector 22 is connected to the light source device, light beams emitted from the light source device are conducted throgh the light guide 26 to the distal end 16 of the insertion section 20.
As shown in FIG. 2, the distal end 16 of the insertion section 20 is fitted with an illumination apparatus 28 embodying this invention. This illumination apparatus 28 comprises an optical element 32 optically connected to the light-issuing end 30 of the light guide 26 and a convex lens 34 fitted to the illumination window 18 so as to face the optical element 32. The optical element 32 is made from a light-permeable material and has a circular truncated conical shape. The end face on the larger diameter side of the optical element 32 acts as a light-receiving surface 36. The optical element 32 is concentrically arranged with the light guide 26. The light-receiving surface 36 faces the light-emitting end 30 of the light guide 26, thereby effecting an optical connection between both elements 32, 36. The end face of the smaller diameter side of the optical element 32 acts as a light-issuing end face 40 and faces the convex lens 34. A conical depression 42 is coaxially formed in the light-issuing end face 40, thereby causing the light-issuing end face to assume an annular form. The shape of the depression 42 is so designed that when the light beams emitted from the light-issuing end face 40 pass through the convex lens 34, the distribution of light beams over the plane S, on which a foreground subject is assumed to be set, indicates the pattern shown in FIG. 3, in which the central portion of the illumination range grows darker, whereas the peripheral portion of the illumination range becomes brighter in the ring form. In other words, the light beams entering the optical element 32 from the light guide 26 are repeatedly reflected on the conical surface 44 of the depression 42 and on the outer peripheral surface 46 of the optical element 32, and are emitted from the light-issuing surface 40 in a ring form. When passing through the convex lens 34, the emitted light beams are converged and distributed in the pattern shown in FIG. 3.
When the inner wall 48 of a canal lying in the celiac cavity of, for example, a human body taken as a foreground subject, is illuminated by the illumination apparatus constructed as described above, light beams are concentrated on the inner wall of said celiac canal taken as the field of view X, thereby preventing the light beams from being uselessly emitted straight through the celiac canal.
As shown in FIG. 5, the light-issuing surface 40 of the optical element 32 assumes a conjugate position with respect to the plane S on which the foreground subject is assumed to be set, causing light beams emitted from one point on the light-issuing surface to be converged on the plane S after passing through the convex lens 34.
With the modification of FIG. 6, the optical element 32 is so positioned as to cause the light-issuing surface 40 to be displaced from the conjugate point shown in FIG. 5 toward the convex lens 34 at a distance g. As used herein, the distance g is defined by the following formula:
|g|≧D/2 tan α
α: Emission angle (degrees) of a light beam
D: Diameter (mm) of the depression 42 measured in the plane of the light-issuing surface.
With the above-mentioned modification, light beams emitted from the light-issuing surface 40 of the optical element 32 in the ring form are focused due to a passage through the convex lens 34 having a positive focal point. Since, however, the light-issuing surface 40 of the optical element 32 is displaced from the conjugate point at the distance g, the light beams are not completely focused on the plane S on which a foreground subject is supposed to be set, but are irradiated on the plane S in the defocused form. Like the aforementioned embodiment, therefore, the modification of FIG. 6 offers the advantages that the illumination range can be broadened, and that light beams are irradiated on the plane S in a blurred form, thereby minimizing the irregular emission of light beams within the specified illumination range.
When, an shown in FIG. 7, the diameter D of the base of the conical depression 42 is larger than 2 g·tan α, light beams are not gathered in the same places on the plane S, giving rise to an irregular illumination.
FIG. 8 shows a second embodiment of the invention. This second embodiment is substantially the same as the first embodiment, except that the convex lens 34 of the first embodiment is replaced by a double convex lens 45. This double convex lens 45 has such a cross-sectional outline as is obtained when the convex lens 34 of the first embodiment is rotated around the axis of the optical element 32. The double convex lens 44 has such an action that light beams emitted from the neighborhood of the inner peripheral portion of the light-issuing surface 40 of the optical element 32 illuminate the outer peripheral portion of the ring-shaped illumination range 47, and that light beams issued from the neighborhood of the outer peripheral portion of the light-issuing surface 40 are cast on the inner peripheral portion of the illumination range 47.
With the second embodiment of FIG. 8, therefore, the distribution of light beams has the pattern as shown in FIG. 9. Namely, the illumination peaks lie nearer to the inner peripheral portion of the ring-shaped illumination range 47 than in FIG. 3 representing the first embodiment. The amount of light progressively reduces as it moves toward the outside of the illumination range 47. When, the inner walls of the celiac canal are illuminated by the illumination apparatus, according to the second embodiment as shown in FIG. 4, a maximum amount of light beams is emitted to the remotest portions of the inner walls, and a smaller amount of light beams is irradiated on those portions of the inner walls which lie nearer to the light-issuing surface 40 of the optical element 32. As a result, a uniform illumination can be realized throughout the inner walls of the celiac canal.
When, as seen from FIGS. 10 and 11, the light-issuing surface 40 of the optical element 32 is displaced from the conjugate point toward the lens 45 at the distance g, the illumination range can be broadened, and any irregularities of illumination within the specified range can be reduced.
FIG. 12 shows a third embodiment of the invention. This third embodiment is substantially the same as the first embodiment except that the convex lens 34 of the first embodiment is replaced with a concave lens 49.
With this third embodiment, the light beams 50 having the greatest intensity among those emitted from the light-issuing surface 40 of the optical element 32 are initially conducted in parallel with the optical axis of the element 32. However, the light beams 50 are diverted outward toward the periphery by the action of the concave lens 49. Therefore, a ring-shaped illumination is realized with the intensity of the light beams gently distributed as shown in FIG. 13.
With the modification of FIG. 14, the optical element 32 and concave lens 49 assume such a position that the distance g between the point L at which the foreground subject plane S produces a virtual image, and the light-issuing surface 40 of the optical element 32 assumes a value determined by the following equation:
g≧D/2 tan α
α: Emission angle of light beams
D: Diameter of the depression measured in the plane of the light-issuing surface.
Like the aforementioned modification, the modification of FIG. 14 offers the advantage that the illumination range can be broadened, and illumination irregularities can be reduced.
When the diameter D of the base of the conical depression 42 is larger than 2g tan α as shown in FIG. 15, light beams are not gathered in some places on the plane S on which the foreground subject is assumed to be set, thereby giving rise to illumination irregularities.
A description may now be made with reference to FIG. 16 of an illumination apparatus according to a fourth modification. With this fourth modification, an annular projection 52 is integrally formed on the outer periphery of the light-issuing surface 40 of the optical element 32 in order to increase the diameter of the outer peripheral portion of the light-issuing surface 40. The provision of the annular projection 52 has the effect that the quantity per unit area of the light beams emitted from the neighborhood of the outer periphery of the light-issuing surface 40 is reduced more than the quantity per unit area of the light beams issued from the neighborhood of the inner peripheral of the light-issuing surface 40. Therefore, the illumination on the outer peripheral portion of the annular illumination range is decreased more on the inner peripheral portion thereof, therby giving rise to the light beam distribution illustrated in FIG. 17.
FIG. 18 shows a fifth modification of the invention. With this modification, an annular projection 54 is integrally formed on the inner peripheral wall of the conical depression 42 of the optical element 32 in order to broaden the inner peripheral edge portion of the light-issuing surface 40 of the optical element 32. The provision of the annular projection 54 has the effect that the guantity per unit area of the light beams issued from the neighborhood of the inner peripheral portions of the light-issuing surface 40 is reduced more than the quantity per unit area of the light beams sent forth from the neighborhood of the outer peripheral portions of the light-issuing surface 40. As compared with the second embodiment, therefore, the fifth modification of FIG. 18 is characterized in that the illumination is more uniformly reduced from the inside toward the outside of the annular illumination range as illustrated in FIG. 19.
It will be noted that this invention is not limited to the foregoing embodiments and modifications, but that it is also practical with further changes and modifications.
For instance, the light-receiving surface and light-issuing surface of the optical element need not be flat, but may assume any other form, for example, a concave, convex, or nonspherical form. Further, the optical element need not assume a circular truncated conical shape, but may be formed in the shape of a rounded column, key, or hourglass. The depression need not assume a conical form, but may be formed in a spherical or angular conical shape. The inner peripheral wall of the depression need not be linear, but may be concave, convex or curved.
The outer peripheral wall of the optical element and the inner wall of the depression need not be prepared from a transparent material, but may be formed of a translucent or light-reflecting material.
The optical element may be provided by grinding glass material or may be formed of synthetic resin. Synthetic resin molding particularly facilitate the manufacture of the optical element. The optical element has only to be optically connected to the light-issuing surface of a light guide, and need not be physically pressed against the light-issuing plane. | An illumination apparatus for an endoscope is provided at the distal end of the insertion section of the endoscope. The apparatus has a light guide which extends through the insertion section, has a light-issuing end located adjacent to the distal end opening of the insertion section. The light guide conducts light beams emitted from a light source device. An optical element made of a light-permeable material is arranged to face the light-issuing end of the light guide, and a lens is arranged in the distal end opening. The optical element has a light-receiving surface facing the light issuing end and a light issuing surface opposite to the lens. A depression is formed in the center of the light-issuing surface. Light beams emitted from the end of the light guide pass through the optical element and lens, and are distributed by the depression in the annular pattern whose central portions grow dark and whose peripheral portions are rendered bright. | 0 |
SUMMARY OF THE INVENTION
Useful pharmaceutical activity is exhibited by compounds having the formula ##STR2## In formula I, and throughout the specification, the symbols are as defined below.
R can be hydrogen, halogen, alkyl, alkoxy, alkylthio, trifluoromethyl, nitro, amino, or cyano;
A can be a straight or branched chain alkylene group having 2 to 8 carbon atoms; and
M CAN BE 2, 3, OR 4.
The broken line in the piperidine nucleus represents the optional presence of ethylenic unsaturation.
The term "alkyl," as used throughout the specification, refers to alkyl groups having 1 to 4 carbon atoms.
The term "alkoxy," as used throughout the specification, refers to groups having the formula Y-O- wherein Y is alkyl as defined above.
The term "alkylthio," as used throughout the specification, refers to groups having the formula Y-S- wherein Y is alkyl as defined above.
The term "halogen," as used throughout the specification, refers to fluorine, chlorine, bromine, and iodine; fluorine, chlorine, and bromine are the preferred halogens.
DETAILED DESCRIPTION OF THE INVENTION
The compounds of formula I, and their pharmaceutically acceptable salts, are useful in treating various allergic conditions in mammalian species such as mice, cats, dogs, etc., when administered in amounts ranging from about 1 milligram to about 500 milligrams per kilogram of body weight per day. The compounds can be used prophylactically or therapeutically to treat various allergic and immunological disorders and in particular to treat certain types of asthma, hay-fever, and rhinitis. A preferred dosage regimen would be from about 3 milligrams to about 200 milligrams per kilogram of body weight per day administered in a single dose or plurality of divided doses.
The compounds of formula I, and the pharmaceutically acceptable salts thereof, are anti-allergics which inhibit the effects of certain antigen-antibody reactions and in particular inhibit the release of mediators such as histamine. The antiallergy activity of these compounds is determined by the reaginic antibody induced passive cutaneous anaphylaxis (PCA) reaction in rats. (See Bach, Immediate Hypersensitivity: Laboratory Models and Experimental Findings, Ann. Rep. Med. Chem., 7: 238-248 (1972), for a discussion of the pedictability of clinical efficacy of compounds active in the PCA).
A compound of formula I, or a salt thereof, can be administered by the inhalation of an aerosol or powder as described in U.S. Pat. No. 3,772,336 (i.e., breathing finely divided particles of the active ingredient into the lungs), orally, or parenterally. Powders can be prepared by comminuting the active ingredient with a similarly comminuted diluent such as starch or lactose. Suitable forms for oral administration include capsules, tablets, and syrups, and a suitable form for parenteral administration is a sterile injectable. Such unit dosage forms are prepared by compounding with a conventional vehicles, excipients, binders, preservatives, stabilizers, flavoring agents or the like as called for by acceptable pharmaceutical practice. Also, the compounds of this invention can be formulated with other pharmaceutically active compounds such as bronchodilators, steroids, antihistamines, etc.
The products of formula I can be prepared using as starting materials compounds having the formulas ##STR3##
X' -- A -- X IV. In formula IV, and throughout the specification, the symbols X and X' can be the same or different and can be halogen (preferably chlorine or bromine), alkylsulfonate (e.g., methanesulfonate), or arylsulfonate (e.g., toluenesulfonate).
Reaction of a compound of formula II with a compound of formula IV yields an intermediate having the formula ##STR4## The reaction can be run in a polar organic solvent, e.g., dimethylsulfoxide or dimethylformamide, in the presence of alkali.
Reaction of an intermediate of formula V with a pyridine derivative of formula III yields an intermediate having the formula ##STR5## The reaction can be run in an organic solvent, e.g., benzene, toluene, etc., preferably in the presence of an organic or inorganic base, e.g., a tertiary amine such as ethyldiisopropylamine or an alkali metal carbonate such as sodium carbonate. While reaction conditions are not critical, the reaction will most conveniently be run at the reflux temperature of the solvent.
An intermediate of formula VI can be converted to the corresponding product of formula I via acid hydrolysis. This is most conveniently carried out by extracting the reaction product of an intermediate of formula V and a pyridine derivative of formula III with a mineral acid (hydrochloric acid is preferred) and allowing the acid solution to stand for about 1 week. The hydrolysis can be accelerated by heating.
Other procedures for preparing the compounds of formula I are available. For example, an intermediate of formula VI can be prepared by first reacting a compound of formula II with an appropriate base, e.g., potassium hydroxide or thallous ethoxide. The resultant salt is reacted with a compound having the formula ##STR6## to yield an intermediate of formula VI. The compounds of formula I can then be prepared by acid hydrolysis as described above.
In still another method for preparing the compounds of formula I, a compound having the formula ##STR7## is reacted with a compound having the formula ##STR8## to yield the products of formula I directly.
The compounds of formula I can be converted into their pharmaceutically acceptable salts using procedures well known in the art. Acid addition salts such as the hydrohalides, nitrate, phosphate, sulfate, tartrate, maleate, fumarate, citrate, succinate, methanesulfonate, benzenesulfonate, toluenesulfonate, and the like, are specifically contemplated. Basic salts are also specifically contemplated. The compounds of formula I form salts with bases such as alkali metal hydroxides, sodium hydroxide, potassium hydroxide, etc.), alkaline earth metal hydroxides (e.g., calcium hydroxide, magnesium hydroxide, etc.), alkali metal carbonates (e.g., sodium carbonate, etc.) and alkali metal bicarbonates (e.g., potassium bicarbonate, etc.).
The following examples are specific embodiments of this invention.
EXAMPLE 1
5-[[4-(3,6-Dihydro-4-Phenyl-1(2H)-Pyridinyl)Butyl]Amino]-5-Oxopentanoic Acid, Hydrochloride (1:1)
A. n-(4-bromobutyl)glutarimide
Sodium (5g) is dissolved in 100 ml of absolute ethanol and the sodium ethoxide solution is added to a solution of 23 g of glutarimide in 160 ml of warm absolute ethanol. The mixture is allowed to cool to 25° C with stirring and the solvent is removed under vacuum. To the residue is added 70 ml of dimethylformamide and 60 ml of 1,4-dibromobutane and the mixture is refluxed for 10 minutes. The solvent is removed under vacuum and the residue is shaken with hexane to remove excess 1,4-dibromobutane. The hexane layer is decanted off, the residue is taken up in ether and the insoluble material is filtered off. The ethereal filtrate is washed with 10% sodium hydroxide, 10% hydrochloric acid, water, and dried over sodium sulfate. The solvent is removed under vacuum to yield 26 g of N-(4-bromobutyl)glutarimide.
B. 5-[[4-(3,6-dihydro-4-phenyl-1(2H)-pyridinyl)butyl]amino]-5-oxopentanoic acid, hydrochloride (1:1)
4-Phenyl-1,2,3,6-tetrahydropyridine hydrochloride (10 g) is converted to its free base and combined with 11.0 g of N-(4-bromobutyl)glutarimide and 18 g of sodium carbonate in 200 ml of toluene. The mixture is refluxed for 5 hours, cooled to 25°C and 50 ml of water is added. After stirring for 15 minutes, the layers are separated and the organic layer is filtered through fritted glass to remove insoluble material and then extracted with 10% hydrochloric acid. The acid solution is allowed to stand in an open beaker for 1 week during which time the product precipitates out. It is filtered off and dried at 70° C, 0.1 mm of Hg, for 12 hours to yield 6.3 g of the title compound, melting point 163°-165°C.
EXAMPLES 2-55
Following the procedure of Example 1, but substituting the compound listed in Column I for glutarimide, the compound listed in Column II for 1,4-dibromobutane and the compound listed in Column III for 4-phenyl-1,2,3,6-tetrahydropyridine hydrochloride, yields the compound listed in Column IV.
__________________________________________________________________________ExampleColumn I Column II Column III Column IV__________________________________________________________________________ 2 glutarimide 1,2-dibromoethane 4-(4-chlorophenyl)1,2,3, 5-[[2-[3,6-dihydro-4-(4- 6-tetrahydropyridine chlorophenyl)-1(2 -H)-pyri- dinyl]ethyl]amino]-5-oxo- pentanoic acid, hydro- chloride 3 glutarimide 1,3-dibromopropane 4-(4-bromophenyl)-1,2,3, 5-[[3-[3,6-dihydro-4-(4- 6-tetrahydropyridine bromophenyl)-1(2 -H)-pyri- dinyl]propyl]amino]-5- oxopentanoic acid, hydro- chloride 4 glutarimide 1,5-dibromopentane 4-(2-methylphenyl)-1,2, 5-[[5-[3,6-dihydro-4-(2- 3,6-tetrahydropyridine methylphenyl)-1(2 -H)-py- ridinyl]pentyl]amino]-5- oxopentanoic acid, hydro- chloride 5 glutarimide 1,5-dibromohexane 4-(3-methoxyphenyl)- 5-[[6-[3,6-dihydro-4-(3- 1,2,3,6-tetrahydropyri- methoxyphenyl)-1(2 -H)-py- dine ridinyl]hexyl]amino]-5- oxopentanoic acid, hydro- chloride 6 glutarimide 1,7-dibromoheptane 4-(4-methylthiophenyl)- 5-[[7-[3,6-dihydro-4-(4- 1,2,3,6-tetrahydropyri- methylthiophenyl)-1(2 -H)-py- dine ridinyl]heptyl]amino]- 5-oxopentanoic acid, hy- drochloride 7 glutarimide 1,8-dibromooctane 4-(4-trifluoromethylphen- 5-[[8-[3,6-dihydro-4-(4- yl)-1,2,3,6-tetrahydro- trifluoromethylphenyl)- pyridine 1(2 -H)-pyridinyl]octyl]- amino]-5-oxopentanoic acid, hydrochloride 8 glutarimide 1,3-dibromo-2- 4-(3-nitrophenyl)-1,2,3,- 5-[[3-[3,6-dihydro-4-(3- methylpropane 6-tetrahydropyridine nitrophenyl)-1(2 -H)-py- ridinyl]-2-methylpropyl]- amino]-5-oxopentanoic acid, hydrochloride 9 glutarimide 1,2-dibromoethane 4-(2-aminophenyl)-1,2,3,- 5-[[2-[3,6-dihydro-4-(2- 6-tetrahydropyridine aminophenyl)-1(2 -H)-pyri- dinyl]ethyl]amino]-5- oxopentanoic acid, hydro- chloride10 glutarimide 1,3-dibromopropane 4-(2-cyanophenyl)-1,2,3,- 5-[[3-[3,6-dihydro-4-(2- 6-tetrahydropyridine cyanophenyl)-1(2 -H)-pyri- dinyl]propyl]amino]-5- oxopentanoic acid, hydro- chloride11 succinimide 1,2-dibromoethane 4-phenyl-1,2,3,6-tetra- 4-[[2-(3,6-dihydro-4- hydropyridine phenyl-1(2 -H)-pyridinyl)- ethyl]amino]-4-oxobutan- oic acid, hydrochloride12 succinimide 1,8-dibromooctane 4-(2-chlorophenyl)-1,2,3, 4-[[8-[3,6-dihydro-4-(2- 6-tetrahydropyridine chlorophenyl)-1(2 -H)-pyri- dinyl]octyl]amino]-4-oxo- butanoic acid, hydrochlo- ride13 succinimide 1,3-dibromopropane 4-(2-ethylphenyl)-1,2,3,- 4-[[3-[3,6-dihydro-4-(2- 6-tetrahydropyridine ethylphenyl-1(2 -H)-pyri- dinyl]propyl]amino]-4- oxobutanoic acid, hydro- chloride14 succinimide 1,4-dibromobutane 4-(2-ethoxyphenyl)-1,2,- 4-[[4-[3,6-dihydro-4-(2- 3,6-tetrahydropyridine ethoxyphenyl)-1(2 -H)-pyri- dinyl]butyl]amino]-4-oxo- butanoic acid, hydrochlo- ride15 succinimide 1,5-dibromopentane 4-(2-ethylthiophenyl)-1,- 4-[[5-[3,6-dihydro-4-(2- 2,3,6-tetrahydropyridine ethylthiophenyl)-1(2 -H)- pyridinyl]pentyl]amino]- 4-oxobutanoic acid, hydro- chloride16 succinimide 1,6-dibromohexane 4-(3-trifluoromethyl- 4-[[6-[3,6-dihydro-4-(3- phenyl)-1,2,3,6-tetra- trifluoromethylphenyl)- hydropyridine 1(2 -H)-pyridinyl]hexyl]- amino]-4-oxobutanoic acid, hydrochloride17 succinimide 1,7-dibromoheptane 4-(4-nitrophenyl)-1,2,3,- 4-[[7-[3,6-dihydro-4- 6-tetrahydropyridine (4-nitrophenyl)-1(2 -H)- pyridinyl]heptyl]amino]- 4-oxobutanoic acid, hydro- chloride18 succinimide 1,2-dibromoethane 4-(4-aminophenyl)-1,2,3,- 4-[[2-[3,6-dihydro-4-(4- 6-tetrahydropyridine aminophenyl)-1(2 -H)-pyri- dinyl]ethyl]amino]-4- oxobutanoic acid, hydro- chloride19 succinimide 1,5-dibromo-3- 4-(4-cyanophenyl)-1,2,3,- 4-[[5-[3,6-dihydro-4-(4- methylpentane 6-tetrahydropyridine cyanophenyl)-1(2 -H)-pyri- dinyl]3-methylpentyl]- amino]-4-oxobutanoic acid, hydrochloride20 adipimide 1,2-dibromoethane 4-phenyl-1,2,3,6-tetra- 6-[[2-(3,6-dihydro-4- hydropyridine phenyl-1(2 -H)-pyridinyl)- ethyl]amino]-6-oxohexa- noic acid, hydrochloride21 adipimide 1,3-dibromopropane 4-(3-fluorophenyl)-1,2,- 6-[[3-[3,6-dihydro-4- 3,6-tetrahydropyridine (3-fluorophenyl)-1(2 -H)- pyridinyl]propyl]amino]- 6-oxohexanoic acid, hydro- chloride22 adipimide 1,3-dibromopropane 4-(3-t-butylphenyl)-1,2,- 6-[[3-[3,6-dihydro-4-(3- 3,6-tetrahydropyridine t-butylphenyl)-1(2 -H)-py- ridinyl]propyl]amino]- 6-oxohexanoic acid, hydro- chloride23 adipimide 1,4-dibromobutane 4-(2-ethoxyphenyl)-1,2- 6-[[4-[3,6-dihydro-4-(2- 3,6-tetrahydropyridine ethoxyphenyl)-1(2 -H)-pyri- dinyl]butyl]amino]-6-oxo- 4-oxohexanoic acid, hydrochlo- ride24 adipimide 1,5-dibromopentane 4-(4-ethylthiophenyl)-1,- 6-[[5-[3,6-dihydro-4-(4- 2,3,6-tetrahydropyridine ethylthiophenyl)-1(2 -H)- pyridinyl]pentyl]amino]- 4-oxohexanoic acid, hy- drochloride25 adipimide 1,6-dibromohexane 4-(3-trifluoromethyl- 6-[[6-[3,6-dihydro-4-(3- phenyl)-1,2,3,6-tetra- trifluoromethylphenyl)- hydropyridine 1(2 -H)-pyridinyl]hexyl]- amino]-4-oxohexanoic acid, hydrochloride26 adipimide 1,7-dibromoheptane 4-(3-nitrophenyl)-1,2,- 6-[[7-[3,6-dihydro-4-(3- 3,6-tetrahydropyridine nitrophenyl)-1(2 -H)-pyri- dinyl]heptyl]amino]-4- oxohexanoic acid, hydro- chloride27 adipimide 1,8-dibromooctane 4-(3-aminophenyl)-1,2,3,- 6-[[8-[3,6-dihydro-4-(3- 6-tetrahydropyridine aminophenyl)-1(2 -H)-pyri- dinyl]octyl]amino]-4- oxohexanoic acid, hydro- chloride28 adipimide 1,2-dibromoethane 4-(3-cyanophenyl)-1,2,3,- 6-[[2-[3,6-dihydro-4-(3- 6-tetrahydropyridine cyanophenyl)-1(2 -H)-pyri- dinyl]ethyl]amino]-4- oxohexanoic acid, hydro- chloride29 glutarimide 1,2-dibromoethane 4-(4-chlorophenyl)piperi- 5-[[2-[4-(4-chlorophenyl)- dine piperidinyl]ethyl]amino]- 5-oxopentanoic acid, hy- drochloride30 glutarimide 1,3-dibromopropane 4-(4-bromophenyl)piperi- 5-[[3-[4-(4-bromophenyl)- dine piperidinyl]propyl]amino]- 5-oxopentanoic acid, hy- drochloride31 glutarimide 1,5-dibromopentane 4-(2-methylphenyl)piperi- 5-[[5-[4-(2-methylphenyl)- dine piperidinyl]pentyl]amino]- 5-oxopentanoic acid, hy- drochloride32 glutarimide 1,6-dibromohexane 4-(3-methoxyphenyl)piper- 5-[[6-[4-(3-methoxyphenyl)- idine piperidinyl]hexyl]amino]- 5-oxopentanoic acid, hydro- chloride33 glutarimide 1,7-dibromoheptane 4-(4-methylthiophenyl)- 5-[[7-[4-(4-methylthio- piperidine phenyl)piperidinyl]heptyl]- amino]-5-oxopentanoic acid, hydrochloride34 glutarimide 1,8-dibromooctane 4-(3-trifluoromethyl- 5-[[8-[4-(3-trifluoro- phenyl)piperidine methylphenyl)piperidinyl]- octyl]amino]-5-oxopentan- oic acid, hydrochloride35 glutarimide 1,3-dibromo-2- 4-(3-nitrophenyl)piper- 5-[[3-[4-(3-nitrophenyl)- methylpropane idine piperidinyl]-2-methyl- propyl]amino]-5-oxopen- tanoic acid, hydrochloride36 glutarimide 1,2-dibromoethane 4-(2-aminophenyl)piper- 5-[[2-[4-(2-aminophenyl)- idine piperidinyl]ethyl]amino]- 5-oxopentanoic acid, hydro- chloride37 glutarimide 1,3-dibromopropane 4-(2-cyanophenyl)piper- 5-[[3-[4-(2-cyanophenyl)- idine piperidinyl]propyl]amino]- 5-oxopentanoic acid, hy- drochloride38 succinimide 1,2-dibromoethane 4-phenylpiperidine 4-[[2-(4-phenylpiperi- dinyl)ethyl]amino]-4-oxo- butanoic acid, hydrochlo- ride39 succinimide 1,8-dibromooctane 4-(2-chlorophenyl)piper- 4-[[8-[4-(2-chloro- idine phenyl)piperidinyl]- octyl]amino]-4-oxo- butanoic acid, hydro- chloride40 succinimide 1,3-dibromopropane 4-(2-ethylphenyl)piper- 4-[[3-[4-(2-ethylphenyl)- idine piperidinyl]propyl]- amino]-4-oxobutanoic acid41 succinimide 1,4-dibromobutane 4-(2-ethoxyphenyl)-piper- 4-[[4-[4-(2-ethoxy- idine phenyl)piperidinyl]- butyl]amino]-4-oxobuta- noic acid42 succinimide 1,5-dibromopentane 4-(2-ethylthiophenyl) 4-[[5-[4-(2-ethylthio- piperidine phenyl)piperidinyl]- pentyl]amino]-4-oxo- butanoic acid43 succinimide 1,6-dibromohexane 4-(3-trifluoromethyl- 4-[[6-[4-(3-trifluoro- phenyl)piperidine methylphenyl)piperidinyl]- hexyl]amino]-4-oxobuta- noic acid44 succinimide 1,7-dibromoheptane 4-(4-nitrophenyl)piper- 4-[( 7-[4-(4-nitrophenyl)- idine piperidinyl]heptyl]amino]- 4-oxobutanoic acid45 succinimide 1,2-dibromoethane 4-(4-aminophenyl)piper- 4-[[2-[4-(4-aminophenyl)- idine piperidinyl]ethyl]amino]- 4-oxobutanoic acid46 succinimide 1,5-dibromo-3- 4-(4-aminophenyl)piper- 4-[[5-[4-(4-aminophenyl)- methylpentane idine piperidinyl]-3-methyl- pentyl]amino]-4-oxobuta- noic acid47 adipimide 1,2-dibromoethane 4-phenylpiperidine 6-[[2-(4-phenylpiperi- dinyl)ethyl]amino]-6- oxohexanoic acid, hydro- chloride48 adipimide 1,3-dibromopropane 4-(4-fluorophenyl)piper- 6-[[3-[4-(4-fluorophenyl)- idine piperidinyl]propyl]amino]- 6-oxohexanoic acid, hydro- chloride49 adipimide 1,3-dibromopropane 4-(4-t-butylphenyl) 6-[( 3-[4-(4-t-butylphenyl)- piperidine piperidinyl]propyl]amino]- 6-oxohexanoic acid, hydro- chloride50 adipimide 1,4-dibromobutane 4-(3-ethoxyphenyl)piper- 6-[[4-[4-(3-ethoxyphenyl)- idine piperidinyl]butyl]amino]- 6-oxohexanoic acid, hydro- chloride51 adipimide 1,5-dibromopentane 4-(4-ethylthiophenyl)pip- 6-[[5-[4-(4-ethylthio- eridine phenyl)piperidinyl]pen- tyl]amino]-6-oxohexanoic acid, hydrochloride52 adipimide 1,6-dibromohexane 4-(4-trifluoromethyl- 6-[[6-[4-(4-trifluoro- phenyl)piperidine methylphenyl)piperidinyl]- hexyl]amino]-6-oxohexa- noic acid, hydrochloride53 adipimide 1,7-dibromoheptane 4-(3-nitrophenyl)piper- 6-[[7-[4-(3-nitrophenyl)- idine piperidinyl]heptyl]amino]- 6-oxohexanoic acid, hydro- chloride54 adipimide 1,8-dibromooctane 4-(3-aminophenyl)piper- 6-[[8-[4-(3-aminophenyl)- idine piperidinyl]octyl]amino]- 6-hexanoic acid, hydro- chloride55 adipimide 1,2-dibromoethane 4-(3-cyanophenyl)piper- 6-[[2-[4-(3-cyanophenyl)- idine piperidinyl]ethyl]amino]- 6-oxohexanoic acid, hydro- chloride__________________________________________________________________________ | Compounds having the formula ##STR1## wherein A is a straight or branched chain alkylene group; R is hydrogen, halogen, alkyl, alkoxy, alkylthio, trifluoromethyl, nitro, amino, or cyano; and m is 2, 3 or 4; are useful in the treatment of allergic conditions in mammals. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation application of International Application No. PCT/EP2006/007207 filed Jul. 21, 2006 which claims priority to German Application Nos. 102005037564.2 filed Aug. 9, 2005 and 102006000623.2 filed Jan. 2, 2006. Each of the above-identified applications is expressly incorporated herein by reference in their entireties.
FIELD
[0002] The invention relates to an arrangement of sheet-pile wall components such as sheet piles and carrier elements.
BACKGROUND
[0003] An arrangement consisting of sheet-wall components of the type cited above is disclosed in U.S. Pat. No. 6,715,964. There, several adjacent sheet-pile sections which extend in an arc are joined by means of connecting profiles with sheet-pile sections held in the soil which serve as anchorages. The regions, which are called open cells, partly surrounded by the sheet-pile sections extending in an arc are filled with soil at least up to the level of the sheet-pile sections, whereas the outer regions which are isolated from the surrounded regions by the sheet-wall sections are filled with soil to a lower height. In this manner the sides of the sheet-wall sections that point in the outward direction partly protrude from the soil. This so-called open cell structure is used in harbor construction, for example, where the sides of the sheet-wall sections which face out form the harbor wall facing the water.
[0004] In the arrangement known from U.S. Pat. No. 6,715,964, sheet piles provided with simple locks in the form of header bars with an oval cross-section and C-shaped claw bars are used as the straight sheet-pile wall sections which extend in an arc. A star shaped profile at the end of which header bars with an oval cross-section are formed as locks serves as the connecting profile with which the sheet-pile wall sections are secured to the anchorage.
[0005] A disadvantage of the sheet-pile wall components used there is that the connecting profile joining the sheet-pile wall sections to the anchorages is under extremely high tensile forces particularly due to the soil pressure of the ground held back from the surrounding area.
[0006] In view of the above, an object of the present invention is to develop an arrangement in which the connecting profile joining the sheet-pile wall sections and the anchorage can also withstand extremely high tensile forces without the mutually engaged locks failing.
SUMMARY
[0007] The above-object is achieved according to the present invention by an arrangement of sheet-pile wall components such as sheet piles and carrier elements. The arrangement comprises two sheet-pile wall sections which include sheet-pile wall components extending in an arc or polygonal shape, and which are joined by means of locks. The sheet-pile wall components of the two sheet-pile wall sections provide on the ends of the two sheet-pile wall sections, which are arranged immediately adjacent one another, locks hooked into two lock profiles of a connecting profile. The provided connection is hooked via a third lock profile into the lock of an anchorage, and the sheet-pile wall components are provided on the respective other ends of the sheet-pile wall sections being secured in their positions such that each of the two sheet-pile wall sections partially encloses a region which serves as an open cell structure. The design at least one of the lock profiles of the connecting profile along with the lock of the sheet-pile wall components, or the anchoring being engaged with said profile in such a way that the lock profile of the connecting profile and the lock engaged therewith hook into one another and surround each other such that they are adjacent and mutually abutting, at least at three points, in at least one installation position when seen in cross-section.
[0008] According to the invention, it is disclosed that at least one of the lock profiles of the connecting profile and the lock of the sheet-pile wall components or the anchorage in engagement therewith be designed so that, when seen in cross-section, they form at least one so-called three point connection. The lock profile of the connecting profile and the lock of the sheet-pile wall components or anchorage engaged therewith are designed such that they surround each other and hook into each other in a mutual fashion in such a way that the locks adjoin and abut each another at least at three points when seen in cross-section. When tensile force impinges upon the sheet-pile wall components or the anchorage in the direction of contact, the two locks support each other at these three points in such a way that the tensile force is distributed over all three points of impact. This way the combination of a connecting profile and sheet-pile wall components or an anchorage in engagement therewith is able to withstand relatively high tensile forces which prevent the lock connections from becoming loose.
[0009] Further advantageous developments of the invention derive from the following description and the drawings.
[0010] It is particularly beneficial when the three-point connection described is formed between each lock profile of the connecting profile and the lock of the sheet-pile wall components in engagement therewith, respectively. In this manner the combination of connecting profile, sheet-pile wall components and anchorage is able to resist the influence of extremely high tensile forces without one of the lock profiles or one of the locks unintentionally opening.
[0011] Furthermore, in a particularly preferred embodiment of the arrangement according to the invention, a connecting profile is used wherein the two lock profiles at which the two sheet-pile wall components of the sheet-pile wall sections are hooked on have mirror-symmetrical contours relative to the superficial center of gravity of the connecting profile. This causes the tensile forces impinging upon the lock profiles of the connecting profile, as a result of the sheet-pile wall components, to come to bear on the connecting profile from mirror-symmetrical directions so that normally, when at least approximately equal tensile forces impinge upon the sheet-pile wall sections, the forces cancel each other out in part, and this prevents the connecting profile from being warped or twisted by forces of varying magnitude.
[0012] It is further proposed that the arrangement according to the invention be lengthened or expanded by hooking at least one of the two sheet-pile wall sections onto an additional connecting profile by means of the lock on the other end of the sheet-pile wall components of the section, and connecting the additional connecting profile to an additional sheet-pile wall section and an additional anchorage. By means of this modular construction, it is possible to build structures with correspondingly large dimensions because it is possible to anchor the free ends of the sheet-pile wall sections directly to carrier elements such as double-T carriers, T carriers, or pipe piles, for example.
[0013] It is further disclosed that a given number of sheet-pile wall sections be provided, extending in the shape of an arc or polygon, and each consisting of sheet-pile wall components that are each part of the sheet-pile wall sections being joined to an immediately adjacent sheet-pile wall section by means of a connecting profile, and each connecting profile in turn is engaged with an anchorage embedded in the soil.
[0014] In both applications described above, the connecting profiles that are used are advantageously identically constructed. In a first instance, this makes it easier to set up the arrangement. In addition, when all the connecting profiles have the same dimensions, the arrangement does not contain a weak point at the joint.
[0015] It is beneficial when the anchorage comprises a carrier element which is secured in the soil, preferably a double-T carrier, a T carrier, or a pipe pile which has been driven into solid ground by ramming or vibration. The connecting profile can then be secured directly to the carrier element which is provided with a corresponding lock bar, for instance a weld-on profile, for this purpose. Alternatively, the connecting profile is coupled or joined to the carrier element indirectly. An additional sheet-pile wall section formed from sheet-pile wall components is suitable for this, which serves as a supporting wall or retaining wall. In order to further increase the anchoring effect, Z-piles or U-piles can be used as sheet-pile wall components for the other sheet-pile wall section. The Z or U shape of the sheet piles causes the tensile forces and shearing forces impinging between the connecting profile and the anchorage to be partly reduced by the additional friction and retention forces impinging between the Z or U shaped sheet piles and the ground, thereby relieving the anchorage. This way, the overall arrangement has a higher resistance to forces impinging from the outside.
[0016] When the arrangement according to the invention is constructed as a quay wall, for example, it is proposed that the area that is partly surrounded by the sheet-pile wall sections extending in the shape of an arc or polygon be filled with soil, while the side of the sheet-pile wall sections averted from the surrounded area protrude from the soil so that the sheet-pile wall sections hold back the soil contained in the surrounded areas.
[0017] In a particularly preferred embodiment of the connecting profile for the arrangement according to the invention, the directions of contact, with which the directions of main force impact on the sheet-pile wall components which are joined with the connecting profiles and on the anchorage are aligned, lie at a 120 degree angle to one another. The working point of every lock profile, which bears the impact of the resulting tensile force with the sheet-pile wall components hooked on so as to extend in the direction of contact or with the anchorage hooked on, is the same radial distance from the superficial center of gravity of the connecting profile as the working points of the other two lock profiles. One effect of such a configuration of the connecting profile wherein the working points are the same radial distance from the connecting profile's superficial center of gravity is that the tensile forces impinging upon the connecting profile as a result of the sheet-pile wall sections, and the anchorage that is hooked on, are evenly distributed across the connecting profile so that they at least partly cancel one another out. Secondly, the installation position of the connecting profile is immaterial. The connecting profile can be rammed into the ground with one face side as well as the other. Furthermore, it is also immaterial which lock profile of the connecting profile the respective sheet-pile wall components or anchorage engages with. In the past it has been demonstrated that the use of asymmetrical connecting profiles to join three sheet-pile wall sections always causes problems. Frequently the connecting profiles are rammed into the ground on construction sites without checking if they are in the proper position. But when asymmetrical connecting profiles are in the wrong position, the course of the sheet-pile wall sections relative to each other does not correspond to the optimal flow of forces, so in the worst case there is a danger that the forces impinging upon the sheet-pile wall sections will be insufficiently diverted to the anchorage.
[0018] In order to achieve the greatest possible flexibility in the construction of the arrangement according to the invention, it is proposed that a connecting profile be used wherein the lock profiles are designed so that the lock of the sheet-pile wall components and the anchorage in which the lock profile of the connecting profile is hooked are slewable at least 15 degrees in the lock profile.
[0019] The effect of such a connecting profile construction is that the sheet-pile wall components and the anchorage move relatively freely when in the inner lock chambers of the lock profiles of the connecting profile, which all but completely rules out the possibility of the locks tilting in the lock profiles of the connecting profile when the piles are driven into the ground. In addition, imprecision in the course of the sheet-pile wall sections and the anchorage which are joined to the connecting profile can be compensated for.
[0020] It is particularly beneficial to use a connecting profile for the arrangement according to the invention wherein each lock profile comprises a thumb bar with a middle ridge, at which a thumb is formed which extends transverse to its longitudinal direction and protrudes beyond the middle ridge, along with a curved finger bar, the free end of which points in the direction of the thumb bar, forming an inner lock chamber with an at least approximately elliptical or oval cross section and, together with the end of the thumb pointing in the direction of the finger bar, defining a mouth for the lock of the sheet-pile wall section being hooked on and to the lock of the anchorage. The lock of the sheet-pile wall section is hooked on and the lock of the anchorage consists of a curved finger bar and a thumb bar which have corresponding dimensions.
[0021] When the lock profiles of the connecting profiles and the locks of the sheet-pile wall components and the anchorage are designed in a complementary fashion accordingly, the cross-section of the engaged lock profiles and locks corresponds to the described three-point connection. Now the thumb of the lock of the sheet-pile wall components or the anchorage is received in the locking chamber of the lock profile of the connecting profile, whereas the thumb of the connecting profile is received in the locking chamber of the lock of the sheet-pile wall components or the lock of the anchorage. When tensile force impinges upon the sheet-pile wall, components or the anchorage in the direction of contact, the two thumbs brace against each other and the finger bars of the other lock, respectively, such that the two locks, when viewed in cross-section, abut at three points respectively, which is to say they mutually support each other.
[0022] This three-point connection is capable of resisting extremely high tensile forces which may amount to several tens of thousands of kilonewtons due to the fact that the interaction of the thumb bars and finger bars of the locks engaging one another makes it all but impossible for the finger bars to bend or the thumb bars to break off under normal tensile forces. At the same time, the lock configuration guarantees that the engaged locks can pivot relative to one another at least to a limited degree without becoming loose. That simplifies the construction of the arrangement in a first instance. It is also makes it easer to configure the sheet-pile wall components in a circle relative to one another in the area of the connecting profile as required in order to construct the open cell structure.
[0023] It is further proposed in a particularly preferred embodiment of the connecting profile described above which is used for the arrangement according to the invention that at least one of the lock profiles be designed in such a way that it extends at an angle relative to its given direction of contact, when viewed in cross-section, such that the direction of main force impact on the lock of the sheet-pile wall components which is hooked into the lock profile pivots at least 8 to 12 degrees in either direction about the given direction of contact.
[0024] It has been shown that with a lock profile formed from a thumb bar and finger bar, if it is aligned precisely at the base relative to the given direction of contact, the pivoting of the sheet-pile wall components out of the given direction of contact is limited in the direction of the thumb bar, while the sheet-pile wall components' pivoting motion out of the given direction of contact in the opposite direction is possible many times over. Designing the lock profile at the base so that it is at an angle to the given direction of contact gives the sheet-pile wall components the ability to be pivoted in both possible directions by at least approximately the same maximum angles relative to the given direction of contact with their lock in the lock profile of the connecting profile according to the invention.
[0025] It is also beneficial when the lock profile in the connecting profile used for the arrangement extends with the main axis of its inner lock chamber, which has an elliptical or oval cross-section, at an angle of 5 to 10 degrees relative to its given direction of contact, with its thumb bar angled away from the given direction of contact. As long as the lock profile extends at such an angle relative to the base, the sheet-pile wall components can pivot in other directions relative to the given direction of contact by approximately the same angle. It is particularly beneficial when the lock profile comprises an angle of 7 to 8 degrees.
[0026] It is further provided that, in order for all the sheet-pile wall components to be able to pivot relative to the given directions of contact in opposite directions by at least approximately the same angle, all lock profiles should extend at an angle of 5 to 10 degrees relative to the directions of contact, with the two lock profiles whose thumb bars are formed at the base immediately adjacent one another being angled toward one another.
[0027] But if installation position is not a problem, it is also possible to use a connecting profile wherein the lock profiles whose thumb bars are formed at the base immediately adjacent one another are farther from the superficial center of gravity of the connecting profile than the other of the three lock profiles. This allows the arrangement's sheet-pile wall components which are hooked into the lock profiles with immediately adjacent thumb bars to have enough room to pivot so that they do not collide with the connecting profile's base.
[0028] In a particularly preferred development of the connecting profile, the ratio between the opening width of the mouth of each lock profile and the maximum opening width of the inner lock chamber of the respective lock profile is between 1 to 2 and 1 to 2.5 so that the locks of the sheet-pile wall components have enough room to pivot inside the connecting profile's lock profiles. Here, it is also beneficial when the ratio of the length of the thumb bar, as viewed transverse to the longitudinal direction of the middle ridge, and the maximum opening width of the inner lock chamber is between 1 to 1.2 and 1 to 1.4 in every lock profile of the connecting profile. When the thumb is appropriately constructed, the lock of the sheet-pile wall components and the lock of the anchorage are guaranteed to be able to pivot in the inner locking chamber, and at the same time the lock is guaranteed to sufficiently hook into the lock profile which prevents the locks engaged with one another from inadvertently becoming loose.
[0029] In order to improve the ability of the sheet-pile wall components to pivot, in a development of the connecting profile, it is further provided that the middle ridge of the thumb bar be constructed so that the ratio between the thickness of the middle ridge, observed transverse to its longitudinal direction, and the opening width of the mouth is between 1 to 1.2 and 1 to 1.4.
[0030] The three design features described above, namely the ratio between the opening width of the mouth and the opening width of the locking chamber, the ratio between the length of the thumb and the opening width of the inner lock chamber, and the ratio between the thickness of the middle ridge and the opening width of the mouth, can each be realized jointly, separately, or partially in at least one of the lock profiles.
[0031] In order to ensure that the forces impinging upon the lock profiles, which are frequently on the order of several thousand kilonewtons, do not damage the lock profile, it is further proposed that in each lock profile of the connecting profile used, the ratio between the thickness of the middle ridge, observed transverse to the longitudinal direction thereof, and the length of the thumb, observed transverse to the middle ridge's longitudinal direction, is between at least 1 to 2.3 and 1 to 2.5. The length of the thumb is a particularly important determinant of the ability of the lock of the sheet-pile wall components to pivot because the lock is pivoted about the thumb of the thumb bar, and the lock is supposed to engage with the thumb of the thumb bar in particular, partly surrounding it, thereby guaranteeing a secure hold in the inner lock chamber. The result of this is that the thickness of the middle ridge at which the thumb is formed is only allowed to be dimensioned such that the lock is able to be pivoted without impediment in the inner lock chamber, on one hand, and so that, on the other hand, the thumb bar is prevented from becoming deformed or breaking off.
[0032] In order to give the connecting profile that is used sufficient stability, it is further provided that the wall thickness of the curved finger bar of each lock profile in the area of the maximum opening width of the inner lock chamber be larger by a factor of 1.1 to 1.3 than the thickness of the middle ridge, observed transverse to its longitudinal direction, in the area of the maximum opening width of the inner lock chamber.
[0033] In a particularly preferred embodiment of the connecting profile, the three directions of contact of the three lock profiles run at a 120° offset relative to one another so that sheet-pile wall sections can be connected which approach the connecting profile at a mutual offset of 120 degrees. The present invention also contemplates designing the connecting profile in such a way that, for example, two of the lock profiles stick out of the base in opposite directions of contact, in other words at a 180 degree offset, while the third lock profile runs at a 90 degree angle relative to the other two.
[0034] The base body of the utilized connecting profile can be designed in the shape of a cylinder from which the lock profiles stick out radially in the different directions of contact. But in the alternative it is also possible to design the base in the shape of a star; i.e., with ridges sticking out in the three directions of contact in the shape of a star, at the ends of which the lock profiles are formed. A connecting profile with this configuration is particularly well suited to bridging large distances between individual sheet-pile wall components that have to be joined.
BRIEF DESCRIPTION OF THE DRAWINGS
[0035] The invention will now be described in detail with the aid of an exemplifying embodiment and modifications thereof, and with reference to the accompanying drawing in which:
[0036] FIG. 1 is a plan view of an arrangement according to the invention with multiple open cells whose ends are secured in the ground by pipe piles;
[0037] FIG. 2 is a sectional view along the line A-A in FIG. 1 showing the construction of one of the open cells in a side view;
[0038] FIG. 3 is a first enlarged section of the arrangement according to FIG. 1 showing three sheet-pile wall sections and two anchorages, with two sheet-pile wall sections joined to one anchorage in each case by means of a connecting profile;
[0039] FIG. 5 is a section corresponding to the section shown in FIG. 3 but with a modified anchorage of the open cell structure;
[0040] FIG. 6 is a plan view of the face side of an exemplifying embodiment of a connecting profile used in the arrangement according to FIG. 1 with three lock profiles which are offset 180 degrees to one another;
[0041] FIG. 7 is a plan view of the connecting profile according to FIG. 6 in which a total of three flat profiles are hooked in as sheet-pile wall components;
[0042] FIG. 8 is a plan view of the face side of a first modification of the exemplifying embodiment shown in FIGS. 6 and 7 wherein the working points of the lock profiles are the same radial distance from the superficial center of gravity;
[0043] FIG. 9 is a plan view of a second modification of the exemplifying embodiment represented in FIGS. 6 and 7 wherein the lock profiles are not angled relative to the directions of contact;
[0044] FIG. 10 is a plan view of a third modification of the exemplifying embodiment represented in FIGS. 6 and 7 wherein the base is curved and the two lock profiles whose thumb bars face each other are formed at the ends of the curved base;
[0045] FIG. 11 is a plan view of a fourth modification of the exemplifying embodiment represented in FIGS. 6 and 7 wherein a ridge bar is fashioned on the base at the ends of which one of the lock profiles is formed;
[0046] FIG. 12 is a plan view of a fifth modification of the exemplifying embodiment represented in FIGS. 6 and 7 wherein the base comprises three rounded star-shaped ridge bars at the ends of which the lock profiles are formed;
[0047] FIG. 13 is a plan view of a sixth modification of the exemplifying embodiment represented in FIGS. 6 and 7 wherein the base comprises three straight star-shaped ridge bars at the ends of which the lock profiles are formed;
[0048] FIG. 14 is a plan view of a seventh modification of the exemplifying embodiment represented in FIGS. 6 and 7 wherein the base comprises three reinforced star-shaped ridge bars at the ends of which the lock profiles are formed; and
[0049] FIG. 15 is a plan view of an eighth modification of the exemplifying embodiment represented in FIGS. 6 and 7 wherein the base comprises three rounded and reinforced star-shaped ridge bars at the ends of which the lock profiles are formed.
DETAILED DESCRIPTION
[0050] FIG. 1 is a plan view of a section of an arrangement 10 configured according to the invention. The arrangement 10 is formed from multiple arc-shaped sheet-pile wall sections 12 which are joined by means of connecting profiles 16 to first anchorages 14 which are secured in the ground. Each arc-shaped sheet-pile wall section 12 forms a so-called open cell 18 with two first anchorages 14 . The end of the sheet-pile section 12 represented in FIG. 1 is connected to a pipe pile 20 that has been driven into the ground, which serves as a closing element for the arrangement 10 , as will be explained further below.
[0051] FIG. 2 is a view representing a section taken along line A-A in FIG. 1 . As the view shows, the open cell 18 which is partly surrounded by the arc-shaped sheet-pile wall section 12 is filled with soil, whereas the area outside the open cell 18 (left-hand side of FIG. 2 ) is a shoreline area which is secured by means of the arrangement 10 in this example. The sheet-pile wall sections 12 have only been partly driven into the ground, so the water pressure of the impinging water (W) on one side and the ground pressure inside the open cell 18 on the other support the sheet-pile wall sections 12 laterally, while in the downward direction the sheet-pile wall section 12 is only partially driven into the ground. In order to prevent the sheet-pile wall sections 12 from coming out of the ground, they are secured in solid ground by the anchorage 14 and 20 .
[0052] FIG. 3 is an enlarged plan view representing a section of the arrangement 10 for purposes of laying out the construction of the arrangement 10 in greater detail. The sheet-pile wall section 12 represented in FIG. 12 consists of a total of nine sheet piles 22 , in this case union flat profiles, which are driven into the ground in an arc configuration and hooked into each other. The last two sheet piles 22 of the sheet-pile wall section 14 , disposed at either end, are hooked into the lock profiles of two connecting profiles 16 whose construction will be described in detail further below. As FIG. 1 shows, additional arc-shaped sheet-pile wall sections 12 are hooked into the other lock profiles of the two connecting profiles 16 accordingly.
[0053] The third lock profile of each connecting profile 16 is engaged with a supporting wall 24 which is formed from sheet piles 22 , in this case as well union flat piles. The supporting wall 24 is joined, by means of a weld-on profile 26 , with a double-T carrier 28 which has been rammed into the ground. The supporting wall 26 and the double-T carrier 28 joined therewith form the first anchorage 14 .
[0054] As made abundantly clear by the arrangement represented in FIG. 1 , deviations in the course of sheet-pile wall sections 12 can be compensated by means of the connecting profile 16 , which is especially important where multiple sheet-pile wall sections have to be joined at a common point.
[0055] FIG. 4 represents another section of the arrangement 10 in an enlarged plan view. This section represents the securing of the end of the sheet-pile wall section 12 , for instance in solid ground on the shoreline. Stabilization is facilitated by means of the second anchoring 20 , which in this example consists of a pipe pile 30 that has been driven into the ground. The last sheet piles 22 of the sheet-pile wall section 12 are stabilized by means of a weld-on profile 26 which is welded onto the shell of the pipe pile 30 .
[0056] Lastly, FIG. 5 represents one possible modification of the first anchorage 14 represented in FIG. 3 . In order to relieve the double-T carrier 28 of extremely high tensile and shearing forces, which could be transferred from the sheet-pile wall sections 12 to the double-T carrier 28 by means of the supporting wall 24 , and in order to increase the resistance of the overall anchorage 14 to any tensile forces and shearing forces that might occur, the supporting wall 24 is made of a total of four sheet piles 22 instead of two. Furthermore, the four sheet piles 22 have been driven into the ground at an angle of 10 degrees out of alignment in an alternating fashion, from a cross-sectional perspective, in order to be able to counteract the tensile and shearing forces impinging in alignment upon the supporting wall 24 by means of greater frictional and holding forces. It would also be possible to use U shaped or Z shaped sheet piles driven into the ground for the supporting wall 24 instead of the angled configuration of the sheet piles 22 .
[0057] FIGS. 6 and 7 represent a plan view of an exemplifying embodiment of a connecting profile 16 which is used in the arrangement 10 , which has a constant cross-section over its entire length. The connecting profile 16 serves for joining two sheet-pile wall sections 12 with the supporting wall 24 . The connecting profile 16 represented in FIGS. 6 and 7 has three prescribed directions of contact X, Y and Z, which are at a 120 degrees offset relative to one another. Direction of contact X, Y or Z in this sense means the direction in which the sheet piles 22 form a so-called three-point connection with the connecting profile 16 in cross-section when the piles are hooked on.
[0058] The connecting profile 16 has a base 32 from which three lock profiles 34 , 36 and 38 project in directions of contact X, Y and Z. Since lock profiles 34 , 36 and 38 are identical, the construction of lock profiles 34 , 36 and 38 will be described below with reference to FIG. 6 with the aid of lock profile 34 as represented in FIG. 6 above.
[0059] The lock profile 34 has a thumb bar 40 which projects from the base 32 and, disposed at a remove therefrom, a finger bar 42 , the two of which protrude from base 32 together and partly surround an inner lock chamber 44 .
[0060] The thumb bar 40 is formed by a middle ridge 46 which emerges from the base 32 , at the free end of which a thumb 48 is formed, extending transverse to the longitudinal direction of the ridge, which extends beyond the ridge 46 in both directions.
[0061] The finger bar 42 also emerges from the base 32 and extends toward the thumb bar 40 in a curved manner. The finger bar 42 ends together with the exterior surface of the thumb 48 in a tangential plane (not represented) and defines a mouth 50 together with the end of the thumb 48 that points in the direction of the finger bar 42 .
[0062] The transitions between the base 32 and the middle ridge 46 , between the middle ridge 42 and the thumb 48 , and between the base 32 and the finger bar 42 are rounded and their shape conforms to that of an ellipse so that the inner lock chamber 44 has an inner cross-section that is at least approximately elliptical.
[0063] In the connecting profile 16 the sheet piles 22 that will be hooked on can be pivoted in a defined fashion with their locks 52 in the inner lock chambers 44 of the lock profiles 34 , 36 , and 38 during which time a secure hold of the lock 52 of the sheet pile 22 in the chamber 44 of the connecting profile 16 is still guaranteed in every pivot position of the sheet pile 22 .
[0064] In order to simplify pivoting, the following design features are additionally provided for the connecting profile 16 according to the invention. First the ratio between the opening width (a) of the mouth 50 and the maximum opening width (b) of the inner lock chamber 24 is approximately 1 to 2.1. The ratio between the thickness (c) of the middle ridge 46 , as viewed transverse to its longitudinal direction, and the opening width (a) of the mouth 50 is 1 to 1.3 in turn. The ratio between the thickness (c) of the middle ridge 46 , as viewed transverse to the longitudinal direction thereof, and the length (d) of the thumb 48 , as viewed transverse to the longitudinal direction of the middle ridge 46 , is 1 to 2.3. Furthermore, the ratio of the length (d) of the thumb 48 , as viewed transverse to the middle ridge 46 , and the maximum opening width (b) of the inner lock chamber 44 is 1 to 1.25.
[0065] This design feature guarantees that the lock 52 of the sheet pile 22 retains its ability to pivot some 16 degrees without the lock 52 of the sheet pile 22 jumping out of the locking profile 34 , 36 or 38 of the connecting profile 16 .
[0066] But in order to guarantee that the locking profile 34 , 36 and 38 is able to resist the arising holding forces and does not break despite the potential ability of the sheet-pile wall components to pivot, the bars 40 and 42 which form the locking profile 34 , 36 and 38 are dimensioned accordingly.
[0067] The wall thickness (e) of the curved finger bar 42 of each locking profile 34 , 36 and 38 in the area of the maximum opening width b of the inner lock chamber 44 is larger by a factor of 1.2 than the thickness (c) of the middle ridge 46 as viewed transverse to its longitudinal direction in the area of the maximum opening width (b) of the inner lock chamber 44 . Since the tensile force portion impinging on the thumb bar 40 along the longitudinal direction of the middle ridge 46 is greater than the transverse force portion, the middle ridge 46 of the thumb bar 40 can be constructed weaker than the finger bar 42 . In contrast, at the finger bar 42 the impinging transverse force is greater, so a relatively large bending momentum impinges upon the finger bar, which the finger bar must absorb.
[0068] In order to ensure that the sheet piles 22 to be hooked on can pivot at least approximately over the same angle range relative to the directions of contact X, Y and Z respectively, the three locking profiles 34 , 36 and 38 are constructed on the base 32 such that they tilt relative to the directions of contact X, Y and Z, as explained below.
[0069] The locking profile 34 represented at the top of FIG. 6 is at an angle α, in this case a 7.5 degree angle, relative to direction of contact X, in which case the thumb bar 42 is angled away from direction of contact X.
[0070] The two other locking profiles 36 and 38 are also fashioned on the base 32 at a 7.5 degree angle to directions of contact Y and Z respectively, with the thumb bars 32 being angled away from the directions of contact Y and Z again here.
[0071] Since the two locking profiles 36 and 38 represented at the bottom of FIG. 6 are disposed closer to each other by virtue of being angled, in turn the distance from the two locking profiles 36 and 38 to the superficial center of gravity (S) of the connecting profile 16 is greater than the distance between the top locking profile 34 and the same point. This ensures that the sheet piles 22 that will be hooked into the two locking profiles 36 and 38 do not touch even when moved as close together as possible.
[0072] FIG. 7 represents the connecting profile 16 according to the invention with the union flat profiles represented in FIGS. 1 to 5 as sheet piles 22 hooked into locks 52 on its lock profiles 34 , 36 and 38 . The pivoting range within which the sheet pile 22 can be hooked on the connecting profile 16 is represented in FIG. 7 for the lock profile 34 represented at the top of the figure. In this example, the sheet pile 22 can be hooked on the connecting profile 16 in a pivoted position, said pivot comprising an angle of some 8.5 degrees between a first end position and a second end position, proceeding from a starting position in which the direction of main force impact F on the sheet pile 22 is parallel to the direction of contact X, so the pivot range is approximately 8.5 degrees as indicated by the two arrows, and the engaged locks 34 and 52 make contact at three points from a cross-sectional perspective.
[0073] FIG. 8 shows a first modification of the connecting profile 16 represented in FIGS. 6 and 7 . In this modified connecting profile 16 a the lock profiles 34 a, 36 a and 38 a are also fashioned on the base 32 a at a 120° offset from each other. A unique aspect of this connecting profile 10 a is that the working point A of each lock profile 34 a, 36 a and 38 a upon which the resulting tensile force impinges if the sheet pile 22 has been hooked on so as to extend in direction of contact X, Y or Z is the same radial distance (f) from the superficial center of gravity (S) of the connecting profile 16 a as the working points A of the two other lock profiles 36 a, 38 a and 34 a respectively. This configuration of the connecting profile 16 a whereby the working points (A) are the same radial distance from the superficial center of gravity (S) of the connecting profile 16 a causes the tensile forces impinging upon the connecting profile 16 a as a result of the hooked-on sheet piles 22 to be evenly distributed across the connecting profile 16 a and to at least partly cancel each other out. Another consequence is that the installation position of the connecting profile 16 a is variable, so one can integrate the connecting profile 16 a in any position without having to pay any attention to the course of the lock profiles 34 a, 36 a and 38 a when hooking on the sheet piles 22 .
[0074] FIGS. 9 to 15 represent additional modifications of the connecting profile 16 wherein the base 32 consists of ridge bars in, for instance, a star configuration, at the free ends of which the lock profiles 34 , 36 and 38 are fashioned. However, it should be noted that in all the modifications shown the design features with respect to the opening width of the mouth 50 , the opening width (b) of the inner lock chamber 44 , the thickness (c) of the middle ridge 46 , the length (d) of the thumb 48 , and the wall thickness (e) of the finger bar 42 are realized in an analogous manner. In the modifications represented in the figure, the lock profiles 34 , 36 and 38 are not at an angle to directions of contact X, Y and Z but configured such that the inner lock chamber 44 at its maximum opening width (b) extends approximately at a right angle to the direction of contact X, Y and Z.
[0075] It bears noting, however, that in these modifications too it is possible for at least one of the lock profiles 34 , 36 and 38 to extend at an angle relative to the directions of contact X, Y and Z as described above with reference to FIGS. 6 and 7 .
[0076] FIG. 9 represents a second modification 16 b of the connecting profile 16 utilized for the arrangement 10 according to the invention, wherein the lock profiles 34 b, 36 b and 38 b do not extend at an angle to the directions of contact X, Y and Z.
[0077] In contrast, FIG. 10 represents a third modification 16 c of the connecting profile 16 utilized for the arrangement 10 according to the invention, wherein the base 32 c extends in a curved manner, and the two lock profiles 36 c and 38 c are fashioned at the ends of the curved base 32 c. The third lock profile 34 c, on the other hand, is fashioned in the center of the curved base 32 c.
[0078] FIG. 11 is a plan view representing a fourth modification 16 d of the connecting profile 16 utilized for the arrangement 10 according to the invention, wherein a ridge bar 54 d is fashioned at the base 32 d at the ends of which one of the lock profiles 34 d is formed.
[0079] FIG. 12 is a plan view representing a fifth modification 16 e of the connecting profile 16 utilized for the arrangement 10 according to the invention, wherein the base 32 e comprises three rounded ridge bars 54 e extending in a star configuration at the ends of which the lock profiles 34 e, 36 e and 38 e are fashioned. The purpose of the rounded course of the ridge bars 54 e is to better dissipate the stresses impinging upon the lock profiles 34 e, 36 e and 38 e.
[0080] FIG. 13 is a plan view representing a sixth modification 16 f of the connecting profile 16 utilized for the arrangement 10 according to the invention, wherein the base 32 f comprises three straight ridge bars 54 f extending in a star configuration at the ends of which the lock profiles 34 f, 36 f and 38 f are fashioned.
[0081] FIG. 14 is a plan view representing a seventh modification 16 g of the connecting profile 16 utilized for the arrangement 10 according to the invention, wherein the base 32 g comprises three reinforced ridge bars 54 g extending in a star configuration at the ends of which the lock profiles 34 g, 36 g and 38 g are fashioned. The reinforcement of the ridge bars 54 g prevents the lock profiles 34 g, 36 g and 38 g from breaking under extreme tensile force.
[0082] Lastly, FIG. 15 is a plan view representing an eighth modification 16 h of the connecting profile 16 utilized for the arrangement 10 according to the invention, wherein the base 32 h comprises three rounded and reinforced ridge bars 54 h extending in a star configuration at the ends of which the lock profiles 34 h, 36 h and 38 h are fashioned. Here too the rounded shape is meant to improve the dissipation of stress.
[0083] The represented exemplifying embodiments are only some of the possible configurations. For instance, the base 32 can also be fashioned such that the lock profiles 34 , 36 and 38 project in different directions of contact. That makes it possible to arrange the open cells 18 of the arrangement 10 at different angles relative to each other. | An arrangement of sheet-pile wall components includes two sheet-pile wall sections. The ends of the two sheet-pile wall sections are arranged. Their locks are hooked into two lock profiles of a connecting profile which is hooked via a third lock profile into the lock of an anchorage. The respective other ends of the sheet-pile wall sections are secured such that each of the two sheet-pile wall sections partially encloses a region. At least one of the lock profiles and the lock of the sheet-pile wall component of the anchorage in engagement therewith are configured in such a way that the lock profile of the connecting profile and the lock in engagement therewith are hooked one inside the other and grip around one another. As viewed in cross section, they bear on one another and are supported against one another by at least three points in at least one installed position. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to hydrostatic bearings in which a shaft and the static bearing to be fitted on the shaft are rotatable or slidable relative to one another, and more particularly to a hydrostatic bearing utilizing a ferromagnetic fluid as a working fluid.
2. Description of the Prior Art
There has been proposed a hydrostatic bearing of a conventional type as shown by FIG. 12.
This conventional type bearing comprises a rotary shaft 2 fitted within a hydrostatic bearing 1. The inner face of the hydrostatic bearing 1 is provided with an oil chamber 3 supplied with working oil under a predetermined pressure, annular recovering grooves 4 disposed at both axial ends of the bearing spaced apart at a predetermined distance, and a pair of sealing grooves 5, each of which is also disposed at both axial extremities of the bearing. The oil chamber 3 is supplied with the working oil from an exterior oil pump 7 through a vent port 6. Working oil axially squeezed out from the oil chamber 3 is recovered from the recovering grooves 4 and returned to an oil tank 9 via a vent port 8. The sealing groove 5 is supplied with hydrostatic sealing gas from a pressurized sealing gas source 10 via a pressure regulating valve 11 and a port 12 so that the operating oil squeezed out of the recovery grooves 4 can be prevented from escaping.
U.S. Pat. No. 3,439,961 discloses a bearing entitled "Bifluid Hydrodynamic Bearing" which uses a high pressure gas as a hydrostatic gas and seals the operating high pressure gas by magnetically attracting a ferromagnetic fluid containing fine ferrite particles by means of a magnetizing coil.
However, since the conventional bearing as shown by FIG. 12 is constructed in such a manner that the working oil is prevented from escaping by keeping the pressure balance between the working oil and the sealing fluid, it becomes impossible to shut out the hydrostatic system from the exterior atmosphere. Additionally, another problem is that such air sealing cannot be applied to such facilities for making semiconductors which must be carried out in a vacuum.
It was contemplated to use a mechanical seal in place of an air seal with an intention to obviate such drawbacks, but in this way it was inevitable that some extent of air exists around the sealing means in the oil recovering means as a shock absorbing medium so as to maintain the sealing function of the device when the hydrostatic bearing is started, at the time of load variation and against thermal expansion, and therefore, it is also inevitable that a slight extent of seal gas may be squeezed out.
Moreover, roller bearings instead of hydrostatic bearings have also been used, however, such bearings require grease as a lubricant and the oil contained in the grease may evaporate and thus contaminate the outer atmosphere.
The bearing of U.S. Pat. No. 3,439,961 is constructed to seal the high pressure gas by a ferromagnetic fluid, but because of the high extent of compressibility of the high pressure gas used as a hydrostatic fluid as compared with liquid, it cannot be used since it is not possible for such bearing to supplement high pressure gas during running, so it would not be able to function as a hydrostatic bearing when some extent of high pressure gas has been squeezed out due to long periods of use.
An object of the present invention has been set by taking the problems encountered in the aforesaid prior art bearings into consideration, and it aims to provide a hydrostatic bearing using ferromagnetic fluid which can solve the above-mentioned problems by virtue of utilizing noncompressive ferromagnetic fluid as the working fluid of a hydrostatic bearing and by preventing this ferromagnetic fluid from escaping outside of the bearing.
Another object of the present invention is to provide a hydrostatic bearing utilizing ferromagnetic fluid capable of improving the efficiency of impelling the ferromagnetic fluid by providing suitable impelling means for returning the ferromagnetic fluid to the fluid chamber of the bearing.
SUMMARY OF THE INVENTION
In order to accomplish the aforesaid objects, a first aspect of the present invention is directed to a hydrostatic bearing system which comprises a shaft, a hydrostatic bearing provided with fluid chamber(s) at positions confronting the shaft for hydrostatically holding ferromagnetic fluid, means for sealing at both axial ends of the chamber, and being movable relative to each other. The hydrostatic bearing further comprises recovery grooves disposed at both axial ends of the chamber for collecting ferromagnetic fluid squeezed out from the fluid chamber, magnetic sealing means disposed at the portion from which the ferromagnetic fluid is squeezed out, circulating passages formed for circulating the ferromagnetic fluid between the recovery groove and the fluid chamber and impelling means disposed within the passage for impelling the ferromagnetic fluid toward the fluid chamber.
A second aspect of the present invention is directed to a hydrostatic bearing system which comprises, a shaft and a hydrostatic bearing fitted around said shaft, movable relative to each other, and provided with fluid chamber(s) at positions confronting the shaft for hydrostatically holding ferromagnetic fluid and means for sealing at both axial sides of the chamber. The hydrostatic bearing further comprises recovery grooves for collecting the ferromagnetic fluid squeezed out from the chamber, a circulating passage connecting the recovery grooves and the chamber, impelling means relating axially to the side portion of the recovery groove for impelling the ferromagnetic fluid, and magnetic sealing means disposed at the portion from where the ferromagnetic fluid is squeezed out. The impelling means consists of a flexible membrane which constitutes a side wall of the recovery groove, a plurality of impeller ring members concentrically stacked around the passage and abutted to the outside of the flexible membrane of the recovery groove so as to be actuated axially and reciprocally, and means for changing the flow resistance of the ferromagnetic fluid being located at the end connecting the circulating passage to the recovery groove near the impeller ring.
According to the first aspect of this invention, ferromagnetic fluid at a predetermined pressure is supplied to the fluid chamber defined between the shaft and the bearing. The bearing function is attained by static pressure of the ferromagnetic fluid contained in the fluid chamber. In addition, the ferromagnetic fluid is prevented from escaping outward by virtue of the magnetic seal disposed at the axial ends of the bearing. Since both the circulating passages and the impelling means are disposed within the bearing, the travel length of the magnetic fluid can be made shorter, giving rise to a reduced amount of magnetic fluid required by the bearing system.
With respect to the second aspect of this invention, since the magnetic fluid is supplied at a predetermined pressure by the impelling means to the fluid chamber defined between a guide shaft and the bearing, the bearing function is attained by the static pressure of the ferromagnetic fluid contained in the fluid chamber. In addition, the magnetic fluid is securely prevented from escaping outward by virtue of the magnetic seal disposed at both axial ends of the fluid chamber. Since the impelling means for returning the magnetic fluid to the fluid chamber is disposed adjacent to the recovery grooves, the area of applying pressure by the impelling means can be made larger and thereby improves the efficiency of impelling the fluid.
Explanation will now be made of several preferred embodiments in accordance with the present invention by referring to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional side elevation showing a first embodiment of the present invention;
FIG. 2 is a right side front view of FIG. 1;
FIG. 3 is a sectional side elevation showing a second embodiment of the present invention;
FIG. 4 is a sectional side elevation showing a third embodiment of the present invention;
FIG. 5 is a transverse plan view taken along line I--I of FIG. 4;
FIGS. 6 through 8 are side elevations, respectively, showing other modifications of the impelling means applicable to the present invention;
FIG. 9 is a sectional side elevation showing a fourth embodiment of the present invention;
FIG. 10 is an enlarged sectional plan view showing one example of an impelling means applicable to the fourth embodiment of the present invention;
FIG. 11 is an enlarged sectional view showing another example of the impelling means; and
FIG. 12 is a sectional side view showing a prior art bearing.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Both FIG. 1 and FIG. 2 are sectional views showing a first embodiment of the invention.
In the drawings, numeral 1 denotes a hydrostatic bearing, and 2, a rotary shaft rotatably and slidably fitted adjacent to the inner surface of the hydrostatic bearing.
The hydrostatic bearing 1 comprises a cylindrical casing 21 fabricated of nonmagnetic material such as a nonferrous metal, an alloy, or a synthetic resinous material having a diameter slightly larger than the outside diameter of the rotary shaft 2.
At the central portion on the inner surface of the casing 21, there are disposed fluid chambers 22, each formed as a recess in the inner surface of the casing 21, for hydrostatically holding a ferromagnetic fluid as a working fluid. The recesses are formed at four positions on the inner peripheral surface of the casing in such a manner that the chambers are positioned to confront with each other in the x and y direction.
The ferromagnetic fluid to be used for the present invention is a kind of colloidal fluid which has been prepared by stably dispersing fine magnetic particles, such as ferrite, in a carrier in liquidous phase. The ferromagnetic fluid behaves as if the fluid itself has apparent magnetic properties without being susceptible to any sign of coagulation or precipitation under a newtonian field or magnetic field.
Both axial ends on the inner peripheral surface of the casing 21 are provided with magnetic seals 23L and 23R, respectively. Each of the magnetic seals 23L and 23R is composed of an annular permanent magnet 24 magnetized to have N-S poles in the axial direction and a pair of magnetic yokes 25a and 25b, each of which attach to a respective axial end of each magnet 24. In this instance, the inner diameter of the magnetic yokes 25a and 25b are selected to be slightly larger than the outside diameter of the rotary shaft 2, and the ferromagnetic fluid, as described in further detail below, can be magnetically attracted by the magnetic field established between these magnetic yokes 25a and 25b, thereby preventing the magnetic fluid from escaping.
Annular recovery grooves 28L and 28R are formed at the portions between the fluid chamber 22 and each magnetic seal 23L and 23R. The recovery grooves are allowed to communicate with the fluid chamber 22 through a slight clearance defined between lands 26 and the outer face of the rotary shaft 2. Within the casing 21 is provided a circulating passage 29 which communicates with both the recovery grooves 28L and 28R and the fluid chamber 22 through a fixed throttling O.
A pair of impelling means 30L and 30R are disposed around the circulating passage 29 to move the ferromagnetic fluid toward the fluid chamber 22 and thereby maintain the hydrostatic pressure of the ferromagnetic fluid in the fluid chamber 22 at a predetermined level. The impelling means 30L and 30R are composed of three phase exciting coils 31a, 31b, 31c, supplied by circuit 32, which generate a moving magnetic field by successive supplying of electricity of three phase alternative current of preselected frequency attracting the ferromagnetic particles and impelling the attracted particles toward the center of the fluid chamber 22, for example, at a flow rate and a discharge pressure of about 0.06 cc/sec and 5 Kg/cm 2 respectively.
In the drawing, numeral 33L and 33R are dust seals disposed outside the respective magnetic seals 23L and 23R for preventing dust from entering from outside.
During operation, when the rotary shaft 2 is in a stationary state, no electric current is supplied from the circuit 32 connected to the impelling means 30L and 30R. As such, no moving magnetic field is created in the impelling means 30L and 30R and the ferromagnetic fluid is stationary so that the hydrostatic pressure within the fluid chamber becomes zero and the rotary shaft 2 contacts, and is supported by, the lands 26 of the hydrostatic bearing 1. Under such condition, the ferromagnetic fluid is distributed throughout the fluid chamber 22, the recovery grooves 28L and 28R, and the circulating passage 29, and due to the magnetic seals 23L and 23R, leakage or escaping of the ferromagnetic fluid outwards of the bearing is prevented by the fact that the ferromagnetic fluid is attracted by the magnetic force exerted by said magnetic seals.
When it is required to hydrostatically support the rotary shaft 2 during rotation, the actuating circuit 32 is started so as to supply electric current to the exciting coils 31a, 31b, 31c connected to the impelling means 30L and 30R to create a shifting magnetic field directed towards the central part of the fluid chamber 22. The magnetic field acts to impel the ferromagnetic fluid toward the fluid chamber 22, and as such, the ferromagnetic fluid in the fluid channel 22 is kept at a predetermined pressure.
Upon pressurization of the ferromagnetic fluid, as mentioned above, a thin film of ferromagnetic fluid is formed within a bearing cavity defined between the inner face of the hydrostatic bearing 1 and the outer peripheral face of the rotary shaft 2, resulting in a uniform clearance in the radial direction. This allows the rotary shaft 2 to float in the bearing cavity of the hydrostatic bearing 1 ensuring smooth rotation of the shaft.
The ferromagnetic fluid squeezed out of the fluid chamber 22 is collected by the recovery grooves 28L and 28R and then returned to the impelling means 30L and 30R via the circulating passage 29. Any ferromagnetic fluid squeezed further outside the recovery grooves 28L and 28R is prevented from escaping by means of the magnetic seals 23L and 23R, thereby preventing the exterior atmosphere from contamination as well as assuring remarkable reduction in the loss of ferromagnetic fluid in use.
Furthermore, since both the circulating passages and the impelling means are disposed within the casing 21, it is rendered possible to reduce the overall length of the circulating passage 29, giving rise to a reduction in the amount of expensive ferrofluid required as a working fluid resulting in reduced production costs.
Although the first embodiment is explained with respect to a bearing for supporting a rotary shaft having a circular cylindrical outer face, it is also possible for this invention to be applied to other bearing types which are applied to a fixed shaft in place of the rotary shaft upon which the hydrostatic bearing 1 is slidably moved in an axial direction; namely, a so-called slider.
A second embodiment of the present invention will be described with reference to FIG. 3. When the fixed shaft 34 is of the type having a square cross sectional shape, the central opening of the casing 1 is also made to be square in cross section. The inner faces of said casing confronting each face of the stationary shaft 34 are formed to have independent fluid chambers 22a, 22b, 22c, 22d. Lands 35a, 35b, 35c, 35d are formed alongside the fluid chambers 35a to 35d, respectively, and recovery grooves 36a, 36b, 36c, 36d are formed correspondingly so that the ferrofluid collected by the recovery grooves can be circulated toward the fluid chambers 22a through 22d by means of the independent impelling means 37a, 37b, 37c, 37d via circulating passages 0.
The relative displacement in both x and y directions between the hydrostatic bearing 1 and the fixed shaft 34 in a plane perpendicular to the axis is detected, respectively, by displacement detectors 38 and 39 as shown schematically in FIG. 3. As a result, the amount of ferromagnetic fluid to be delivered is adjusted in accordance with the detected value by respective impelling means 37a through 37d. As such, the hydrostatic bearing 1 can be floatingly supported with the clearance between the outer surface of the fixed shaft 34 and the inner surface of the hydrostatic bearing 1 kept uniform.
The above embodiments were explained with respect to the applications, where the hydrostatic bearing 1 is fitted around the rotary shaft 1 or the fixed shaft 34, however, it is similarly practicable that a cylindrical hydrostatic bearing is fitted around a fixed shaft.
A third embodiment of the present invention will be described with reference to FIGS. 4 and 5.
In this embodiment a hydrostatic bearing is applied as a radial and thrust bearing to a rotary shaft composed of a tapered portion 2a, the outer diameter of the peripheral surface of which becomes larger toward its downward portion, and a flat portion 2b, which intersects the tapered portion 2b at a right angle to the axial direction of the shaft. The hydrostatic bearing 1 comprises a radial bearing portion 1a for receiving tapered portion 2a and a thrust bearing portion 1b for receiving the flat portion 2b.
The radial bearing portion 1a comprises a cylindrical casing body 42 comprising a cylindrical inner face 41a, adjacent to the cylindrical outer face of the rotary shaft 2, and a tapered inner face 41b, contiguously formed with the cylindrical face 41a and adjacent to the tapered portion 2a of the rotary shaft 2. The top or outer end portion in the cylindrical inner face 41a is provided with a dust seal 43 and a magnetic seal 44. The tapered inner face 41b is provided with fluid chambers 45 and 46 each being disposed at four equally spaced apart portions in the circumference and being aligned in two arrays in the axial direction. Annular recovery grooves 47 and 48 are disposed between the fluid chamber 45 and magnetic seal 44 and between the fluid chambers 45 and 46, respectively. Moreover, there are provided recovery grooves 50 each being disposed via a land 49. The interior of the casing body 42 is provided with a supply passage 51 and a recovery passage 52. One end of the supply passage 51 communicates with the axially central portion of each fluid chamber 45 and 46 through fixed restriction O 1 and the other end opens at the lower end face of the cylindrical casing body 42. One end of recovery passage 52 communciates with the recovery grooves 47, 48 and 50 and the other end opens at the lower end face of the cylindrical casing body 42.
The thrust bearing portion 1b is composed of a circular casing body 53 which is fitted to the lower end face of the bearing portion 1a in a fluid tight manner. At its central part, adjacent to the flat end face 2b of the rotary shaft 2, a fluid chamber 54 is formed as a circular recess, and there is also formed an annular recovery groove 55 located adjacent to the peripheral end portion of the rotary shaft 2. The casing body 53 is also provided with a supply passage 56, one end of which communicates with the fluid chamber 54 via the fixed orifice O 2 and a recovery passage 57, one end of which communicates with the recovery passage 55. In addition, the supply passage 56 communicates with the supply passage 51 of the radial bearing portion 1a, while the recovery passage 57 and the recovery passage 52 communicate with each other. The other ends of both the supply passage 56 and the recovery passages 57 communicate with each other so as to constitute a circulating circuit.
At the halfway point, or thereabout, of the circulating circuit, there is interposed an impelling means 30 having a construction the same as that of the aforesaid impelling means 30L and 30R which constitute a travelling magnetic field.
During operation, the hydrostatic pressure of the ferromagnetic fluid in the fluid chambers 45, 46 and 54 can be maintained at a predetermined level by impelling, by means of the impelling device 30, the ferromagnetic fluid toward the fluid chambers 45 and 46 of the radial bearing portion 1a as well as the fluid chamber 54 in the thrust bearing 1b. As a result, the rotary shaft 2 is floatingly supported by the hydrostatic bearing 1 by means of the aforesaid hydrostatic pressure. The radial force is received by the hydrostatic pressure given by the fluid chambers 45 and 46 and the thrust force is received by that given by the fluid chamber 54.
The ferromagnetic fluid squeezed out from each fluid chamber 45, 46 and 54 is collected in the recovery grooves 47, 48, 50 and 55, and the thus collected ferromagnetic fluid is moved through the recovery passages 52 and 57 by means of the impelling device 30 and further delivered to each fluid chamber 45, 46 and 54 through the supply passages 51 and 56.
Since a magnetic seal 44 is provided at the upper end of the radial bearing portion 1a, the ferromagnetic fluid is magnetically attracted by the magnetic force imparted by said seal 44, thereby preventing leakage of the ferromagnetic fluid outside the bearing system. In addition, since the radial bearing portion 1a and the thrust bearing portion 1b are fitted in a fluid tight configuration with each other, leakage of ferromagnetic fluid through the gap between the two mating bearing portions is prevented.
By virtue of the construction of the third embodiment shown by FIGS. 4 and 5, since the axial end of the rotary shaft 2 is formed with a tapered shape, and correspondingly the radial bearing portion 1a of the hydrostatic bearing 1 is formed to have a tapered inner face, each of the bearing members is pre-pressurized to raise the stiffness as a hydrostatic bearing and thereby enables the rotary shaft to be floated without fail.
The clearance between the hydrostatic bearing 1 and the rotary shaft 2 may be uniformly maintained by controlling the force of the impelling means 30 based on the value of displacement in the x and y directions in the plane perpendicular to the lengthwise axis of the rotary shaft 2. Although in the foregoing explanation on the fluid chambers in the embodiments 1 through 3, two opposing recesses in both the x and y directions were referred to, it is not required to be restricted to such disposition, but any other suitable arrangement, such as composed of three opposing fluid chambers or more, may be optionally selected.
Although the explanation on the first through the third embodiment has been made with respect to the impelling means 30 forming a shifting magnetic field 30, such is not required. Means comprising a fluid pump can be made in such a manner as shown in FIG. 6 comprising a cylindrical chamber 73 having a flexible diaphragm 72 formed as a part of the circulating passage 71, magnets 74 and 75 disposed before and after the cylinder chamber 73 for changing resistance to the travel of the ferromagnetic fluid so as to raise apparent viscosity of the fluid, and an actuating means 76 such as a piezo-electric element or an electromagnetic solenoid or the like which is vibrated up and down in a predetermined cycle. During operation the magnets 74 and 75 are ON-OFF controlled in synchronization with the vibration of actuating means 76 so that magnet 74 is kept OFF while magnet 75 is ON thereby attracting the ferromagnetic fluid collected in the recovery groove and passing through the circulating passage. Subsequently, magnet 74 is switched ON and magnet 75 OFF as actuating means 76 is extended to depress the diaphragm 72. As a result, the apparent viscosity of the ferrofluid at the side of magnet 74 becomes high and that at the side of the magnet 75 becomes low, and thus the flow of the ferromagnetic fluid during the time of pressure rise caused by the depression on the diaphragm 72 is toward the magnet 75 because the resistance to flow is higher at the side of the magnet 74 than that at the side of magnet 75. Such a fluid pump that impels the ferromagnetic fluid within the cylinder chamber 73 toward the fluid chamber can also be utilized.
In this case, by selecting the impelling frequency of the diaphragm 72, actuated by the impelling means 76, for 300 Hz and assuming that the surface area of the diaphragm 72 is 2 cm 2 , the diaphragm can display a flow rate of 0.06 cc/sec and a discharge pressure of 5 Kg/cm 2 .
Alternatively, the diaphragm 72 and the cylinder chamber 73 can be dispensed with and a part of the circulating passage 71 is composed of a flexible tube to which an impelling member such as a piezo-electric element is engaged with or pressed on.
Alternatively, as shown in FIG. 7, a set of check valves 80 and 81, each having a valve seat 77 with a ball 79 urged against the valve seat by a spring 78 can be used instead of the magnets 74 and 75.
Alternatively, as shown by FIG. 8, the impelling means can be constructed in such a manner that three ringular shaped impelling members 82a, 82b, 82c, made of piezo-electric elements, are concentrically stacked one after another, and are disposed at the branch point of the circulating passage 83. Each impelling member is lowered successively, from the state as shown in FIG. 8, so that the outermost impelling member 82c is lowered first, then the intermediate member 82b, and finally the innermost member 82a, and thus these three members may constitute an impelling pump to deliver the ferromagnetic fluid in the system toward the fluid chamber 22.
Alternatively, the impelling means can be constructed by winding a magnetic coil or coils around the circulating passage. Exciting current is applied to the coils so as to generate magnetic flux directed toward the fluid chamber thereby impelling the ferromagnetic fluid. In short, the impelling means has only to be constructed to be capable of impelling or delivering the ferromagnetic fluid with pressure toward the fluid chamber.
In addition, the casing 21 or 42 is not limited to be formed as a cylindrical configuration, but may be made to have a partly cut ringular cross section. In such a case, magnetic seals are to be formed not only on both axial ends, but also on the circumferential ends of the cut portion.
A fourth embodiment of the present invention will be described with reference to FIG. 9.
The hydrostatic bearing 1 comprises a cylindrical casing 21 fabricated of a nonmagnetic material similar to that shown in FIG. 1 of the aforesaid first embodiment.
The casing 21 is axially divided into three sections 21a, 21b, 21c which are joined together in a fluid tight manner.
At the central portion on the inner surface of section 21b, there are disposed fluid chambers 22, for hydrostatically holding a ferromagnetic fluid as a working fluid, at four places on the inner peripheral surface of the casing in such a manner that the two pairs are positioned to oppose each other in the x or y direction.
The ferromagnetic fluid to be used for the present invention is a colloidal fluid such as having been prepared by stably dispersing fine magnetic particles such as ferrite in a carrier in liquidous phase, so that the ferromagnetic fluid behaves as if the fluid itself has apparent magnetic properties without being susceptible to any sign of coagulation or precipitation under a newtonian field or magnetic field.
The outermost axial ends on the inner peripheral surface of sections 21a or 21c, at which ferromagnetic fluid is squeezed out, are provided with magnetic seals 23L and 23R, respectively. Each of these magnetic seals 23L and 23R is composed of an annular permanent magnet 24 magnetized to have N-S poles in the axial direction, and a pair of magnetic yokes 25a and 25b each of which is attached to a respective axial end of each magnet 24. In this instance, the inner diameter of the magnetic yokes 25a and 25b are selected to be slightly larger than the outside diameter of the rotary shaft 2. The ferromagnetic fluid, as explained later, can be magnetically attracted by the magnetic field established between these magnetic yokes 25a and 25b, thereby preventing the magnetic fluid from escaping outwards.
Annular recovery grooves 28L and 28R are formed at positions on the inner periphery of the casing 21 between the fluid chamber 22 and each magnetic seal 23L and 23R. The recovery grooves communicate with the fluid chamber 22 through a slight clearance 27 defined between lands 26 and the outer face of the rotary shaft 2. The casing 21 is provided with a circulating passage 29 which connects the recovery grooves 28L and 28R with the fluid chamber 22 through a fixed restriction O. A pair of impelling means 90L and 90R are disposed within the recovery grooves 28L and 28R adjacent to the axially outer part thereof, so as to impel the ferromagnetic fluid toward the fluid chamber 22 thereby maintaining the hydrostatic pressure of the ferromagnetic fluid in the fluid chamber 22 at a predetermined level.
As shown in enlarged scale in FIG. 10, each of the impelling means 90L and 90R is provided, at a position adjacent to the recovery groove 28L and 28R, within an annular recess 91 concentric with the rotary shaft 2. Fixedly attached to said impelling means is a flexible membrane 92, such as a diaphragm, by which the recess 91 and the recovery groove 28L or 28R are isolated from each other.
Two impelling cylinders 93 and 94, composed of piezo-electric elements, are disposed within the annular recess 91, being radially stacked and axially compressible. There is further provided, at the side close to the circulating passage 29 apart from the annular recess 91, a magnet 95 which operates as a means for resistance variation for preventing counterflow of the ferromagnetic fluid from occurring. Each impelling cylinder 93 and 94 is supplied with electric current of a pre-selected cycle and in a pre-selected order by means of an actuating circuit 96 disposed outside the casing 21. When actuated, the axial length of the impelling cylinders 93 and 94 are enlarged or shortened, and the magnet 95 is also energized and actuated by the actuating circuit 96 synchronously with the supply of electric current to the impelling cylinders 93 and 94.
At the beginning of an operating cycle of the impelling means 90L and 90R, each cylinder 93 and 94 is not supplied with electric current and their innermost ends project slightly beyond the opened end of the annular recess 91. The volume of the recovery grooves 28L and 28R is large as the inflow of ferromagnetic fluid from the circulating passage side 29 is restrained by increasing the apparent viscosity of the ferromagnetic fluid by magnetizing the magnet 95 and thereby changing the resistance to travel of the ferromagnetic fluid at the position where the magnet is disposed. Then, as the ferromagnetic fluid is squeezed out from the fluid chamber 22 through the clearance defined between the land 26 and the outer peripheral face of the rotary shaft 2, it is recovered inside the recovery grooves 28L and 28R, thus increasing said volume of fluid within the grooves. Electric current is supplied through the actuating circuit 96, to the inner cylinder 93 to elongate it and let it contact the confronting wall of casing 21b to confine the ferromagnetic fluid. Electric current is subsequently supplied to the outer cylinder 94 forcing it to contact the wall of the casing 21b in a manner similar to cylinder 93 and at the same time, the power supply to the magnet 95 is cut off by means of the actuating circuit 96, thus reducing the resistance to travel of the ferromagnetic fluid through circulating passage 29.
When the rotary shaft 2 is in a stationary state and no electric current is supplied from the actuating circuit 96 to the actuating cylinders 93, 94 and the magnet 95 of the impelling means 90L and 90R, then the cylinders 93 and 94 of the impelling means are in a contracted state and, accordingly, hydrostatic pressure of the ferromagnetic fluid in the fluid chamber is zero. As such, the rotary shaft 2 contacts, and is supported by, the lands 26 of the hydrostatic bearing 1. Under such condition, the ferromagnetic fluid is distributed throughout the fluid chamber 22, recovery grooves 28L and 28R and the circulating passage 29, and since there are disposed the magnetic seals 23L and 23R, leakage or escaping of the ferromagnetic fluid from the bearing is prevented by the fact that the ferromagnetic fluid, otherwise liable to be squeezed out, is attracted by the magnetic force exerted by the aforesaid magnetic seals.
When it is required to hydrostatically support the rotary shaft 2 for its rotation, the actuating circuit 96 is stared and the magnet 95 is excited by electric current. As a result of excitation of magnet 95, the apparent viscosity of ferromagnetic fluid adjacent the magnet 95 becomes high, which, in turn, restrains inflow of ferromagnetic fluid from the circulating passage 29 to the recovery grooves 28L and 28R. Concurrent with or slightly after supplying current to magnet 95, electric current is supplied from the actuating circuit 96 to cylinder 93, so it is elongated and its inner end contacts the wall of casing 21b, thereby confining the ferromagnetic fluid within the space between the magnet 95 and the cylinder 93.
Next, the electric current, having been supplied to the magnet 95 from the actuating circuit 96, is cut off. The apparent viscosity of the ferromagnetic fluid contained in the space between the recovery grooves 28L and 28R is lowered and the ferromagnetic fluid flows readily outward through the circulating passage 29.
Concurrent with or slightly later than this, electric current is supplied from the actuating circuit to the cylinder 94, which is elongated. Accompanying this elongation, the ferromagnetic fluid which has been confined between the magnet 95 and the cylinder 93 is impelled toward the circulating passage 29 and is further delivered to the fluid chamber 22 through passage 29 and the fixed orifice O. Consequently, the hydrostatic pressure of the ferromagnetic fluid within the fluid chamber 22 increases dependent upon the difference between the amount of ferrofluid being impelled and that squeezed out through the space between the land 26 and the rotary shaft 2. As such, the ferromagnetic fluid in the fluid chamber can be maintained at a predetermined level by repeatedly impelling the ferromagnetic fluid through the impelling means 90L and 90R.
When the ferromagnetic fluid in the fluid chamber 22 is kept at a predetermined constant level, the rotary shaft 2 is floated upward away from the land of the hydrostatic bearing 1. Subsequent rotation of the rotary shaft under this condition is made very smoothly, by virtue of the greatly reduced frictional resistance between the rotary shaft 2 and the hydrostatic bearing 1.
The ferromagnetic fluid axially squeezed out from the fluid chamber 22 is collected by the recovery grooves 28L and 28R, returned to the impelling means 90L and 90R, and is forcibly circulated via the circulating passage 29. The ferromagnetic fluid squeezed further outside the recovery grooves 28L and 28R is prevented from escaping outside the casing 21 by means of the magnetic seals 23L and 23R. This prevents the exterior atmosphere from contamination as well as assuring remarkable reduction in the loss of ferromagnetic fluid in use.
Furthermore, since both the circulating passages and the impelling means are disposed within the casing 21, it is rendered possible to reduce the overall length of the circulating passage, giving rise to a reduction in the amount of expensive ferrofluid required as a working fluid, resulting in reduced production costs.
Although the fourth embodiment has been explained with respect to a bearing for supporting a rotary shaft having a circular cylindrical outer face, it is also possible for this invention to be applied to other types of bearings, such as may be applied to a fixed shaft, in place of the rotary shaft, to which the hydrostatic bearing 1 is slidably moved in an axial direction; namely, a so-called slider.
Also, in the fourth embodiment described above, the hydrostatic bearing 1 is fitted around the rotary shaft 2. It is, however, similarly possible to apply the hydrostatic bearing inside a hollow cylindrical rotary shaft.
Alternatively, in the fourth embodiment mentioned above impelling means 90L and 90R were described as composed of two impelling cylinders 93 and 94 made of piezo-electric elements radially stacked together but, they may be composed of impelling cylinders composed of three layers or more and may be actuated successively. In addition, the impelling cylinder is not required to be made of a piezo-electric element, but some other actuating means of a non-compressive type which may be controllably advanced or retracted by some discrete actuating means such as an electromagnetic solenoid may be used.
Furthermore, flow resistance variation means to be used for this invention, for restraining inflow of ferromagnetic fluid into the recovery grooves 28L and 28R, is not limited to a magnet or magnets, but may be replaced by a check valve 104, shown in FIG. 11, which is composed of a ball 103 urged by a spring 102 so as to contact the valve seat 101.
Furthermore, the piezo-electric elements 93 and 94 of the impelling means 90L and 90R are not required to be so limited that each of their end faces confronts directly with the side wall forming each of recovery grooves 28L and 28R. The impelling means can be constructed, as shown in FIG. 11, such that an intermediate seat 106 is disposed within an annular recess 105 forming a recovery groove so that the end face of the intermediate seat can contact the end face of the piezo-electric element 93 or 94.
In addition, the casing 21 is not limited to a cylinder, but can be formed as a channel or groove by axially cutting away a part of the cylinder forming a U-shaped cross-sectional configuration. In such case, the magnetic seal to be applied to this kind of casing shall be applied not only on the axial ends, but also to the peripheral end or ends of the cut-away opening to prevent ferromagnetic fluid from escaping.
As explained heretofore, according to the first embodiment of the present invention, ferromagnetic fluid is utilized as a fluid for generating hydrostatic pressure for floating a hydrostatic bearing relative to a shaft, and the subject fluid is impelled to a fluid chamber or chambers formed on the face of the bearing adjacent the shaft thereby floatingly supporting the shaft. In addition, a magnetic seal is disposed at the position where the ferromagnetic fluid is likely to escape.
The bearing system of this invention prevents the ferromagnetic fluid from escaping without any use of working gas by virtue of the magnetic seal. Such a configuration eliminates the possibility of entrapping gas in the fluid as well as contamination of the exterior atmosphere caused by the leakage of ferromagnetic fluid used in the bearing system, allowing its use in a vacuum environment with no trouble. Moreover, since the bearing system incorporates at least a passage and means for impelling the ferromagnetic fluid within the bearing itself, it has been rendered possible for this bearing system to reduce the volume of the entire fluid system and also to simplify and reduce the size of the entire device, thus minimizing the amount of expensive ferromagnetic fluid used as a working fluid.
According to the second embodiment of the present invention, ferromagnetic fluid is utilized as a fluid for generating hydrostatic pressure for floating a hydrostatic bearing relative to a shaft. The subject fluid is impelled to a fluid chamber or chambers formed on the face of the bearing adjacent to the shaft and thereby a thin film of ferromagnetic fluid is interposed between the shaft and the hydrostatic bearing, allowing relative movement between the two members to be effected very smoothly. In addition, since impelling means have been disposed confronting with the recovery grooves for collecting the escaping ferromagnetic fluid, the area for pressurizing the ferromagnetic fluid can be made large, and thereby the amount of the impelled fluid, as well as the delivery pressure can be increased, as required. Moreover, at least one magnetic seal is disposed at the positions where the ferromagnetic fluid is likely to escape from the bearing system of this invention to prevent the ferromagnetic fluid from escaping outside without any use of working gas by virtue of the magnetic seal. As such, there arises no fear of entrapping exterior gas into the fluid as well as contamination of exterior atmosphere caused by the leakage of ferromagnetic fluid used in the bearing system, allowing its use in a vacuum environment with no trouble.
While certain embodiments of the invention have been described in detail above in relation to a hydrostatic bearing utilizing a ferromagnetic fluid, it will be apparent to those skilled in the art that the disclosed embodiment may be modified. Therefore, the foregoing description is to be considered exemplary rather than limiting, and the true scope of the invention is that defined in the following claims. | A hydrostatic bearing system utilizing ferromagnetic fluid exclusively as working fluid including that used for sealing for preventing the ferromagnetic fluid itself from escaping outside the bearing. In order to accomplish the objects and function, the hydrostatic bearing system proposed here comprises, in addition to ordinary parts or components used in the conventional type, a fluid chamber for containing the ferromagnetic fluid as a working fluid, a circulating passage, at least a recovery groove for collecting the fluid squeezed out of the fluid chamber, a magnetic seal to prevent the fluid from escaping and at least an impelling device to forcibly deliver the ferromagnetic fluid at a predetermined pressure and flow rate. The impelling device can be constructed utilizing a shifting magnetic field, or multilayered rings fabricated of piezo-electric components, or of impelling cylinders having axially lengthenee or reduced in length. | 5 |
FIELD OF THE INVENTION
The present invention relates to a hand held shower head with filter replacing pre-alarm assembly, and more particularly to one implemented by an added device to generate pre-alarm upon a total quantity of flowing water passing through the filter embedded therein. Upon reaching an effective critical point, it can initiate alarms to remind the user to replace the filter assembly timely in order to ensure filtered water of a good quality.
BACKGROUND OF THE INVENTION
Nowadays, our tap water in daily living is full of pesticides, chemical constituents and varieties of impurity, owing to rivers being polluted by industrial and household waste water, garbage and livestock excretion caused by modern industrialization as well as lacking of environmental protection. Although it has been purified in the public waterworks treatment by chlorinating, such water with some remaining chloride residuals becomes harmful to the health of a human being. Thus, civil consumers usually obtain their potable water from purification equipment they've purchased. Many households even have their own purification equipment installed at home on the shower to get a better quality of bathing water. The principle herewith is to adsorb or remove pesticides, chemical constituents and varieties of impurity in the water by means of embedded adsorbents such as activated carbon, metallic sulfite, KDF therein.
Presently, there are some conventional devices of hand held showerheads with filter assemblies such as the devices in the prior art of US Pat. Nos. 4,107,046; 6,016,977 and 6,270,023. Though these devices can filter the shower water efficiently in some degree, it will fail at the critical point of filter assembly (or service life) after operating for a certain period of time, depending on the specified maximum quantity of water filtered by accumulated flux therethrough.
For example, if a maximum quantity of water that can be filtered is 1500 gallons, then such is the critical point of filter assembly. Once the filter assembly reaches this critical point, it will be spent and deteriorated, then lose its filtering function due to accumulated impurities. It can resume its filtrating ability only by replacing with a new filter. However, for those filters of devices in the current marketplace, the label or tag attaching thereon provided by vendors only specifies its critical point (or Service Life) in terms of quantity in gallon unit, neither the measuring instrument nor the tool thereof is provided by vendors.
Therefore, upon purchasing a new filter assembly, the consumer is always reminded by vendor to replace the filter in a half year or some other number of months. But if the consumer replaces the filter prematurely before reaching its critical point, it becomes wasteful as an increasing economic burden. To the contrary, if a consumer replaces the filter beyond its critical point, the filtering function of the filter may fail due to an abundance of accumulated dirt. Thus, the user of the purification equipment may get a filtered water whose quality is much dirtier and worse than that of tap water—without a malfunctioned filter, which ingested by a human being can severely jeopardize health even more.
However, the time for reaching the critical point of hand held shower head with a filter assembly is subject to differences of the number of users in each family. For example, if the average daily usage of water quantity for each person is 2 gallons, then the filter assembly, which is embedded in the hand held shower head, can be operated validly for 250 days in a family of 3 users; however, it can be only operated validly for 125 days in a family of 6 users. In other words, the aforementioned filter assembly of the prior art neither offers a feature of pre-alarm upon reaching its critical point nor having precise measurement control or record-keeping, having the consequences of missing replacement times and still continuing to use the malfunctioned filter, causing skin discomfort such as allergy or itchiness. Even more, the chronic exposure of chlorine on the skin may make a user susceptible to cancer. Obviously, the customary filter assemblies of the preceding prior art are neither practical nor ideal in effectiveness.
SUMMARY OF THE PRESENT INVENTION
Accordingly, the present invention adds a device on the filter within the handhold of the hand held shower head for measuring water quantity by accumulated flow and initiating pre-alarm.
The main object of the present invention is to eliminate all the drawbacks of the foregoing conventional prior art devices, which are handicapped by lack of pre-alarm upon reaching critical point of the filter assembly therein. By the added device herein described ably measuring water quantity by accumulated flow and initiating pre-alarm, the user is reminded to replace the filter at the proper time to assure the filtered water is of good quality.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view of a handheld shower head with filter replacing pre-alarm assembly according to a first preferred embodiment of the present invention.
FIG. 2 is an exploded sectional view of the above first preferred embodiment of the present invention.
FIG. 3 is a circuit block diagram of a signal conversion display of the present invention.
FIG. 4 is a sectional view of a handheld shower head with filter replacing pre-alarm assembly according to a second preferred embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1 to 3 , a hand held shower head with filter replacing pre-alarm assembly according to a first preferred embodiment of the present invention comprises a shower head 10 , a base seat 20 , a cover seat 30 , a propeller wheel 40 and a signal circuit device 50 .
Referring to FIGS. 1 and 2 , the shower head 10 has a hollow body and a water inlet 11 which is having screw threads 111 formed thereon, and provided to connect with a filter hand hold 60 . In front of the shower head 10 has firmly mounted a cover member 12 by means of a screw 121 , and said cover member 12 has a plurality of spray holes 122 to allow the water spray out of the shower head 10 . To the rear of the shower head 10 is tightly affixed a LCD display circuit 56 , is used in displaying an instruction sent by the microprocessor 51 of the signal circuit device 50 (as shown in FIG. 3 ).
Referring to FIGS. 1 and 2 , the base seat 20 , the cover seat 30 and the propeller wheel 40 are totally affixed in the inner of the shower head 10 , wherein the bottom surface of the base seat 20 forms an indented water chamber 21 . The base seat 20 has a water inlet channel 22 and a outlet channel 23 which is formed at the two sides of the water chamber 21 and through with each other. A rotation axle 24 is downwardly protruded from central area of a top surface of the water chamber 21 of the base seat 20 .
Referring to FIG. 2 , The cover seat 30 is tightly affixed on the bottom side of the base seat 20 with the bottom surface of the base seat 20 abutting to a top surface of the cover seat 30 . The cover seat 30 has a water inlet 31 which has two ends corresponding to the inlet channel 22 and the water inlet 11 respectively and is formed on a side surface of the cover seat 30 . The cover seat 30 has a water outlet 32 which is corresponding to the outlet channel 23 and is formed on a top surface of the cover seat 30 . A supporting axle 33 is upwardly protruded from a central area of a top side of the cover seat 30 , and the opposite side is downwardly protruded a threaded hole 341 of central dowel 34 .
Referring to FIG. 2 , The propeller wheel 40 is a circular body which has a plurality of curved propeller blades are extended radically from the circular body. Two central axial recesses 41 are coaxially at a center of top side and a bottom side of the propeller wheel 40 respectively. A magnetic element 42 is embedded on a top side of the propeller wheel 40 . The propeller wheel 40 is situated and supported in the water chamber 21 of the base seat 20 in rotatable manner that, the rotation axle 24 and the supporting axle 33 are fitted into the two central axial recesses 41 located in the center of the water chamber 21 of the base seat 20 (as shown in FIG. 1 ).
Referring to FIG. 3 , The signal circuit device 50 of the present invention comprises a microprocessor 51 , a DC power supply 52 electrically connected to the microprocessor 51 , a transducer 53 electrically connected to the microprocessor 51 , a reset switch 54 electrically connected to the microprocessor 51 , a rest switch 55 electrically connected to the microprocessor 51 , a LCD display circuit 56 electrically connected to the microprocessor 51 , a buzzer 57 electrically connected to the microprocessor 51 and a signal receiver 58 which is closed at the top surface of base seat 20 and corresponding to the magnetic element 42 (as shown in FIG. 1 ).
As shown in FIG. 1 , Assemble the base seat 20 , the cover seat 30 and the propeller wheel 40 by means of the screws 121 , 121 a and affixed to the inner of the shower head 10 , so that the water inlet 31 , the inlet channel 22 , the water chamber 21 , the outlet 23 and the water outlet 32 define a water flowing passage.
Referring to FIGS. 1 and 3 , In accordance with an operating mode of the present invention a water supply pipe is connected to the filter handhold 60 . Water flow enters the water chamber 21 through the water inlet 31 and inlet channel 22 , forcing the propeller wheel 40 to rotate, and flows out through the outlet channel 23 , the water outlet 32 and the spray holes 122 of the cover member 12 . When the propeller wheel 40 rotates, the magnetic element 42 induces the signal receiver 58 of the signal circuit device 50 , so that the signal receiver 58 receives a sensor signal and transmit to the microprocessor 51 via the transducer 53 . Such continuous signals are transmitted to the microprocessor 51 and will process sending corresponding signals to the LCD display circuit 56 , An accurate quantity of flow can be calculated according to the equation:
Quantity of Flow( Q )=Cross Sectional Area( A )×Flow Velocity( V )
The total water making volume value, that is a total volume of flowing water made by the filtration element 62 of the filter handhold 60 , is formatted and input into the microprocessor 51 as a predetermined reference value which is a digital standard reference value showing the service life (critical point) of the respective filtration element. When the total flowing volume value reach to the service life of the filter handhold 60 , the microprocessor 51 will sending a signal to the buzzer 57 for advancing a warning alarm to notify that it is the time for the user to replace a new filtration element of the filter handhold 60 . Therefore, the user can avoid in consequence of missing replacement timing and still continuously using the malfunctioned filter.
Referring to FIG. 4 , a hand held shower head with filter replacing pre-alarm assembly according to a second preferred embodiment of the present invention is illustrated in which the propeller wheel 40 has the same structure and the signal circuit device 50 is the same as in the above first preferred embodiment. The second embodiment is modification made to the shower head 10 .
In accordance with the second preferred embodiment, the shower head 100 of the second preferred embodiment has a hollow body which is secured at a elongate thread portion 101 , and provided to connected with a filter hand hold 60 . A water chamber 102 formed in the bottom surface of the elongate thread portion 101 . The shower head 100 has a water inlet 103 and a water outlet 104 are formed at the two sides of the water chamber 102 respectively and through with each other. In front of the shower head 100 has firmly mounted a cover member 105 which has a plurality of spray holes 106 to allow the water spray out of the shower head 100 . To the rear of the shower head 10 is tightly affixed a LCD display circuit 56 , is used in displaying an instruction sent by the microprocessor 51 of the signal circuit device 50 (as shown in FIG. 3 ). The propeller wheel 40 is situated and supported in the water chamber 102 of the shower head 100 in rotatable manner that, and the signal receiver 58 is mounted and corresponding at the top of the magnetic element 42 of the propeller wheel 40 .
Referring to FIG. 4 , In accordance with an operating mode of the second embodiment of the present invention a water supply pipe is connected to the input end portion 61 of the filter handhold 60 , water flow enters the water chamber 102 through the water inlet 103 , forcing the propeller wheel 40 to rotate, and flows out through the water outlet 104 and the spray hole 106 of the cover member 105 . When the propeller wheel 40 rotates, the magnetic element 42 induces the signal receiver 58 of the signal circuit device 50 , so that the signal receiver 58 receives a sensor signal and transmits to the microprocessor 51 via the transducer 53 . Such continuous signals are transmitted to the microprocessor 51 and will process sending corresponding signals to the LCD display circuit 56 . An accurate quantity of flow can be calculated according to the equation:
Quantity of Flow( Q )=Cross Sectional Area( A )×Flow Velocity( V )
The total water making volume value, that is a total volume of flowing water made by the filtration element of the filter handhold 60 , is formatted and inputted into the microprocessor 51 as a predetermined reference value which is a digital standard reference value showing the service life (critical point) of the respective filtration element. When the total flowing volume value reach the service life of the filter handhold 60 , the microprocessor 51 will send a signal to the buzzer 57 for advancing a warning alarm to notify that it is the time for the user to replace the filtration element of the filter handhold 60 . Therefore, the user can avoid the consequence of missing the replacement time and continuing to use a malfunctioned filter.
In conclusion by summing up the description mentioned above, the present invention has the following creative effects:
To allow the filter in a hand held shower head produce a maximum amount of filtered water for effective utilization thereof;
To generate audible and visible alarms to inform the user when the filter in a hand held shower head reaches (or nearly reaches) its critical point; and
To allow a user to timely replace the malfunctioned filter in a hand held shower head to meet the goal of making the best use of any resources or asset, to let it serve to its proper purpose in maximum practical efficiency and economical gain. So, it has inherently extreme value in industrial application of its own. | A hand held shower head with a filter replacing pre-alarm assembly includes a propeller wheel with a magnetically induced signal emitter and a correspondingly placed signal receptor, as well as a digital display connected to the signal receptor. Upon a total accumulated quantity of water flow through a filter positioned within a hand held portion, a pre-alarm signal is generated, and upon reaching a critical point, a buzzer is activated to remind the user to replace the filter to ensure a quality filtered water. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method for preparing a solid device for use as an oxide superconducting material, and more particularly to a method for preparing a solid device, the surface of which is utilized for oxide superconducting material wherein an important improvement is imparted to the properties of the material at the surface o portion close to the surface. to provide a highly reliable surface utilizing-device.
2. Description of the Related Art
Recently, considerable attention has been directed toward oxide superconducting materials. This began with the development of a Ba--La--Cu--O type of oxide superconducting material in the IBM research laboratories in Zurich, Switzerland. In addition to this, an yttrium type of oxide superconducting material is also known, which has provided the obvious possibility for the practical application of a solid device at the temperature of liquid nitrogen.
On the other hand, superconducting materials using metals such as Nb 3 Ge have been well known conventionally. Trials have been conducted in fabricating solid devices such as the Josephson element using this metal superconducting material.
After a dozen years of research, a Josephson device using this metal is close to being realized in practice. However, the temperature of this superconducting material at which the electrical resistance becomes zero (which is hereinafter referred to as Tco) is extremely low, that is 23 %, so that liquid helium must be used for cooling. This means that practical utility of such a device is doubtful.
With a superconducting material made of this metal, the components on both the surface and in the bulk of the material can be made completely uniform because all the material is metal.
On the other hand, when the characteristics of the oxide superconducting material which has been attracting so much attention recently are examined, a deterioration of the characteristics (lowering of reliability) is observed at the surface or portion close to the surface (roughly 200 Å deep), in comparison with the bulk of the material.
It has been possible to prove experimentally that the reason for this is that the oxygen in the oxide superconducting material can be easily driven off.
Further, when observed with an electron microscope, an empty columnar structure is seen with an inner diameter of 10 Å to 500 Å, and usually 20 Å to 50 Å in the oxide superconducting material, and in other words, the oxide superconducting material is found to be a multiporous material having indented portions in micro structure. For this reason the total area at the surface or portion close to the surface is extremely large, and when this oxide superconducting material is placed in a vacuum, the oxygen is broken loose as if absorbed gas was driven off.
The basic problem is determined that whether the material has superconducting characteristics or simply normal conducting characteristics is dependent on whether the oxygen is present in ideal quantities or is deficient.
SUMMARY OF THE INVENTION
An object of the present invention is to provide, with due consideration to the drawbacks of such conventional devices, a method for preparing a superconducting device which is kept superconductive at the surface or portion close to the surface of the oxide superconducting material.
This is accomplished in the present invention by the provision of a blocking film (passivation film), which is uniformly coated over the spaces or micro-holes in the surface portion of the superconducting material, to prevent the removal of oxygen from that surface.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other objects, features, and advantages of the present invention will become more apparent from the following description of the preferred embodiments taken in conjunction with the accompanying drawings, in which:
FIG. 1(A) to FIG. 1(E) are a diagram indicating the method of preparing the superconducting device of the present invention and showing the distribution of the oxygen concentration.
FIG. 2(A) and FIG. 2(B) are an enlarged sectional drawing of a superconducting material for implementing the method of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the embodiments of the present invention, a blocking film or passivation film is uniformly coated over the spaces or micro-holes in the surface portion of the superconducting material to prevent the removal of oxygen from that portion. Subsequently, a means is added by which the amount of oxygen in the inside surfaces of the superconducting material which tend to become oxygen deficient, can be precisely controlled. The superconducting material therefore has the same conductivity characteristics at the surface portion as at the internal portion.
In the present invention, a film is formed on the surface of the superconducting material at a thickness of 10 Å to 2μm using an photo CVD method superior in stepped coverage, which is a method of exciting a reactive gas using ultraviolet light for coating a film onto a film forming surface. In particular, if this film is to be an insulated or half-insulated film for use in a Josephson element, it is formed at a thickness of 10 Å to 10 Å. Also, in the case where it is to be used as a passivation film, it is formed in a thickness of from 1000 Å to 2 μm.
After this, by means of methods such as the ion injection method or hot oxidation method, oxygen is added onto the surface or portion close to the surface, and the entire body is heat treated, so that the added oxygen is positioned in the appropriate atom location. In addition, this film is converted by heat treatment to a highly dense insulating material to provide a more complete blocking layer. This film is oxidized on a metal or semiconductor and is formed to function as an insulating film. Further, by solid phase to solid phase diffusion of the oxygen in this film, that is diffusion of the oxygen from a solid film into another ceramic which is solid, the oxygen concentration in the region at the surface or close to it, generally at a depth of about 200 Å, can be appropriately controlled.
The films used for this purpose may be insulating films such as silicon nitride, aluminum nitride, oxidized aluminum, oxidized tantalum, oxidized titanium and the like.
In addition, a metal or semiconductor which becomes an oxidized insulating film after oxidizing treatment can be used as this film. Specific examples are, in a metal, aluminum, titanium, copper, barium, yttrium, or in a semiconductor, silicon or germanium. These materials, by oxidation, can be made into aluminum oxide, titanium oxide, tantalum oxide, copper oxide, barium oxide, and yttrium oxide. Also, silicon can be converted into silicon oxide, and germanium into germanium oxide.
With the present invention, an oxide superconducting material formed into tablets, or a superconducting material formed into a thin film can be used. Especially with the use of a thin film structure, the screen printing method, sputtering method, M8E (molecular beam epitaxial) method, CVD (chemical vapor deposition) method, photo CVD method, and the like can be used.
One example of an oxidized superconducting material used in the present invention can be generally represented as (A 1-x B x ) y Cu z O w , where x=0 to 1, y=2.0 to 4.0 or, preferably, 2.5 to 3.5, z=1.0 to 4.0 or, preferably, 1.5 to 3.5, and w=4.0 to 10.0 or, preferably, 6.0 to 8.0. A is one or a plurality of elements which can be selected from the group of Y (yttrium), Gd (gadolinium), Yb (ytterbium), Eu (europium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium), Lu (lutetium), Sc (scandium), and other elements in Group III of the Periodic Table. B can be selected from among elements in Group IIa of the Periodic Table, such as Ra (radium), Ba (barium), Sr (strontium), Ca (calcium), Mg (magnesim), and Be (beryllium). In particular, as a specific example, (YBa 2 )Cu 3 O 6-8 can be used. In addition, lanthanide elements or actinide elements in the Periodic Table other than those outlined above can be used as A.
In the present invention, when the insulating film is of a thickness capable of causing a tunnel current of 5 Å to 50 Å to flow, another superconducting material can be positioned on the upper surface of this insulating film to provide a Josephson element structure.
In addition, it can also be used as a passivation film, that is a film to prevent deterioration, at a thickness of from 1000 Å to 2 μm.
Specifically, after the film is formed on the oxide superconducting material, oxygen can be added, or, added oxygen can be positioned in an appropriate location, by use of a heat treatment at from 300° C. to 900° C., for example 600° C., for 0.5 to 20 hours, for example, 3 hours, in an atmosphere of inert gas, air, or oxygen, so that the surface of the material or the portion close to the surface can be superconductive.
As a result, the oxygen concentration of this surface can be maintained in an ideal status when maintained at the temperature of liquid nitrogen. Specifically, a passivation film can be created.
In this way, the problem which has existed up until the present time, that is, the problem that the superconducting state close to the surface of an oxide superconducting material disappears for unknown causes, is corrected, and the superconductive state of the surface can be effectively utilized with long-term stability.
As a result, the surface utilizing device, especially a Josephson element, can be activated with long term stability and high reliability.
FIRST EXAMPLE
Now referring to FIG. 1(A) to FIG. I(E), the structure of a first example of the present invention and the characteristics of the relative distribution of the concentration of oxygen in this embodiment are shown.
FIG. 1(A) shows a superconducting material, for example YBa 2 Cu 3 O 6-8 . The copper component may be 3 or less. The starting material (FIG. 1(A)(1)) was formed from such a superconducting material in tablet or thin film form, having a monocrystalline or polycrystalline structure.
When this material was placed in a vacuum in a vacuum device, the oxygen in the area close to the surface (1) was removed, so that the deterioration of electrical characteristics occurred in a depth range up to about 2OO Å.
When this surface was observed through an electron microscope, deep spaces or micro-holes were seen to be formed from the surface to the interior of the material, as shown in FlG. 2 (A). These spaces have an internal diameter of 10 Å to 500 Å, and usually from 20 Å to 50 Å. The oxygen density corresponding to FIG. 1(A) is shown in FIG. 1(D). And, it has been confirmed that the oxygen at the surface or close to the surface can be easily removed. A region 1 in the diagram had a normal oxygen concentration, while there was a deficiency of oxygen in a region 1'. The depth of the region 1' with a deficiency of oxygen was 50 Å to 2000 Å. This depth varied depending on the type, structure, and density of the superconducting material, but was generally about 200 Å.
On the surface of this material, a silicon nitride film, a silicon oxide film, or an aluminum film was formed to a depth of 5 Å to 50 Å, for example, 20 Å, by the CVD method, in which a reactive gas is optically excited using ultraviolet light or a laser beam, so that a film is formed on the treated surface. The silicon nitride was formed at a temperature of 250° C. and a pressure of 10 torr, from the following reaction:
3Si.sub.2 H.sub.6 +8NH.sub.3 →2Si.sub.3 N.sub.4 +21H.sub.2
In this way, it was possible to form a film so that the inside of the spaces was adequately coated. In addition to this treatment, ion injection was also carried out. A lower accelerating voltage of 10 KV to 30 KV was applied and doping was carried out, so that the oxygen concentration became uniform at a concentration of 1×10 17 cm -3 to 1×10 21 cm -3 .
Heat treatment was applied to the whole body in an atmosphere of oxygen at 300° C. to 900° C., for example 500° C. for about 5 hours.
As a result of this heat treatment, it was possible to impart the same oxygen density to the surface portion as in the internal portion as shown in FIG. 1(E).
A sample of this embodiment of the present invention was removed from the heat treatment condition and once more stored in a vacuum. A blocking layer 3 formed in this manner on the surface or portion close to the surface of the superconducting material made it possible to produce a highly reliable device, with no oxygen deficiency in that portion.
This insulating film was extremely effective as a passivation film.
SECOND EXAMPLE
In a second example of the present invention, silicon oxide was used for the film.
The silicon oxide was formed at a temperature of 200° C. using ultraviolet light at 185 nm and a pressure of 20 torr, implementing a photochemical reaction as indicated in the following equation :
SiH.sub.4 +4N.sub.2 O→SiO.sub.2 +4N.sub.2 +2H.sub.2 O
The superconducting material was the same as in the first example. Subsequently, a heat treatment in oxygen at 460° C. was carried out and a suitable oxygen concentration obtained.
THIRD EXAMPLE
In a third example of the present invention, metallic aluminum was used for the film.
The aluminum film was formed at a temperature of 250° C. and a pressure of 3 torr, using a photo-CVD process at a wavelength of 185 nm, implementing a photochemical reaction as indicated in the following equation :
2Al(CH.sub.3).sub.3 +3H.sub.2 +2Al+6CH.sub.4
Subsequently, the material was annealed in oxygen at 500° C. for 3 to 10 hours, and, as in the first example, the aluminum on the surface was converted to alumina, and the concentration of oxygen was optimized throughout the superconducting material.
An oxide superconducting material is used in the present invention, and the surface, when examined with a electron microscope, is seen to have a large number of micro-holes or spaces. It is necessary to fill the inside of the spaces or the micro-holes with a solid material to have a high degree of reliability. A film produced by the vacuum evaporation method, hot CVD method, sputtering method and the like cannot cover the internal surface. However, when the photo-CVD method is used in the present invention, an extremely superior coating is possible, so that an extremely minute coating can be obtained on the top surface of the porous substrate material used. In addition, by making this coating more dense, or converting to an oxidized insulating material, a more perfect state can be obtained, and at the same time it is possible to fill the microholes or spaces. In addition, this method by which an improved, dence, superconducting material is obtained is extremely effective because the manufacturing process is very easy.
In the present invention the term "oxide superconducting material" is used, wherein it is clear that in the technical concept of the present invention, the crystal structure may be either monocrystalline or polycrystalline. In particular, in the case of a monocrystalline structure, epitaxial growth may occur on the substrate for use as the superconducting material.
In the present examples, after the film has been formed, oxygen is injected into the superconducting material by ion injection. However, it is possible to add oxygen to the surface or portion close to the surface of the superconducting material in advance by the ion injection method or the like, and the form the film afterward, before effectively positioning the added oxygen in the appropriate atom location by a hot oxidation process when fabricating the superconducting material. | A method for manufacturing a superconducting device comprises the steps of forming a passivation film by photo chemical vapor deposition on the surface of an oxide superconducting material; and then adding oxygen into the oxide superconducting material by ion injection.
This patent application is related to the copending U.S. Pat. application entitled "Method of Adding a Halogen Element Into Oxide Superconducting Materials by Ion Injection" Ser. No. 190,352, filed May 5, 1988, now U.S. Pat. No. 4,916,116. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates in general to a water-saving single temperature or mixing faucet, especially for kitchen sinks and bathroom basins, comprising a movable spout controlling the "open" and "closed" states of the faucet and also to an attachment for converting standard mixing faucets into such water-saving mixing faucets.
2. Prior Art
Mixing faucets are an essential component of modern kitchens and bathrooms, and much thought and ingenuity has been invested in attempts to improve their design and make them more convenient to use. An important part of the convenience, in particular, of a kitchen sink, is a movable spout which can be brought over a particular section of the sink, or can be swung out of the way, so as not to interfere, if not needed. The main object of the above-mentioned efforts at improvement have been directed towards improving such a spout, with two major lines of approach and development: (1) To control, by swiveling of the spout, the flow rate in a continuous range from zero to maximum flow, but not the water temperature (e.g., U.S. Pat. No. 1,790,625); and (2) to control, by swiveling of the spout, both the flow rate and the water temperature (e.g., U.S. Pat. Nos. 2,181,630 and 2,504,610). All these known solutions suffer from two main drawbacks: they are complicated, requiring closely fitting pistons, cams, rollers, multiple-start threads and similar components which are both relatively expensive and failure-prone, especially when used with mineral-rich water. Most important, said solutions forego the great convenience of directing a certain, preset flow at a certain, preset temperature across the entire area of the sink, as any change in the angular portion of the spout will also change either the flow rate or both the flow rate and the temperature, which means that very hot water is obtainably only, say, on the right side of the sink, cold water only on the left, and medium temperatures only in the middle. Flow control, too, is, of course, a function of spout position in said prior art embodiments. Another disadvantage of the known mixing faucets is the fact that the active components of these faucets cannot be fitted to existing mixing faucets of the conventional type.
SUMMARY OF THE INVENTION
It is the object of the present invention, to overcome these drawbacks and to provide a single temperature faucet or a mixing faucet of a simple and reliable design, the movable spout of which can deliver water at a preset flow rate and temperature over the entire effective area of a sink. As will be described hereinafter, with the novel faucet of the present invention tilting the spout in the vertical direction or pushing the spout in either direction close to, or beyond, the edge of the effective sink area, will simply shut off the flow, a great inducement to saving water, as there is no need to turn valves and, incidentally, change the flow-rate and temperature setting.
The present invention achieves these results by providing a water saving faucet particularly for kitchen sinks and bathrooms basins, having at least one water valve, comprising a sink-sweeping movable spout coupled to a spout valve, said spout valve comprising means for blocking the water flow-path between at least one water inlet of said faucet and said spout, wherein movement imparted to said spout is also transmitted to said means of said spout valve and wherein over a first continuous range of selected positions of said movable spout said means are moved to allow the establishment of said flow-path, while in at least one other range of selectable positions of said spout, said means are moved to block said flow-path, whereby the open state of said faucet is substantially unaffected by the sweep of said movable spout across said entire first range of selected positions and the closed state of said faucet is controllable by the movement of said spout within said other range of positions to effect the stop of flow of water through said spout.
The invention further provides an attachment for converting a standard mixing faucet, having a movable spout and hot-water and cold-water valves, into a water-saving mixing faucet, comprising a spout valve inter-connectable between said spout and said faucet body, said spout valve having at least one substantially axial passage leading at one end into the interior of said movable spout, which spout valve is controlled by the movement of said spout so as to selectively establish, over a first continuous range of selected positions, a communication path between a mixing chamber of said faucet and the interior of said spout, to produce a flow of water of preset temperature and flow rate and, in at least one other range of selectable positions, to substantially cut off said communication path and stop said flow, whereby the open state of said faucet is substantially unaffected by the sweep of said movable spout across said entire first range of selected positions and the closed state of said faucet is controllable by the movement of said spout within said other range of positions to effect the stop of flow of water through said spout.
BRIEF DESCRIPTION OF THE DRAWINGS
While the invention will now be described in connection with certain preferred embodiments, it will be understood that it is not intended to limit the invention to these particular embodiments. On the contrary, it is intended to cover all alternatives, modifications and equivalent arrangements as may be included within the scope of the invention as defined by the appended claims. Nevertheless, it is believed that embodiments of the invention will be more fully understood from a consideration of the following illustrative description read in conjunction with the accompanying drawings, in which:
FIG. 1 is a cross-sectional view of an embodiment of the attachment according to the invention for converting a standard mixing faucet into a water-saving mixing faucet;
FIG. 2 is a plane view of the spout valve of the embodiment shown in FIG. 1;
FIG. 3 is a perspective view of an embodiment of the mixing faucet according to the invention having a sweeping spout;
FIG. 4 is a cross-sectional view of another embodiment of the attachment according to the invention;
FIG. 5 is an exploded view of the embodiment shown in FIG. 4;
FIG. 6 is a perspective drawing of the embodiment of the mixing faucet according to FIG. 5 having a tilting spout;
FIG. 7 is a cross-sectional view of part of the mixing faucet shown in FIG. 4, including a partition and check means;
FIG. 8 is a cross-sectional view of a single handle mixing faucet;
FIG. 9 is a cross-sectional view across the line IX--IX of FIG. 8; and
FIG. 10 is a cross-sectional view across the line X--X of FIG. 8.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
There is shown in FIG. 1 an attachment 1 according to the invention, by means of which a standard mixing faucet can be converted into a water-saving mixing faucet. An adaptor 2 in the form of a threaded, flat-bottomed double socket takes the place of the usual union nut which connects the movable spout to the faucet body 4 (indicated by the broken line). This adaptor 2 closes the outlet aperture 6 of the faucet body 4, except for two circular holes 8. The upper half of the adaptor 2, into the smooth bottom of which open the holes 8, constitutes the counterface 10 of the spout valve 12, to the sealing surfaces of which there is attached a sealing layer 14 consisting of a tough, low-friction plastic such as CAPRON or the like. The spout valve 12 is of a generally hollow cylindrical shape, of which the downstream end portion 16 is open towards the spout 20 and the upstream bottom end portion 18 is partly closed. Said spout valve 12 is provided with two oppositely located, substantially circular, slot-like openings 22 of an angular extent of less than 180°, seen to better advantage in FIG. 2. Between the respective ends of these slot-like openings 22 there are left solid bottom sections 24, which, at their narrowest point are at least as wide as the width of the circular slot-like openings 22, which width, in turn, is substantially equal to the diameter of the holes 8 in the counterface 10. The holes 8 and the slot-like openings 22 are located on the same pitch circle, as is shown in FIG. 1. The hollow, cylindrical shank of the spout valve 12 fits into the spout 20, to which it is rigidly connected by means of at least one pin 26, so that every swivel movement imparted to the spout 20 is also transmitted to the spout valve 12. The spout 20, being mostly of a standard size, could conceivably be the original spout of the mixing faucet to be converted, in which case the user would have to drill a hole through the spout end and through the inserted shank of the spout valve 12, to accommodate the pin 26. However, for convenience, the spout 20 is preferably delivered in the assembled state, as part of the attachment according to the invention.
The spout valve 12 is held down with minimum clearance by a nipple 28 which screws into the adaptor 2 and has a cylindrical bore providing an easy fit for the spout 20 which passes through it. The spout 20 is sealed off as in standard faucets by an O-ring 30 held down by a retaining nut 32. A gasket 34 ensures a tight fit between the adaptor 2 and the outlet nipple of the faucet body 4.
With reference now also to FIG. 3 the spout valve 12 functions as follows: As long as the circular holes 8 in the counterface 10 are within the angular range of, and register with, the slot-like openings 22, the spout 20 is in the "open" position. This angular range would correspond to the range A (FIG. 3) along any point of which the spout 20 will deliver a flow of water at a temperature and rate preset with the aid of the hot- and cold-water valves 60 and 62. It is a characteristic feature of the attachment according to the invention that as long as the spout 20 remains in its sweep across the sink within this range A, the open state of the faucet, as preset, remains substantially unaffected by the actual position of the spout. When the spout 20 is moved beyond this range A and into either of the ranges B, the spout valve 12, moving together with the spout 20, causes the circular holes 8 to increasingly come within the angular range of, and become covered by, the solid bottom portions or sections 24 (FIG. 2) of the spout valve 12, thereby cutting off the flow from the spout 20, even though the hot- and cold-water valves are still in their preset state of openness. Returning the spout 20 to any point within the range A will immediately restore delivery at the preset temperature and flow rate. Advantageously, the shut-off range B has an angular extent of about 20° to 35° and preferably about 30°, which is the angular extent through which the spout needs be moved to change the flow rate from its preset maximum to complete cut-off.
Another attachment or arrangement according to the invention is shown in cross section in FIGS. 4 and 5 with reference also to FIG. 6. The spout valve in this embodiment has the form of a "ball-and-socket" joint, comprising a spherical valve head 40 at the end of a substantially cylindrical shank 42. A bore 44 passes through the spout valve in a substantially axial direction. The shank 42 is fixedly mounted in an intermediate piece 46, the downstream end of which has the form of a threaded nipple with a central bore large enough to accommodate the upstream end of the spout 20 held in position, but still rotatable, by the commonly used device of a rolled-in groove in the spout, a sealing ring 30 and a retaining nut 32. Due to the intermediate piece 46, the valve shank 42 and, thus the entire valve body, is held in rigid axial alignment with the spout 20, i.e., any tilting movement imparted to the spout 20 is also transmitted to the valve body. The "socket" of this "ball-and-socket" arrangement is formed by an annular valve seat 48 made of a suitable material such as TEFLON or the like and housed in a valve-seat support 50 tightly inserted into the outlet socket of the faucet 4 to be converted. The spout valve is maintained within the valve-seat support 50 and pressed against the valve seat 48 by a sealing ring 52 held down by an adaptor 54 screwed onto the threaded outlet socket of the faucet 4 to be converted or fitted therewith.
The spout valve according to this embodiment works as follows: in a non-tilted first position of the spout 20 (solid lines in FIG. 6) the ball-side end of the bore 44 is located within the central opening of the valve seat 48, as clearly seen in FIG. 4, allowing the water to pass from the faucet 4 via the valve bore 44 into the interior of the spout 20. However, in a tilted position of the spout 20 (broken lines in FIG. 6), the ball-side end of the bore 44 moves beyond the central opening of the annular valve seat 48, preventing passage of water therethrough.
While the valve bore 44 could conceivably be straight over its entire length, the angular extent (designated B in FIG. 6) of the tilt required to shut off the flow of water can be substantially reduced if, as is shown in FIG. 4, a length of the ball-side end of the bore 44 is slanted with respect to the axis of the valve body. In this embodiment, too, the flow-stopping spout movement (in this case, a tilt) extends advantageously over an angular range of about 20° to 35° only, and preferably about 25°.
The operational difference between the embodiments shown in FIG. 1 and FIG. 4 is that in the embodiment of FIG. 1, the sink-sweeping spout movement and the flow-stopping spout movement are co-planar swiveling movements about the same, substantially vertical axis, while in the embodiment of FIG. 4, the sink-sweeping spout movement and the flow-stopping spout movement are, respectively, a swiveling and a tilting movement about two different, intersecting axes.
FIG. 7 shows an arrangement, part of a faucet according to FIG. 4 of the invention and advantageously provided in the first embodiment also, which prevents the infiltration of hot water into the cold-water mains, and of cold water into the hot-water mains. Such an infiltration may happen when pressures in the hot- and cold-water mains are unequal and the flow of water is shut off only by means of the spout, while the hot- and cold-water valves are still fully or partly open. To prevent this situation the tubular yoke or faucet body 4 of the faucet, which connects the outlet chambers of the hot- and cold-water valves, is divided into a hot-water chamber 70 and a cold-water chamber 72 by a water-tight partition 74, each of these two chambers being connected to a common mixing chamber 76 by a separate passage 78, which passages are provided with check means in the form, e.g., of ball valves 80 opening only when pressure is applied from below. This arrangement permits flow from the hot- and cold-water chambers 70 and 72 into the mixing chamber 76, but prevents flow from the mixing chamber 76 into the hot- and cold-water chambers 70 and 72. A grid 82 lets the water pass, but prevents the check balls 80 from leaving their seats more than required for their proper functioning.
If the attachments shown in FIGS. 1 or 4 are to be used on one temperature faucets or mixing faucets not provided with these or other anti-infiltration means, (check valves in the hot- and/or cold-water mains), the infiltration problem can be solved to some degree by adjusting whatever spout valves are used, in such a way that water flow cannot be completely cut off by means of the spout which, even in its extreme swiveling or tilting position, will have a small trickle. This insubstantial trickle will serve as a reminder to the user, that the hot- and cold-water valves must still be turned off.
Heretofore have been described having faucets comprising a hot-water valve 60 and a cold-water valve 62, wherein the flow rate and the temperature are exclusively controlled by the movable spout and the "open" state of the faucet is substantially unaffected by the sweep A of the movable spout 20 across the effective area of the sink.
In FIG. 8 there is illustrated a single handle mixing faucet 84 according to the invention which permits control of faucet output temperature and rate by moving a single handle only. The embodiment shown includes the features of a single control handle and a sweeping spout wherein after the initial adjustment of the desired water temperature and flow rate, the sweeping spout may be tilted in a vertical plan to open or close the output flow.
As seen in the figures, the handle 86 is pivotally attached to a central stem 88 having a cut-out section 90. The stem is disposed within a tubular housing portion 92 having two diametrically opposite inlet apertures 94 and a further outlet aperture 96. A closed bottom tubular sleeve 98 having inlet apertures 100 and an outlet aperture 102 corresponding to apertures 94 and 96, is slidingly disposed between housing portions 92 and 104. Housing portion 104 is also provided with apertures 106 and 108 in alignment with apertures 94 and 96. A spout 110 is hingedly coupled at 112 to a fitting 114 for movement in a horizontal plane while said fitting is hingedly affixed to the interior of the faucet for movement in a vertical plane. For achieving the latter movements, the base 116 of the fitting is provided with a cylindrical joint 118 which is held inside a seat 120 being a portion of the sleeve 98. Conduits 122 and 124 supply the hot and cold water to the interior of the faucet.
The hot and cold water entering the faucet through the conduits 112 and 124 pass through the apertures 106, 100 and 94, are mixed and flow out the apertures 96, 102 and 108 when all apertures are suitably aligned. As can be seen to better advantage in FIG. 9, the rotation of the handle 86 will govern the opening size of the apertures leading, respectively, to the hot and cold conduits while when the handle 86 is raised or lowered, the outlet aperture 96 will be partly or entirely blocked by the stem, depending on the position of the cutout 90 relative the aperture 96.
After the setting of the handle to a desired position for supplying water at the selected rate of flow and desired temperature, when the spout 110 is tilted upwardly, the sleeve 98 will slide downwardly and block the inlet as well as outlet apertures to cut-off the water flow. The mere lowering of the spout 110 will again allow the water to flow at the preselected temperature and flow rate.
It should be realized that the known thermostatically controlled faucets having a single flow-rate control valve could also be fitted with a sweeping and/or tilting spout according to the present invention. Moreover, while the present invention is particularly applicable for mixing faucets, it could obviously be applied in the same manner for single water temperature faucets.
Furthermore, although in the embodiment shown, the spout is coupled to, and controls the movement of a spout valve having at least one opening establishing a flow-path between the water inlet or inlets and the spout, it should be appreciated that instead of this spout valve, the spout may be coupled to a simple valve, comprising merely a movable plate member which is adapted to be displaced by the movement of the spout across the water inlet(s) to establish a flow-path or to block the same as selected by the movement of the spout.
Also, it should be added that for convenience and safety of the user, the spout is advantageously provided with, or covered by, thermally insulating means.
Finally, it will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments and that the present invention may be embodied in other specific forms without departing from the essential attributes thereof, and it is, therefore, desired that the present embodiments be considered in all respects as illustrative and not restrictive, reference being made to the appended claims, rather than to the foregoing description in which it is intended to claim all modifications coming within the scope of the invention. | A water-saving faucet, particularly for kitchen sinks and bathroom basins, is provided. The faucet comprises at least one water valve, a sink-sweeping movable spout and a spout valve means coupled to the spout. The open and closed states of the faucet are controllable by the movable spout and the open state of the faucet is substantially unaffected by the sweep of the movable spout across the effective area of the sink or basin. An attachment for converting a standard mixing faucet having a movable spout into a water-saving mixing faucet is also provided. | 8 |
FIELD OF THE INVENTION
The present invention relates to a method for improving a molded polymer article produced by the simultaneous polymerization and molding of a metathesis polymerizable monomer in the presence of a metathesis polymerization catalyst. More particularly, the invention relates to a method for forming an interpenetrating network (IPN) composed of a mixture of a metathesis polymer and a radical polymer by the radical polymerization of a vinyl monomer taking advantage of the fact that a compound used as an agent for reducing the residual monomer in a metathesis polymerization system forms a redox system with a transition metal of a metathesis polymerization catalyst and generates a radical.
BACKGROUND OF THE INVENTION
It is known that ring-opened polymers are produced from cycloolefins by the use of a metathesis polymerization catalyst system. Therefore, a process has been proposed to obtain a molded polymer article by carrying out the polymerization and molding of a metathesis polymerizable cycloolefin, such as dicyclopentadiene (DCPD), in one step in a mold using a metathesis polymerization catalyst. More particularly, a process has been proposed to obtain a molded polymer article, taking advantage of the fact that a metathesis polymerization catalyst system is composed of two components consisting of a catalyst component such as tungsten chloride and an activator component such as an alkylaluminum, by using two solutions, each of which contains one of the above components and a monomer, quickly mixing the solutions and injecting the mixture into a mold (for example, U.S. Pat. No. 4,400,340).
Such processes are very attractive from an industrial viewpoint because large-sized molded articles having good mechanical properties can be produced, using an inexpensive low-pressure mold. However, it has been found with the progress of practical application that some improvements are desirable.
One of the required improvements is the reduction of residual monomers in the molded article. In general, unreacted monomers are left in a molded article produced by the simultaneous polymerization and molding of metathesis polymerizable cycloolefins. Metathesis polymer molded article frequently contains up to several percent of residual monomer. Since cycloolefins generally have a characteristic unpleasant odor, the molded article also emits the particular odor. Furthermore, the residual monomer decreases the heat-deformation temperature of the molded article by its plasticizing action.
Accordingly, the reduction of the amount of residual monomer has become important from the viewpoint of widening the application field of the product.
U.S. Pat. No. 4,481,344 discloses that hydrocarbon compounds having a trihalogenated carbon group and hydrocarbon compounds having a halogen atom activated by a double bond at β-position can be used as a residual monomer reducing agents. The inventors of the present invention have also found, independently, that carboxylic acid halides, carboxylic acid anhydrides, silicon halides and phosphorus halides also have residual monomer reducing effects.
As a result of intensive investigation on the mechanism of the effect of the above compounds to reduce the residual monomer content, the following facts have been found.
The transition metal element forming the catalyst of a metathesis polymerization catalyst system is generally used in the state of its highest atomic valence. However, the element is reduced by the action of an activator to a state of lower atomic valence. This reduction can be observed, for example, by the fading of the dark red purple color of a catalyst based on tungsten hexachloride to an extremely light color upon mixing with an alkylaluminum-based activator.
When the system contains a halogenated compound, e.g. as taught by U.S. Pat. No. 4,481,344, it is believed that a redox system is formed between that compound and the reduced transition metal to cause the oxidation of the transition metal back to its original valence, and the reduction of the halogenated compound into a halide anion and a residue remaining in the form of a radical formed by the extraction of halogen. This reaction can be observed also by the fact that the red purple color of a molded polymer article is intensified as compared with a molded article lacking the halogenated compound.
There are at least two possible explanations for the reduction of residual monomers by the redox reaction. One of the explanations is the activation of the metathesis polymerization capability of the reoxidized transition metal. Another possible explanation is that the radical produced by reduction of the halogenated compound decreases the remaining monomer by radical polymerization of the cycloolefin. The correct explanation has not been clearly confirmed.
For the further clarification of the mechanism, tungsten hexachloride was solubilized by complexing with a phenolic compound. The solubilized tungsten hexachloride and an amount of dichlorodiphenylmethane equivalent to that used as a typical monomer-reducing agent according to U.S. Pat. No. 4,481,344 were added to methyl methacrylate and heated. No radical polymerization was observed. On the contrary, when tungsten pentachloride solubilized in the same manner was heated in methyl methacrylate together with dichlorodiphenylmethane of an amount equivalent to the tungsten content of the solubilized tungsten chloride, the methyl methacrylate was polymerized.
SUMMARY OF THE INVENTION
The inventors of the present invention have conceived the idea, from the above confirmed facts, that, if a radically polymerizable monomer is included with a metathesis polymerizable monomer in the presence of a residual monomer reducing agent, radical polymerization will take place simultaneously with metathesis polymerization to form an IPN containing both polymers.
It has been also clarified that a radically polymerizable vinyl monomer can participate in the metathesis polymerization reaction and act as a chain-transfer agent depending on the structure of the vinyl monomer. Thus, a monomer having a second double bond conjugated with the vinyl group and which is free of active hydrogen should be used to avoid the above problem. Moreover, the conjugated vinyl monomer is also preferably because the radical polymerization property is improved by the conjugate stabilization effect.
The present invention is a process for producing a molded polymer article by the simultaneous polymerization and molding of a monomer mixture comprised of a metathesis polymerizable cycloolefin monomer and a radically polymerizable vinyl monomer in the presence of a transition metal-based metathesis polymerization catalyst system characterized in that
(a) the monomer mixture also contains a compound capable of generating a radical by redox reaction with a reduced transition metal compound;
(b) at least a portion of the transition metal catalyst component is in a valence state at least one less than its maximum valence and;
(c) the vinyl monomer is free of active hydrogen and contains a second double bond conjugated with the vinyl group.
DETAILED DESCRIPTION OF THE INVENTION
Preferred examples of the metathesis polymerizable cycloolefin monomer used in the present invention are those containing one or two norbornene structures having high metathesis polymerizability, for example, dicyclopentadiene, tricyclopentadiene, cyclopentadiene-methylcyclopentadiene codimer, 5-ethyl-idenenorbornene, norbornene, norbornadiene, 5-cyclohexenylnorbornene, 1,4,5,8-dimethano-1,4,4a,5,6,7,8,8,8a-octahydronaphthalene, 1,4-methano-1,4,4a5,6,7,8,8,8a-octahydronaphthalene, 6-ethyldiene-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-heptahydronaphthalene, 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene, ethylene-bis(5-norbornene), or mixtures of such monomers. Dicyclopentadiene or a monomer mixture composed mainly of dicyclopentadiene is especially preferred.
Other metathesis polymerizable cyclic compounds having a norbornene structure and containing a polar hetero atom such as oxygen, or nitrogen may be used as required. The polar group is preferably ester group, ether group, cyano group or N-substituted imido group can also be employed. Such polar monomers are generally used in combination with dicyclopentadiene.
Examples of the copolymerizing monomer include 5-methoxycarbonylnorbornene, 5-(2-ethylhexyloxy)carbonyl-5-methylnorbornene, 5-phenyloxymethylnorbornene, 5-cyanonorbornene, 6-cyano-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, N-butylnadic acid imide and the like.
It is required that the above-mentioned metathesis polymerizable monomers be those containing the lowest possible amount of impurities which inactivate the metathesis polymerization catalyst.
As the transition metal-based catalyst component of the metathesis polymerization catalyst system used in the present invention are used salts such as e.g. halides of tungsten, rhenium, tantalum, and molybdenum and, especially, tungsten compounds. Among tungsten compounds are preferred tungsten halides, and tungsten oxyhalides. More particularly, tungsten hexachloride and tungsten oxychloride are preferred. Organo-ammonium tungstate and molybdate may be used as well. The tungsten halide compounds undesirably initiate cationic polymerization immediately when added directly to the monomer. It is, therefore, preferable that the tungsten compounds be previously suspended in an inert solvent such as benzene, toluene or chlorobenzene and solubilized by the addition of a small amount of an alcoholic compound or a phenolic compound and inactivated as cationic initiators. A Lewis base or a chelating agent is preferably added to the catalyst in an amount of about 1-5 mol per 1 mol of the tungsten compound in order to prevent undesirable cationic polymerization. Those additives may include acetylacetone, acetoacetic acid alkyl esters, tetrahydrofuran, benzonitrile and the like. Some of the forecited polar monomers are, themselves, Lewis bases and exhibit the above cationic initiation action without addition of the compounds cited above.
The monomer solution (solution A) containing the Lewis base or chelating agent-treated catalyst component has sufficiently high stability for practical use.
The activator components of the metathesis polymerization catalyst system include organometallic compounds chiefly comprising alkylated compounds of metals of group I-group III in the periodic table, preferably, alkyltin compounds, alkylaluminum compounds, alkylaluminum halide compounds and the like such as diethylaluminum chloride, ethylaluminum dichloride, trioctylaluminum, dioctylaluminum iodide, tributyltin hydride and the like. The organometallic compound used as the activator component is dissolved in the monomer to form the other reactive solution (referred to as the solution B).
According to the present invention, the molded polymer articles are produced by mixing the solution A with the solution B. The polymerization reaction, however, starts very rapidly when the above-mentioned composition is used and, consequently, undesirable initiation of hardening often occurs before the mold is completely filled with the mixed solution. In order to overcome this problem, it is preferable to use a polymerization moderating agent as mentioned above.
As such moderators are generally used Lewis bases, particularly, ethers, esters, and nitriles. Examples of the moderators include e.g. ethyl benzoate, butyl ether, and diglyme. Such moderators are generally added to the solution of the activator component comprising an organometallic compound. When a monomer having a Lewis base group is used in the reactive solution, as e.g. the polar monomers mentioned above, the monomer may be used to play the role of the moderator.
As mentioned above, the compounds capable of generating a radical by the redox reaction with a reduced transition metal compound include
(i) compounds having a trihalogenated carbon group;
(ii) hydrocarbon compounds having a halogen atom activated by a double bond at β-site;
(iii) carboxylic acid halides;
(iv) carboxylic acid anhydrides;
(v) halogenosilanes; and
(vi) halogenated phosphorus compounds
Examples corresponding to (i) include, for example, ethyl trichloroacetate, trichlorotoluene and hexachloro-p- or -m-xylene. The compounds corresponding to (ii) include e.g. dichlorodiphenylmethane, bis-p-(dichlorobenzyl)benzene, benzyl chloride, and benzal chloride.
Examples of (iii) are tere- or isophthaloyl chloride and benzoyl chloride and an example of (iv) is benzoic anhydride. Trichlorophenylsilane and dichlorodiphenylsilane are examples of (v) and phosphorus oxychloride is an example of (vi).
Especially preferably compounds are hexachloro-p- or -m-xylene, trichlorotoluene, and dichlorodiphenylmethane.
The vinyl monomer used in the present invention must not be active as a chain-transfer agent during the metathesis polymerization reaction as mentioned above. From this point of view, it is a vinyl monomer having conjugated double bonds. The vinyl monomer includes a monomer having similar polymerizability such as a compound having vinylidene group, vinylene group, etc., as well as the vinyl group in a narrow sense.
The monomer belonging to the above category is further required to be free from polar group containing active hydrogen which would also inhibit the metathesis polymerization.
Furthermore, the monomer must be soluble in a metathesis polymerizable monomer or another vinyl monomer to be used in combination with it and must be capable of forming a liquid mixture with the comonomer even if the monomer is solid at normal temperature. The volatility of the monomer is preferably not high at normal temperature.
Examples of the vinyl monomer are a group of styrene monomers such as e.g. styrene, α-methylstyrene, vinyltoluene, divinylbenzene, vinylnaphthalene, divinylnaphthalene, divinylbiphenyl, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, and tribromostyrene. Styrene, vinyltoluene, divinylbenzene, and dibromostyrene are especially preferable from the viewpoint of industrial availability.
The vinyl monomer further includes esters of acrylic acid and methacrylic acid. Concrete example of the compounds are acrylic acid or methacrylic acid esters of a monoalcohol having a carbon number of 20 or less or its halogen-substituted compound such as methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, 2,3-dibromopropyl acrylate, 2,3-dibromopropyl methacrylate, butyl methacrylate, butyl acrylate, tribromoneopentyl acrylate, tribromoneopentyl methacrylate, hexyl methacrylate, hexyl acrylate, octyl methacrylate, octyl acrylate and the like; polyacrylate or methacrylate of a polyol having 2-6 hydroxyl groups or its halogen-substituted compound such as ethylene diacrylate, ethylene dimethacrylate, butylene diacrylate, butylene dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, dibromoneopentyl glycol diacrylate, dibromoneopentyl glycol dimethacrylate, pentaerythritol tetraacrylate, and pentaerythritol tetramethacrylate; and aryl or aralkyl esters of acrylic acid or methacrylic acid or their halogen-substituted compounds such as phenyl acrylate, phenyl methacrylate, tribromophenyl acrylate, tribromophenyl methacrylate, benzyl acrylate, benzyl methacrylate, m-phenylene bisacrylate and m-phenylene bismethacrylate.
Diesters of maleic acid and fumaric acid may be used also as the above monomers. Since these monomers are not readily homopolymerizable, they are employed as comonomers with other monomers, the amount of addition of these monomers being determined taking consideration of their copolymerizability with the other monomer being employed.
Examples of such monomers are dimethyl maleate, dimethyl fumarate, diethyl maleate, diethyl fumarate, dipropyl maleate, bis(dibromopropyl) maleate, dibutyl maleate, dihexyl maleate, dioctyl maleate, bis(tribromoneopentyl) maleate, diphenyl maleate, and bis(nonylphenyl) maleate, diphenyl maleate, and bis(nonylphenyl) maleate.
Conjugated dienes such as e.g. butadiene, isoprene, cyclopentadiene, and piperylene can be used as the radically polymerizable vinyl monomer. However, these conjugated dienes present various problems in use such as e.g. low boiling points such that they exist in gaseous state at normal temperature or they lack stability and undergo dimerization by Diels-Alder reaction. Accordingly, most of these compounds are difficult to use.
The vinyl monomer further includes a group of compounds containing at least one metathesis polymerizable group and at least one radically polymerizable group in the same molecule. Preferably, the metathesis polymerizable group of these monomers (IV) is the norbornene group and the radically polymerizable group is the above-mentioned styryl group, acrylate group, or methacrylate group. Examples of such compounds are ##STR1## produced by norbornylating a vinyl group of divinylbenzene with cyclopentadiene by Diels-Alder reaction; an acrylate, a methacrylate, a maleate or a fumarate containing norbornene group such as ##STR2## and a compound produced by norbornylating a part of polyol polyacrylate or methacrylate with cyclopentadiene, for example, ethylene monoacrylate (norbornenecarboxylate) ##STR3##
Styrene-type monomers having low polarity are preferable among the above vinyl monomers from the viewpoint of compatibility with metathesis polymerization.
These compounds can be added without causing considerable influence on the progress of metathesis polymerization and are effective in promoting the polymerization. However, it is difficult to obtain IPN's having a wide variety of properties because the selectable range of the monomer structures is narrow.
On the contrary, acrylates, methacrylates, maleates and fumarates have polar ester groups to influence the progress of metathesis polymerization and show a tendency to retard the progress of the polymerization reaction. However, these compounds are advantageous for the production of an IPN having a variety of desired properties because of an extremely wide selection of monomers as shown by examples.
Monomers having a metathesis polymerizable group as well as a radically polymerizable group are preferably used in general in combination with other vinyl monomers because these monomers can serve as crosslinking agents.
The molar ratio of the vinyl monomer to the metathesis polymerizable cycloolefin monomer used in the reaction depends upon the identity of the vinyl monomer and the required properties of the molded polymer article and is generally between 1:1 and 1:0.01. The especially preferred ratio is between 1:0.3 and 1:0.05. In the case of preparing the reaction solution in the form separated into the solution A and the solution B, the vinyl monomer can be added to the solutions in equal amounts or can be added exclusively to one solution or the other depending upon what, if any, interaction takes place between the vinyl monomer and the components of the catalyst system.
When a tungsten compound is used as the catalyst component, the ratio of the metathesis polymerization catalyst system to the cycloolefin monomer is about 500:1-15000:1, and preferably about 1000:1-3000:1 on molar base. When an alkylaluminum compound is used as the activator component, the ratio of the aluminum compound to the above-mentioned cycloolefin monomer is about 100:1-2000:1 and preferably around a ratio of about 200:1-1000:1 on molar base.
The compound capable of generating a radical by a redox reaction with the reduced transition metal of the catalyst system can be present in an amount equivalent on a molar basis to the transition metal. However, the amount is practically and preferably 0.5-5 molar equivalents, more preferably 0.75-3 molar equivalents based on the transition metal element to account for variations of probability and reaction rate.
In the practical radical polymerization, another additional radical initiator can be added to the system when the formation of radical initiator by the above redox reaction cannot be raised to a sufficient level under the reaction conditions by the reduced transition metal.
A variety of additives may be used in the molded polymer article of the present invention to improve or to maintain characteristics of the molded articles. The additives include fillers, pigments, antioxidants, light stabilizers, flame retardants, plasticizers, macromolecular modifiers and the like. These additives must be added to the starting solutions, since they cannot be added after the solutions are polymerized to form a molded polymer article.
They may be added to either one or both of the solution A and the solution B. The additives should be those which are substantially unreactive with the catalyst system such as the highly reactive catalyst component and activator component, the radical-generating compound, the metathesis polymerizable cycloolefin monomer and the radically polymerizable vinyl monomer in the solutions and must have no inhibitory action on the polymerization. If the reaction with the catalyst component is unavoidable but does not essentially inhibit the polymerization, the additives can be mixed with he monomers to prepare a third solution, and the third solution mixed with the first and/or second solutions immediately before polymerization. The mold can be filled with a solid filler before charging the reactive solutions to the mold provided that the filler forms gaps which can be filled sufficiently with reacting solution immediately before or during the polymerization reaction.
The reinforcing agents or fillers used as additives can improve flexural modulus of the polymer. These include glass fibers, mica, carbon black, wollastonite and the like.
The molded polymer article produced by the present invention will normally contain an antioxidant. Preferably, a phenolic- or amine-antioxidant is added to the solution in advance. Examples of the antioxidants include 2,6-t-butyl-p-cresol, N,N'-diphenyl- p-phenylenediamine, and tetrakis-[methylene-(3,5-di-t-butyl-4-hydroxycinnamate)]-methane.
The molded polymer articles produced by the present invention may also contain other polymers, which are added to the monomer solution. Addition of an elastomer as the polymer additive is effective in improving the impact strength of the molded articles and controlling the viscosity of the solution. Examples of the elastomers to be used for the above purpose include a wide variety of elastomers such as styrene butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, ethylene-propylene-diene terpolymer, and nitrile rubber.
As described above, the molded polymer articles of the present invention are prepared by simultaneous molding and polymerization. Such molding methods include, for example, a resin injection process comprising the mixing of a solution A and solution B in advance and the injection of the premix into a mold and a RIM process comprising the impingement mixing of the above-mentioned solution A and solution B containing divided catalyst system in a mix head and the immediate injection of the mixture into the mold. The RIM process is most commonly used.
In both the RIM process and resin injection process, the mixture can be introduced into the mold under relatively low pressure, so that an inexpensive mold is usable.
In the process for producing a molded polymer article of the present invention, the polymerization of a metathesis polymerizable cycloolefin monomer is initiated very quickly by the metathesis polymerization catalyst whereupon the temperature of the system increases. The temperature of the system sometimes reaches 190° C. or more in the case of adiabatic metathesis polymerization reaction using dicyclopentadiene as the exclusive monomer.
The transition metal of the metathesis polymerization catalyst is reduced upon initiation of the metathesis polymerization and a radical polymerization is initiated by the radical formed by the redox reaction with the radical-generating compound. Since the progress of the radical polymerization is slow compared with the metathesis polymerization, it is necessary, in some case, to maintain the temperature of the system and perform sufficient progress of the radical polymerization without quickly removing the heat of the metathesis polymerization reaction. The system temperature is maintained generally between 80° C. and 150° C. and the control of the temperature is preferably continued until the radical polymerization proceeds to the desired level.
An IPN molded article composed of a metathesis polymer and a radical polymer is produced by the above process. Such molded articles can exhibit a variety of required characteristics due to the addition of a radical polymer as compared with the molded article of simple metathesis polymer and are applicable to wider applications.
The invention described herein is illustrated in detail by the following examples. These examples are solely for explanation and do not limit the scope of the invention.
EXAMPLES 1 to 4
Comparative Examples 1 to 4
Commercially available DCP was purified by distillation in a nitrogen stream under reduced pressure to produce purified dicyclopentadiene with a freezing point of 33.4° C. The purity was determined by gas chromatography to be not less than 99%.
Styrene and ethylene bisacrylate (EBA) used in the examples were prepared by distilling commercially available chemicals. 5-Styryl-norbornene (SNB) was produced by reacting commercially available divinylbenzene with cyclopentadiene in the presence of acetonitrile and hydroquinone and separating the desired SNB compound in a purified state by distillation. 5-Hydroxy-methyl- norbornene was reacted with acryloyl chloride to obtain norbornenylmethyl acrylate (NMA), which was used after purification by distillation.
Dichlorodiphenylmethane was prepared according to a known process by reacting benzophenone with phosphorus pentachloride and was used after purification by distillation.
To prepare a catalyst concentrate, 19.80 g (0.05 mol) of high-purity tungsten hexachloride was added to 90 ml of anhydrous toluene under a nitrogen stream. To the resultant mixture was added a solution produced by dissolving 0.925 g of t-butanol in 5 ml of toluene. This was stirred for 1 hour, then a solution consisting of 11.05 g (0.05 mol) of nonylphenol and 5 ml of toluene was added and stirred for 1 more hour under nitrogen purge. 10 g of acetylacetone was added to the mixture and the mixture was purged with nitrogen under stirring overnight to remove the by-product hydrogen chloride gas. A part of the toluene distilled off from the system was replenished to obtain a 0.5M concentrated tungsten solution.
A 1.0M solution of activator was prepared by mixing 5.70 g of di-n-octyl-aluminum iodide, 31.17 g of tri-n-octylaluminum and 13.42 g of diglyme under nitrogen stream and diluting the mixture with DCP to 100 ml in total.
A concentrated solution of the catalyst system and dichlorodiphenylmethane were added in amounts shown in Table 1 to 100 grams each of monomer mixtures having the compositions also shown in Table 1. The solutions A and B were prepared by this procedure. A rod-shaped molded specimen was produced by taking 10 ml each of the solutions A and B and mixing and injecting the solutions with a miniature bench RIM machine. The softening point (by TMA) and the amounts of residual DCPD and residual monomer (IV) were determined on the obtained molded specimen. For comparison, the same properties were measured on a molded specimen prepared, without addition of dichlorodiphenylmethane, using the same reaction conditions as were used in the procedures for the preparation of the above specimens.
The specimen without dichlorodiphenylmethane contains residual radically polymerizable monomer. Furthermore, it contains a large amount of residual DCPD and has very low softening point determined by TMA.
On the contrary, the radically polymerizable vinyl monomer was consumed by radical polymerization in the case of the specimen added with dichlorodiphenylmethane. The presence of the vinyl polymer raised the softening point and gave a useful molded article.
TABLE 1__________________________________________________________________________Composition of Reactive Solutions Example 1 Example 2 Example 3 Example 4__________________________________________________________________________Monomer Composition of DCP 80 DCP 80 DCP 90 DCP 80Solution A (mol %) Styrene 20 SNB 20 EBA 10 NMA 20Addition Amount of Concentrated 1.2 1.42 1.42 2.0Main Catalyst Solution (g)Addition Amount of Dichloro- 0.14 0.17 0.17 0.24diphenylmethane (g)Monomer Composition of DCP 100 DCP 100 DCP 100 DCP 100Solution B (mol %)Addition Amount of Concentrated 2.9 2.56 2.56 1.8Activator Solution (g)__________________________________________________________________________
TABLE 2__________________________________________________________________________Properties of Polymer Molded Articles Comparative Comparative Comparative Comparative Example 1 Example 1 Example 2 Example 2 Example 3 Example 3 Example Example__________________________________________________________________________ 4Softening Point (°C.) 97 60 135 80 112 88 135 94(TMA)Residual DCP 0.7 16.9 1.2 8.5 0.6 1.8 0.2 1.1(wt. % polymer)Residual Monomer Styrene Styrene SNB SNB EBA EBA NMA NMA(IV) (wt. % polymer) 0.05 8.5 0.1 0.1 1.0 2.0 0.3 1.1__________________________________________________________________________ | A process is disclosed for preparing a blend of a metathesis polymer and a radical polymer wherein a norbornene polymer is metathesis polymerized in the presence of a vinyl compound having two double bonds in conjugated relationship. Also included in the system is a compound capable of being reduced to a radical by the reduced valence transition metal element which serves as the catalyst of the metathesis polymerization. Examples of such compounds are specific chlorinated organic and chlorinated inorganic compounds. | 2 |
BACKGROUND OF THE PRESENT INVENTION
[0001] 1. Field of Invention
[0002] The present invention relates to a resonant DC/AC inverter, and more particularly to a resonant half-bridge DC/AC inverter using a piezoelectric transformer to supply power to fluorescent lamps. Usually, the inverter is usually applied to display devices, such as liquid crystal display monitors, liquid crystal display computers or liquid crystal display televisions.
[0003] 2. Description of Related Arts
[0004] CCFLs (cold cathode fluorescent lamps) are wildly employed in display panels. CCFL loads are extensively used to provide backlighting for liquid crystal displays (LCDs), particularly for backlighting LCD monitors and LCD televisions. Such conventional applications require direct current/alternative current inverters (DC/AC inverters) to drive CCFL loads. The critical factors in the design of LCD monitors or LCD televisions include efficiency, cost, size. Additionally, due to liquid crystal display's thin profile, liquid crystal displays can be used in applications where bulkier Cathode Ray Tube (CRT) displays are impractical.
[0005] Recent advances in ceramics technology have yielded a new generation of so-called “piezoelectric transformers (PTs)” that are useful in certain applications. These devices, which are constructed using laminated thin layers of ceramic material, exploit a well-known phenomenon called the “piezoelectric effect” to provide AC voltage gain, in contrast to the magnetic field effects relied upon by conventional wound transformers. In contrast to electromagnetic transformers, piezoelectric transformers have a sharp frequency characteristic of the output voltage to input voltage ratio, which has a peak at the resonant frequency. This resonant frequency depends on the material constants and thickness of materials of construction of the transformer including the piezoelectric ceramics and electrodes. Furthermore piezoelectric transformers have a number of advantages over general electromagnetic transformers. The size of piezoelectric transformers can be made much smaller than electromagnetic transformers of comparable transformation ratio, piezoelectric transformers can be made nonflammable, and produce no electromagnetically induced noise. Like conventional transformers, piezoelectric transformers are fairly rugged and can be used to obtain voltage gain in high-voltage applications. Additionally, due to their thin profile, piezoelectric transformers can be used in applications where bulkier wire-wound transformers are impractical. For example, piezoelectric transformers are used in power supplies that provide high-voltage power to fluorescent lamps used as backlights in portable computers. Due to their thin profiles, piezoelectric transformers used in such applications do not adversely affect the desired sleekness of the portable computer enclosure.
[0006] Piezoelectric transformers operate most efficiently when operated at frequencies at or near a multiple of a fundamental resonant frequency, which is a function of mechanical characteristics of the transformer such as material type, dimensions, etc. However, piezoelectric transformers are high-impedance devices, and therefore their resonance characteristics as well as other characteristics are sensitive to the loading of the transformer output in operational circuits. Resonant frequency, voltage gain at the resonant frequency, and sharpness of the gain-versus-frequency curve all diminish with increased loading.
[0007] The diminishing of resonant frequency and gain with an increase in loading are purposely exploited when a piezoelectric transformer is used to drive a fluorescent lamp. The frequency of the signal applied to the primary inputs of the piezoelectric transformer is slowly swept from a frequency higher than the unloaded resonant frequency toward lower frequencies. As the resonant frequency is approached, the gain increases to the point that the transformer output voltage is sufficiently high to “strike”, or initiate conduction in, the lamp. Once the lamp begins conducting, it presents a much higher load to the transformer, causing the voltage gain and therefore the output voltage of the transformer to drop considerably. The conduction characteristics of the lamp are such that it continues to conduct current at the reduced voltage, so the circuit then enters a stable, lower-voltage operating condition. The intensity of the lamp is regulated by controlling the frequency of the AC drive supplied to the piezoelectric transformer as a function of the lamp current.
[0008] Referring to FIG. 1 of the drawings, FIG. 1 shows a conventional resonant half-bridge DC/AC inverter circuit having a piezoelectric ceramic transformer for driving a CCFL load. As shown in FIG. 1 , the conventional resonant half-bridge DC/AC inverter circuit 100 comprises a half-bridge power switch circuit 110 , a resonant tank 120 , a lamp current sensing circuit 130 , an integrator 140 , a voltage controlled oscillator (VCO) 150 , and a half-bridge drive circuit 160 . The half-bridge power switch circuit 110 comprises two power switches 110 A, 110 B which are in a half-bridge configuration. The resonant tank 120 comprises an inductor 121 and a piezoelectric ceramic transformer 122 . The integrator 140 comprises an error amplifier 141 which integrates the output of the lamp current sensing circuit 130 and this integrated value affects the operating frequency of the VCO 150 . The half-bridge drive circuit 160 provides two driving signals RA and RB.
[0009] The half-bridge power switch circuit 110 is electrically connected to a DC power source 180 and powered by the DC power source 180 . An output terminal of the half-bridge power switch circuit 110 is electrically connected to an input terminal of the resonant tank 120 . An output terminal of the resonant tank 120 is electrically connected to one end of a fluorescent lamp 170 . An input of the lamp current sensing circuit 130 is electrically connected to the other end of the fluorescent lamp 170 . The inverse terminal of error amplifier 141 of the integrator 140 is electrically connected to the output of the lamp current sensing circuit 130 and the error amplifier 141 integrates the output of the lamp current sensing circuit 130 . This integrated value is a voltage-controlled signal RC which affects the operating frequency of the VCO 150 . Hence the voltage-controlled signal RC determines the operating frequency of a pulse signal RD which is generated by the VCO 150 . The output of the VCO 150 is electrically connected to the half-bridge drive circuit 160 . The half-bridge drive circuit 160 generates two sets of fixed duty cycle driving signals RA and RB. The power switches 110 A, 110 B are driven by the driving signals RA and RB respectively. The upper half of the half-bridge power switch circuit 110 is driven out of phase with the lower half of the half-bridge power switch circuit 110 such that when the power switch 110 A is on, the power switch 110 B is off, and conversely, when the power switch 110 A is off, the power switch 110 B is on. Driven in this manner, the output of the half-bridge power switch circuit 110 consists of a square wave voltage.
[0010] The conventional resonant half-bridge DC/AC inverter circuit utilizes the high frequency switching of the power switches 110 A, 110 B to convert a DC voltage powered by the DC power source 180 to a high frequency square wave signal. The high frequency square wave signal is used to drive the resonant tank 120 . The resonant tank 120 is the combination of the inductor 121 and the piezoelectric ceramic transformer 122 . The combination of the inductor 121 and the piezoelectric ceramic transformer 122 forms a resonant circuit. This results in a sine wave at the output of the resonant tank 120 . On the other hand, the resonant tank 120 utilizes the inductor 121 and the piezoelectric ceramic transformer 122 to filter and boost the high frequency square wave signal to a high frequency sine wave signal. The high frequency sine wave signal is used to drive the fluorescent lamp 170 .
[0011] Referring to FIG. 2 of the drawings, FIG. 2 schematically shows output voltage characteristics of a conventional resonant tank with respect to various frequencies input signal. Therefore, the lamp current could be adjusted by controlling switching frequency of the half-bridge power switch circuit. In other words, the lamp current could be adjusted by controlling the switching frequency of the power switches 110 A, 110 B.
[0012] A resonant tank has many resonant frequencies, and a different gain-versus-frequency characteristic in the neighborhood of each. Generally speaking, it is desirable to design that the operating frequency of the resonant half-bridge DC/AC inverter circuit 100 is higher than the operating frequency of the resonant tank 120 . The integrator 140 integrates the output of the lamp current sensing circuit 130 and then generates the stable voltage-controlled signal RC which affects the operating frequency of the VCO 150 . Hence the voltage-controlled signal RC can control the VCO 150 to generate different operating frequencies of a pulse signal RD. According negative feedback theory, the voltage-controlled signal RC can raise the operating frequency of a pulse signal RD while the lamp current is increasing and reduce the operating frequency of a pulse signal RD while the lamp current is decreasing. The half-bridge drive circuit 160 utilizes operating frequencies of a pulse signal RD to provides two fixed duty cycle driving signals RA and RB in order to control the power switches 110 A, 110 B. Therefore, the power switches 110 A, 110 B have the same and fixed duty cycle control to provide a stable and symmetric alternating current to the fluorescent lamp 170 .
[0013] Accordingly, the conventional resonant half-bridge DC/AC inverter circuit can provide stable control of lamp current even though the DC power source 180 provides variable DC voltage. However, in practical the drawback of this prior art is that the efficiency of the conventional resonant half-bridge DC/AC inverter circuit is reduced while the DC power source 180 provides higher DC voltage and the operating frequency of the half-bridge power switch circuit 110 operates far away the neighborhood of the resonant frequency. Hence conventional resonant half-bridge DC/AC inverter circuit could not provide good conversion efficiency while the DC power source 180 provides higher DC voltage and the operating frequency of the half-bridge power switch circuit 110 operates far away the neighborhood of the resonant frequency.
SUMMARY OF THE PRESENT INVENTION
[0014] A main object of the present invention is to provide a resonant half-bridge DC/AC inverter that simultaneously varies the operating frequency of the power switches and the duty cycle of the power switches to regulate the output current in order to improve the efficiency of the inverter regardless of the higher DC voltage applied to the inverter.
[0015] Another object of the present invention is to provide a resonant half-bridge DC/AC inverter using a piezoelectric transformer to supply power to fluorescent lamps which are wildly employed in display panels and are extensively used to provide backlighting for liquid crystal displays (LCDs), particularly for backlighting LCD monitors, LCD televisions, computer systems and portable DVD, wherein the resonant half-bridge DC/AC inverter simultaneously varies the operating frequency of the power switches and the duty cycle of the power switches to regulate the lamp current in order to improve the efficiency of the inverter regardless of the higher DC voltage applied to the inverter.
[0016] Another object of the present invention is to provide a resonant half-bridge DC/AC inverter that provides a symmetric alternating current to supply to fluorescent lamps and a necessary high voltage to ignite fluorescent lamps.
[0017] Another object of the present invention is to provide a resonant half-bridge DC/AC inverter further comprising a protection circuit and a dimming control circuit to protect the resonant half-bridge DC/AC inverter under abnormal operation and to adjust the brightness of fluorescent lamps.
[0018] Accordingly, in order to accomplish the one or some or all above objects, the present invention provides a resonant half-bridge DC/AC inverter, comprising:
[0019] a DC power source providing a DC voltage;
[0020] a half-bridge power switch circuit electrically connected to the DC power source being operative to convert the DC voltage to a pulse signal;
[0021] a resonant tank electrically connected between an output of the half-bridge power switch circuit and an input of a load being operative to boost and filter the pulse signal to generate an AC power supplied to the load; and
[0022] a controller being operative to detect a magnitude of current in the load and a magnitude of a voltage across the load and to generate pulse waveforms for turning on and off the half-bridge power switch circuit, wherein the controller substantially instantaneously varies a frequency of the pulse waveforms and a duty cycle of the pulse waveforms so as to operate the resonant half-bridge DC/AC inverter near a neighborhood of a resonant frequency of the resonant tank regardless of a conduction state of the load.
[0023] One or part or all of these and other features and advantages of the present invention will become readily apparent to those skilled in this art from the following description wherein there is shown and described a preferred embodiment of this invention, simply by way of illustration of one of the modes best suited to carry out the invention. As it will be realized, the invention is capable of different embodiments, and its several details are capable of modifications in various, obvious aspects all without departing from the invention. Accordingly, the drawings and descriptions will be regarded as illustrative in nature and not as restrictive.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] FIG. 1 is a schematic diagram of a conventional resonant half-bridge DC/AC inverter circuit having a piezoelectric ceramic transformer for driving a CCFL load.
[0025] FIG. 2 is a schematic diagram of output voltage characteristics of a conventional resonant tank with respect to various frequencies input signal.
[0026] FIG. 3 is an exemplary circuit diagram of a resonant half-bridge DC/AC inverter circuit having a piezoelectric ceramic transformer according to a preferred embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0027] Referring to FIG. 3 , an exemplary circuit diagram of a resonant half-bridge DC/AC inverter circuit having a piezoelectric ceramic transformer according to a preferred embodiment of the present invention is illustrated. The resonant half-bridge DC/AC inverter circuit 300 includes a DC power source 301 , a half-bridge power switch circuit 302 , a resonant tank 303 , a lamp current sensing circuit 305 , a lamp voltage sensing circuit 306 , a pulse width modulator 307 , a triangle wave generator 308 , a half-bridge drive circuit 309 , a protection circuit 310 , a timer 311 , and a dimming control circuit 312 . The half-bridge power switch circuit 302 comprises two power switches 302 A, 302 B which are in a half-bridge configuration. The power switch 302 A could be a p-type MOSFET. The power switch 302 B could be a n-type MOSFET. However, the power switches 302 A, 302 B are not limited to MOSFET and could be any type of transistor switch such as BJT. The resonant tank 303 comprises an inductor 321 and a piezoelectric ceramic transformer 322 .
[0028] The half-bridge power switch circuit 302 is electrically connected to the DC power source 301 and powered by the DC power source 301 . An output terminal of the half-bridge power switch circuit 302 is electrically connected to an input terminal of the resonant tank 303 . An output terminal of the resonant tank 303 is electrically connected to one end of a fluorescent lamp 304 . An input of the lamp current sensing circuit 305 is electrically connected to one end of the fluorescent lamp 304 . An input of the lamp voltage sensing circuit 306 is electrically connected to the other end of the fluorescent lamp 304 . An output of the lamp current sensing circuit 305 and an output of the lamp voltage sensing circuit 306 are electrically connected to the pulse width modulator 307 and feeds back a lamp current sensing signal and a lamp voltage sensing signal to the pulse width modulator 307 .
[0029] The pulse width modulator 307 comprises an error amplifier 361 , a comparator 364 , an integral resistor 365 , an integral capacitor 366 , a current source 367 , and a switch 368 , wherein an inverse integrator consists of an error amplifier 361 , an integral resistor 365 , and an integral capacitor 366 . An inverting terminal of the error amplifier 361 is electrically connected to the current source 367 via the switch 368 . An output terminal S 1 of the error amplifier 361 is electrically connected to the triangle wave generator 308 via a resistor 362 . An output terminal S 16 of the pulse width modulator 307 is electrically connected to the half-bridge drive circuit 309 . The half-bridge drive circuit 309 is electrically connected to the half-bridge power switch circuit 302 .
[0030] According to the preferred embodiment of the present invention, an output terminal S 2 of the triangle wave generator 308 is electrically connected to a grounding resistor 363 . Additionally, the triangle wave generator 308 comprises another terminal electrically connected to a capacitor 364 . The value of a current S 3 passing through the output terminal S 2 of the triangle wave generator 308 and the capacitance of the capacitor 364 determine the operating frequency of the triangle wave generator 308 . The operating frequency of the triangle wave generator 308 increases when the current S 3 increases. The operating frequency of the triangle wave generator 308 is determined by an output signal at the output terminal S 1 of the error amplifier 361 and the current S 3 because the resistor 362 is connected between the output terminal S 1 of the error amplifier 361 and the output terminal S 2 of the triangle wave generator 308 . In this embodiment of the present invention, when the output signal at the output terminal S 1 of the error amplifier 361 is zero voltage, the resistor 362 is in parallel with the grounding resistor 363 with respect to the output terminal S 2 . Hence the equivalent load resistance with respect to the triangle wave generator 308 is smallest and then the current S 3 passing through the output terminal S 2 of the triangle wave generator 308 is highest. In other words, the operating frequency of the triangle wave generator 308 is highest. On the contrary, when the output voltage at the output terminal S 1 of the error amplifier 361 is close to the voltage at the output terminal S 2 , the current passing through the resistor 362 is zero. Hence the equivalent load resistance with respect to the triangle wave generator 308 is just only the grounding resistor 363 . The current S 3 passing through the output terminal S 2 of the triangle wave generator 308 becomes smaller and then the operating frequency of the triangle wave generator 308 also becomes smaller. When the values of the resistor 362 , the grounding resistor 363 , and the capacitor 364 are fixed, the operating frequency of the triangle wave generator 308 is determined by the voltage at the output terminal S 1 of the error amplifier 361 . In other words, when the voltage at the output terminal S 1 of the error amplifier 361 decreases, the operating frequency of the triangle wave generator 308 increases, and vice versa. In this embodiment of the present invention, the triangle wave generator 308 not only generates a triangle wave S 17 but also a pulse signal S 18 having the same frequency with the triangle wave S 17 , wherein the pulse signal S 18 is supplied to the half-bridge drive circuit 309 to generate driving signals. However, it is not intended to o limit the invention to the triangle wave. It should be appreciated that any ramp signals or sawtooth wave signals could be made in the embodiments described by persons skilled in the art.
[0031] The lamp current sensing circuit 305 is in series with the fluorescent lamp 304 and provides a signal S 4 to indicate the conduction state of the fluorescent lamp 304 and a signal S 5 to indicate the current passing through the fluorescent lamp 304 . The lamp voltage sensing circuit 306 is in parallel with the fluorescent lamp 304 and provides a signal S 6 to indicate the voltage at the end of the fluorescent lamp 304 .
[0032] The half-bridge drive circuit 309 generates two driving signals POUT and NOUT. The timer 311 comprises two sets of comparators 381 , 382 , and a current source 383 . The dimming control circuit 312 comprises a dimming frequency generator 331 generating a triangle wave S 7 and a pulse signal S 15 , a comparator 332 , and an OR gate 333 . The triangle wave S 7 is applied to a non-inverting terminal of the comparator 332 and a dimming control voltage S 8 is applied to an inverting terminal of the comparator 332 . The comparator 332 compares the triangle wave S 7 and the dimming control voltage S 8 to generate a dimming pulse signal S 9 . The OR gate 333 is used to control the timing when the dimming pulse signal S 9 could be applied to the error amplifier 361 of the pulse width modulator 307 .
[0033] In this embodiment of the present invention, the timer 311 utilizes the current source 383 to charge a timer capacitor 384 so that a voltage S 12 across the timer capacitor 384 increases with time. When the voltage S 12 is lower than a reference voltage Vref 1 , the timer 311 utilizes a comparator 381 to output a reset signal S 11 . When the voltage S 12 is larger than a reference voltage Vref 2 , the timer 311 utilizes a comparator 382 to output a time out signal S 10 . The current source 383 is controlled by an indicative signal S 13 outputted from a system voltage source. When a system voltage of the system voltage source is lower than reference voltage Vref 3 , the indicative signal S 13 communicates with the current source 383 to turn off the current source 383 and also grounds the timer capacitor 384 . Therefore, it could be assured that the timer capacitor 384 is charged from zero voltage and the timer 311 should be reset each start of the resonant half-bridge DC/AC inverter circuit.
[0034] In this embodiment of the present invention, the protection circuit 310 comprises a comparator 374 and a logic control circuit 372 . The signal S 4 provided by the lamp current sensing circuit 305 and a reference voltage Vref 4 are applied to the comparator 374 to determine the conduction state of the fluorescent lamp 304 . When the signal S 4 is larger than the reference voltage Vref 4 , the fluorescent lamp 304 is treated as ignition and the comparator 374 outputs a signal S 114 to indicate that the fluorescent lamp 304 is ignited. The protection circuit 310 determines the execution of the protection action or not according to the signal S 14 , the time out signal S 11 , and the pulse signal S 15 .
[0035] Under normal operation, the timer 311 utilizes the current source 383 to charge a timer capacitor 384 so that a voltage S 12 across the timer capacitor 384 increases with time. When the voltage S 12 is lower than a reference voltage Vref 1 , the timer 311 utilizes a comparator 381 to output a reset signal S 11 so that a switch 368 is turned on and the current source 367 is electrically connected to the inverting terminal of the error amplifier 361 . Hence the current source 367 enforces that a voltage at the inverting terminal of the error amplifier 361 is higher than a reference voltage Vref 5 so that the output of the error amplifier 361 is zero. At this time, the output of the pulse width modulator 307 is zero. The operating frequency of the voltage-controlled-frequency triangle wave generator 308 is far way and higher than the resonant frequency of the resonant tank 303 .
[0036] When the voltage S 12 is larger than a reference voltage Vref 1 , the switch 368 is turned off so that the pulse width modulator 307 starts to work. The voltage at the inverting terminal of the error amplifier 361 is lower than the reference voltage Vref 5 plus a conduction voltage of a diode 352 , the output signal of the error amplifier 361 gradually increases because of negative feedback control theory. The comparator 364 compares the output signal of the error amplifier 361 with the triangle wave S 17 to generate a pulse width modulation signal S 16 . The pulse width modulation signal S 16 and the pulse signal S 18 are applied to the half-bridge drive circuit 309 to generate driving signals POUT and NOUT which drive two power switches 302 A, 302 B respectively. The output of the pulse width modulator 307 determines the turned-on duty cycle of the driving signals POUT and NOUT. When the output of the pulse width modulator 307 is higher, it makes larger turned-on duty cycle of the driving signals POUT and NOUT. With such design, the power switches 302 A, 302 B are driven by a higher frequency and less duty cycle signals POUT and NOUT when the supply voltage is higher. When the power switches 302 A, 302 B are driven by less duty cycle signals POUT and NOUT, less power transferred to the load may prevent the operating frequency far away from the resonant frequency of the resonant tank 303 as the prior art.
[0037] Before the ignition of the fluorescent lamp 304 , the voltage at the end of the fluorescent lamp 304 increases because the duty cycle of the pulse width modulation signal S 16 gradually increases and the frequency of the pulse width modulation signal S 16 gradually decreases. The lamp voltage sensing circuit 306 detects the voltage at the end of the fluorescent lamp 304 and provides a signal S 6 to indicate the voltage at the end of the fluorescent lamp 304 . When the voltage of the signal S 6 is greater than the reference voltage Vref 5 plus the conduction voltage of the diode 352 , the output of the error amplifier 361 becomes smaller and then the duty cycle of the pulse width modulation signal S 16 is reduced and the frequency of the pulse width modulation signal S 16 is increased to reduce the power delivery to fluorescent lamp 304 . If this result causes the voltage of the signal S 6 is smaller than the reference voltage Vref 5 plus the conduction voltage of the diode 352 , the output of the error amplifier 361 becomes larger. Therefore, the voltage applied to the fluorescent lamp 304 could be regulated and stabilized because of negative feedback control theory.
[0038] Once the fluorescent lamp 304 is ignited and reaches steady operation, the voltage across the fluorescent lamp 304 will suddenly drop to half of the ignition voltage of the fluorescent lamp 304 so that the lamp voltage sensing circuit 306 does not work because the lamp voltage sensing circuit 306 could not detect an enough high voltage.
[0039] The lamp current sensing circuit 305 provides a signal S 4 to the lamp current sensing circuit 305 and a signal S 5 to the pulse width modulator 307 to stabilize the current passing through the fluorescent lamp 304 at a fixed value via feedback control.
[0040] In this embodiment of the present invention, the function of the diodes 351 and 352 is to utilize the characteristic of the great difference between the ignition voltage and the normal operation voltage of the fluorescent lamp (for example 2˜2.5 times). Before the ignition of the fluorescent lamp 304 , the diode 352 is conductive and the diode 351 is non-conductive so that the signal S 6 provided by the lamp voltage sensing circuit 306 is applied to the pulse width modulator 307 . Once the fluorescent lamp 304 is ignited, the voltage across the fluorescent lamp 304 drops and the lamp current increases so that the diode 352 is non-conductive and the diode 351 is conductive. Hence the signal S 5 provided by the lamp current sensing circuit 305 is applied to the pulse width modulator 307 . As a result, the inverter could provide a stable high voltage to the fluorescent lamp 304 during start operation and a stable current to the fluorescent lamp 304 during normal operation.
[0041] The detail description of the protection circuit in this embodiment of the present invention is described as below:
[0042] Before the fluorescent lamp 304 connected to the inverter, the signal S 14 automatically is delivered to the logic control circuit 372 to indicate that the fluorescent lamp 304 is not ignited. In order to provide enough time to ignite the fluorescent lamp 304 , the time out signal S 10 is delivered to the protection circuit 310 to enforce the logic control circuit 372 to ignore that the signal S 14 indicates the information of the non-ignition of the fluorescent lamp 304 . Once the time reaches the preset value, the inverter utilizes another digital timer to calculate time on the base of the pulse signal S 15 . If the fluorescent lamp 304 still is not ignited after several clock cycles, the logic control circuit 372 outputs a signal S 20 to stop the operation of the half-bridge drive circuit 309 and the conduction of the power switches 302 A, 302 B. In this embodiment of the present invention, once the protection circuit 310 stops the power switches 302 A, 302 B, the inverter 300 must be turned off and restarted to get rid of the protection action.
[0043] When the fluorescent lamp 304 is broken and open during operation, the signal S 14 is delivered to the logic control circuit 372 to indicate the information of the non-ignition of the fluorescent lamp 304 . The logic control circuit 372 receives the time out signal S 10 provided by the timer 311 . The logic control circuit 372 does not work until the time out signal S 10 is delivered to the logic control circuit 372 . Once the time is over the preset value, the inverter utilizes another digital timer to calculate time on the base of the pulse signal S 15 . If the fluorescent lamp 304 still is not ignited after several clock cycles, the logic control circuit 372 outputs a signal S 20 to stop the operation of the half-bridge drive circuit 309 and the conduction of the power switches 302 A, 302 B. In this embodiment of the present invention, once the protection circuit 310 stops the power switches 302 A, 302 B, the inverter 300 must be turned off and restarted to get rid of the protection action.
[0044] The dimming control circuit 312 utilizes a lower frequency than the operating frequency of the fluorescent lamp 304 to stop or recover to deliver power to the fluorescent lamp 304 . The adjustment of the ratio of lightness and darkness is utilized to adjust the brightness of the fluorescent lamp 304 . The dimming frequency control generally is controlled above 200 Hz in order to avoid the user's feeling of flicker caused by lower dimming frequency. The dimming control circuit 312 is enabled by two signals. One is the signal S 14 which indicates the conduction state of the fluorescent lamp. The other is the time out signal S 10 provided by the timer 311 . When the signal S 14 indicates that the fluorescent lamp is conductive or the time out signal S 10 indicates that time is out, a switch 336 is turned on to control the output of the dimming signal. A dimming voltage S 21 of the dimming control circuit 312 is higher than the reference voltage Vref 5 . When the dimming voltage S 21 is delivered to the pulse width modulator 307 through switched 336 , 335 and the resistor 334 , the output voltage of the error amplifier 361 of the pulse width modulator 307 becomes smaller and causes the inverter to stop the power delivery to the fluorescent lamp. When the dimming pulse signal S 9 turns off the switch 335 , the dimming voltage S 21 is not delivered to the pulse width modulator 307 . It is an open circuit between the dimming voltage S 21 and the pulse width modulator 307 so that the inverter recovers to deliver the power to the load.
[0045] In this embodiment of the present invention, the dimming frequency generator 331 generates a triangle wave S 7 . The comparator 332 compares the triangle wave S 7 and the dimming control voltage S 8 to generate the dimming pulse signal S 9 . The dimming pulse signal S 9 has different pulse widths. The present invention utilize a low frequency control to control the ratio of the power stop period or the power supply period each cycle in order to achieve the brightness adjustment. However, the conduction state of the fluorescent lamp 304 could determine when starts to proceed the dimming control and ensure the fluorescent lamp 304 has enough time and continuous power to be ignited.
[0046] In this embodiment of the present invention, in order to the interference between the internal clock of LCD and the low frequency dimming control, the dimming control voltage S 8 could be a low frequency pulse generated by related internal clock of LCD. When the amplitude of the dimming control voltage S 8 is greater than the peak value of the triangle wave S 7 and smaller than the valley value of the triangle wave S 7 , the duty cycle and frequency of the dimming pulse signal S 9 is completely determined by the duty cycle and frequency of the dimming control voltage S 8 . Hence it could reduce the difference frequency interference of user's sense of sight caused by the difference between operating frequency of dimming control and the operating frequency of LCD.
[0047] In order to provide a symmetric alternating current to drive the fluorescent lamp 304 , the upper half of the half-bridge power switch circuit 110 is driven out of phase with the lower half of the half-bridge power switch circuit 110 such that when the power switch 110 A is on, the power switch 110 B is off, and conversely, when the power switch 110 A is off, the power switch 110 B is on. Driven in this manner, the upper half of the half-bridge power switch circuit 110 and the lower half of the half-bridge power switch circuit 110 have the same duty cycle and alternatively turned on and off with 180° phase shift.
[0048] Additionally, while the present invention makes specific reference to CCFLs, the present invention is equally applicable for driving many types of lamps and tubes known in the art, such as: metal halide lamps, sodium vapor lamps, and/or x-ray tubes.
[0049] Furthermore, while the present invention makes specific reference to piezoelectric, the present invention is equally applicable for any types of transformers known in the art, such as: electromagnetic transformers.
[0050] One skilled in the art will understand that the embodiment of the present invention as shown in the drawings and described above is exemplary only and not intended to be limiting.
[0051] The foregoing description of the preferred embodiment of the present invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form or to exemplary embodiments disclosed. Accordingly, the foregoing description should be regarded as illustrative rather than restrictive. Obviously, many modifications and variations will be apparent to practitioners skilled in this art. The embodiments are chosen and described in order to best explain the principles of the invention and its best mode practical application, thereby to enable persons skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use or implementation contemplated. It is intended that the scope of the invention be defined by the claims appended hereto and their equivalents in which all terms are meant in their broadest reasonable sense unless otherwise indicated. It should be appreciated that variations may be made in the embodiments described by persons skilled in the art without departing from the scope of the present invention as defined by the following claims. Moreover, no element and component in the present disclosure is intended to be dedicated to the public regardless of whether the element or component is explicitly recited in the following claims. | A resonant DC/AC inverter includes a DC power source providing a DC voltage, a half-bridge power switch circuit electrically connected to the DC power source being operative to convert the DC voltage to an AC voltage, a resonant tank electrically connected between an output of the half-bridge power switch circuit and an input of a load being operative to boost and filter the AC voltage to generate an AC power voltage supplied to the load, and a controller being operative to detect a magnitude of current in the load and a magnitude of a voltage across the load and to generate pulse waveforms for turning on and off the half-bridge power switch circuit, wherein the controller substantially instantaneously varies a frequency of the pulse waveforms and a duty cycle of the pulse waveforms so as to operate the resonant DC/AC inverter near a neighborhood of a resonant frequency of the resonant tank regardless of a conduction state of the load and improve the efficiency of the inverter regardless of the higher DC voltage applied to the inverter. Particularly, the resonant DC/AC inverter utilizes a piezoelectric transformer to supply power to a fluorescent lamp which is wildly employed in display panels and is extensively used to provide backlighting for liquid crystal displays (LCDs), especially for backlighting LCD monitors and LCD televisions. | 7 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to systems and methods, including computer systems and methods, for recognizing standard collections of audio tracks such as the ones found on audio compact discs, audio DVDs, or their digitized versions and providing additional information to the user regarding these tracks.
[0003] 2. Description of Related Art
[0004] Methods exist for reading table of contents data from compact discs and using the data to lookup information in databases or to monitor and control the playback of a compact disc. For example, U.S. Pat. Nos. 6,230,192 and 6,330,593 (“the '192 and '593 patents”) relate generally to delivering supplemental entertainment content to a user listening to a musical recording. The content is accessed using an Internet Web browser, which is able to control and monitor playback of the recording. Using conventional techniques, an identifier is computed for the CD being played. The identifier may be determined based on the number and lengths of tracks on the CD, which are measured in blocks (frames) of {fraction (1/75)}th of a second. For example, the identifier may be a concatenation of the track lengths. In practice, to shorten the identifier, the track lengths may be expressed in coarser units, e.g., in units of {fraction (1/4)}th of a second.
[0005] The identifier is used to retrieve information from a database relating to the recordings played by the user. Specifically, the identifier is computed upon detection of a disc in the CD player of the user's computer and sent to a remote server hosting a Web site containing information about the CDs produced by a particular record company. The server uses the identifier as a key to lookup a single matching record in a database and outputs the information stored in that matching record. This information includes a Web address (URL) that is related to the audio CD (e.g., that of the artists' home page), simple data such as the names of the songs, and also complementary entertainment, including potentially video clips, which is accessed using the stored URL.
[0006] Among the disadvantages of such a system is that it does not account for differences in track times that may occur in different releases or pressings of CDs of the same recording. Such differences could result in an identifier being computed that does not match the identifier stored in the database, which in turn might prevent retrieval of the data relating to the recording. If the track length differences are large enough, then this problem would arise even if the identifier is expressed in coarser units than the data retrieved from the CD, e.g., rounded to the nearest ¼ second rather than {fraction (1/75)}th second.
[0007] The '192 and '593 patents also purport to describe a “fuzzy comparison algorithm” for determining whether two CDs are the same. The algorithm involves truncating track lengths obtained from table of contents data and summing the total track time and track time differences between two CDs. These values are then used to determine a percentage that is “indicative of how well the two CDs match.” It is unclear from the description in these patents how this algorithm is to be used. If it is used to find a match between a CD being played and an entry in a database, then such an approach has at least two disadvantages. First, this calculation would have to be performed for each and every entry in the database to find a single matching record, which would be extremely inefficient. Second, the truncation of the track lengths raises the possibility that two different CDs might yield the same truncated track lengths and be identified as a match. Or, as discussed above, two different pressings or releases of the same CD might yield different truncated track lengths and therefore would not be identified as a match. In either case, a correct matching record in the database would not be found.
[0008] Thus, the approaches taken in the '192 and '593 patents suffer from a number of disadvantages, because they are predicated on computing a single identifier for a recording and looking up information in a database containing only one matching record. What is needed is a system for efficiently retrieving information relating to a digital audio recording that takes into account differences in track lengths in different pressings or releases of a recording as well as their digitized versions stored on a PC.
SUMMARY OF THE INVENTION
[0009] It is an object of the present invention to provide systems and methods for providing a user with information relating to a digital audio recording by looking up the information in a database using a set of approximate track durations from a collection of the digital audio recordings (e.g. an audio CD).
[0010] It is another object of the present invention to provide systems and methods for accurately looking up information relating to a digital audio recording in a database using table of contents data read from the recording, even if the table of contents data varies due to differences in pressings or releases.
[0011] It is another object of the present invention to provide systems and methods for efficiently generating multiple records for a fuzzy database to account for variations in track duration data, without having to include an undue number of possible permutations of a table of contents data sequence.
[0012] In one aspect, the present invention provides a method and computer code for matching a track set from a digital audio recording to metadata relating to the recording. Track duration data is obtained for the track set, and the track duration data is rounded. A search is performed for matching records in a first database based on the rounded track duration data, each resulting matching record having an identifier. Track duration data is retrieved from a second database based on the identifiers associated with the matching records. If more than one matching record is found, the track duration data retrieved from the second database is compared to the track duration data obtained for the track set to find a best matching record of in the second database. Metadata contained in the best matching record of the second database is output.
[0013] Embodiments of the present invention may include one or more of the following features. For each matching record, the track duration data retrieved from the second database may be compared to the track duration data obtained for the track set to determine if each matching record meets a match quality threshold. The track duration data for the track set may be received by a server from a client device via a network and the metadata may be sent from the server to the client device via the network. Records of the first database may be generated by rounding a sequence of track durations computed from table of contents data for each recording of a collection of digital audio recordings. The computed sequence of track duration data for each recording may be obtained from the second database. The computed sequence of track durations for each recording may be truncated to a predetermined number of tracks. The best matching record of the second database may be determined by computing a sum of squared differences between a sequence of values in the track duration data retrieved from the second database and a corresponding sequence of values in the track duration data obtained for the track set.
[0014] The rounding of the sequence of track durations may include rounding each value in the sequence of track durations in a selected direction to a nearest integer multiple of a rounding factor when the value is not within a predetermined range of an integer multiple of the rounding factor. And, each value in the sequence of track durations may be rounded in both the selected direction and an opposite direction when the value is within the predetermined range of an integer multiple of the rounding factor.
[0015] Multiple records may be generated for the first database from the sequence of track durations when at least one value in the sequence is rounded in both the selected direction and the opposite direction. The multiple records may correspond to all possible permutations of the sequence resulting from values that have been rounded in both the selected direction and the opposite direction.
[0016] In another aspect, the present invention provides a method and computer code for generating records for a matching database for a collection of digital audio recordings. A sequence of track durations is obtained for each recording of the collection of recordings. Each value in the sequence of track durations is rounded in a selected direction to a nearest integer multiple of a rounding factor when the value is not within a predetermined range of an integer multiple of the rounding factor. Each value in the sequence of track durations is rounded in both the selected direction and an opposite direction when the value is within the predetermined range of an integer multiple of the rounding factor. Multiple records are generated from the sequence of track durations when at least one value in the sequence is rounded in both the selected direction and the opposite direction. The multiple records correspond to all possible permutations of the sequence resulting from values that have been rounded in both the selected direction and the opposite direction.
[0017] Embodiments of the present invention may include one or more of the following features. The sequence of track durations for each recording of the collection of recordings may be obtained from a second database containing a record corresponding to each recording, each record including metadata relating to the recording.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a block diagram illustrating a number of clients connected to a Track Set Server through a network.
[0019] FIG. 2 is a block diagram illustrating a computer having local track durations databases.
[0020] FIG. 3 is a flow chart illustrating a preferred embodiment of the present invention.
[0021] FIG. 4 is a diagram illustrating a rounding technique employed by the present invention.
[0022] FIG. 5 is a diagram illustrating the generation of multiple entries for the fuzzy track durations database.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0023] Speaking generally, the present invention is practiced by deriving track duration data for a collection of audio tracks from table of contents (TOC) data stored on a digital audio recording using a computer or other playback device. Alternatively, track durations may be read directly from a collection of audio files (e.g. an album that has been digitized and store on a computer using an audio player). The track duration data, which includes information regarding the length of each track and the number of tracks into which a recording is divided, is used to look up information about the audio recording, such as the title and artist, in a database generated using a fuzzy algorithm.
[0024] As used herein, the term “computer” may refer to a single computer or to a system of interacting computers. Generally speaking, a computer is a combination of a hardware system, a software operating system and perhaps one or more software application programs. Examples of computers include, without limitation, IBM-type personal computers (PCs) having an operating system such as DOS, Microsoft Windows, OS/2 or Linux; Apple computers having an operating system such as MAC-OS; hardware having a JAVA-OS operating system; graphical work stations, such as Sun Microsystems and Silicon Graphics Workstations having a UNIX operating system; PalmPilots; and Pocket PCs.
[0025] “Network” means a connection between any two or more computers, which permits the transmission of data. An example of a network, although it is by no means the only example, is the Internet.
[0026] “Web page” means any documents written in mark-up language including, but not limited to, HTML (hypertext mark-up language) or VRML (virtual reality modeling language), dynamic HTML, XML (extended mark-up language) or related computer languages thereof, as well as to any collection of such documents reachable through one specific Internet address or at one specific Web site, or any document obtainable through a particular URL (Uniform Resource Locator).
[0027] “Web site” means at least one Web page, and more commonly a plurality of Web pages, virtually connected to form a coherent group.
[0028] “Web browser” means any software program which can display text, graphics, or both, from Web pages on Web sites. Examples of Web browsers include, without limitation, Netscape Navigator and Microsoft Internet Explorer.
[0029] “Web server” refers to a computer or other electronic device which is capable of serving at least one Web page to a Web browser.
[0030] The phrase “display a Web page” includes all actions necessary to render at least a portion of the information on the Web page available to the computer user. As such, the phrase includes, but is not limited to, the static visual display of static graphical information, the audible production of audio information, the animated visual display of animation and the visual display of video stream data.
[0031] “Metadata” generally means data that describes data. In the context of the present invention, it means data that describes the contents of a digital audio recording. Such metadata may include, for example, artist information (e.g., name, birth date, discography, etc.), album information (e.g., title, review, track listing, sound samples, etc.), relational information (e.g., similar artists and albums), and other types of supplemental information.
[0032] “Frame”, in the context of the present invention, refers to the smallest unit of time on a compact disc, which is {fraction (1/75)}th of a second (2352 bytes of digital audio data).
[0033] For the present invention, a software application could be written in substantially any suitable programming language, which could easily be selected by one of ordinary skill in the art. The programming language chosen should be compatible with the computer by which the software application is executed, and in particular with the operating system of that computer. Examples of suitable programming languages include, but are not limited to, Object Pascal, C, C++, CGI, Java and Java Scripts. Furthermore, the functions of the present invention, when described as a series of steps for a method, could be implemented as a series of software instructions for being operated by a data processor, such that the present invention could be implemented as software, firmware or hardware, or a combination thereof.
[0034] With reference to FIG. 1 , the system includes a track set (TS) server 100 , which for example may be a Web server, operably connected to a network 105 , e.g., the Internet. The TS server 100 includes a full track set database 110 that holds track duration data and information relating to digital audio recordings. The TS server 100 also includes a fuzzy track set database 115 that holds similar information, but is configured to allow more efficient data retrieval by using a fuzzy algorithm to generate matching keys, as described in detail below. Also connected to the network are a number of client devices 120 , Client 1 through Client n, that are configured to read digital audio recordings and associated track duration data from media such as compact discs (CD) or local hard drives and send the track duration data to the TS server 100 to retrieve information relating to the recording. The client devices may be for example personal computers (Client 1 ), component CD players (Client 2 ) and portable CD players (Client 3 ). Other possibilities for client devices exist as well.
[0035] Each client 120 has hardware and software for communicating with the TS server 100 . For example, a client computer may have an operating system with a graphical user interface (GUI) to access the Internet, and is preferably equipped with graphical World Wide Web (Web) browser software, such as Netscape Navigator™ or Microsoft Internet Explorer™, operable to read and send Hypertext Markup Language (HTML) forms from and to a Hypertext Transport Protocol (HTTP) server on the Web. Client CD players may have built-in interfaces that enable them to communicate with the TS server via the Internet, either directly or through a computer. For example, a CD player may have a data interface, such as a RS-232 or USB, that enables it to send and receive data from a computer, which in turn is connected to the Internet.
[0036] Likewise, the TS server 100 includes hardware and software for communicating with the clients 120 . For example, the TS server 100 may have HTTP compliant software, an operating system and common gateway interface (CGI) software for interfacing with clients 120 via the Internet. Alternatively, the TS server 100 and clients 120 may run proprietary software that enables them to communicate via the Internet or some other type of network.
[0037] It will be readily appreciated that the schematic of FIG. 1 is exemplary only, and that numerous variations are plainly possible. For example, the TS server 100 may be connected to a local area network (LAN), which in turn may be connected to the network. The TS server 100 may be implemented using multiple Web servers. Also, the network 105 may be a local area network (LAN) or a wide area network (WAN) other than the Internet.
[0038] Alternatively, as shown in FIG. 2 , the invention may be implemented without client-server architecture and/or without a network; instead, all software and data necessary for the practice of the present invention may be stored on a storage device associated with the digital audio playback device. For example, a computer 125 may have a CD drive 127 to playback compact disc 129 digital audio. The computer 125 also may have a local fuzzy track set database 130 and a local full track set database 135 stored on a hard disk 140 , each containing a complete set or a subset of the information available in the corresponding databases on the TS server 100 . These databases 130 and 135 may be loaded onto the hard disk 140 from a CD-ROM 145 , or the databases may be downloaded and updated from a remote host 150 via a network 155 . For example, the databases may be downloaded from a Web site via the Internet. Other variations exist as well.
[0039] In a preferred embodiment of the present invention, track duration data may be derived from table of contents (TOC) data for a digital audio recording, such as a compact disc (CD). TOC data is stored on a CD using a format specified in the “Red Book” (Compact Disc Digital Audio System Description, Philips Corp., May 1999), which provides the standards for digital audio CDs. The TOC data consists of a string of concatenated track start times for every track on the disc, expressed as six-digit hexadecimal values. The track start times are provided in units of frames, and each frame is {fraction (1/75)}th of a second. The final six-digit value in the TOC data is the total disc time in frames. For example, the TOC data for a CD may be given by the following:
0000096004187006F2500C77C010EF0015F9A01DC95021F28025439028F23
This TOC data specifies a disc that is 37 minutes, 16 seconds, and 15 frames long: 028F23h=167715 frames=2236.2 seconds=37 min 16.2 s
[0042] This TOC data specifies the track start times as:
Track Start Time 1 000096h 2 004187h 3 006F25h 4 00C77Ch 5 010EF0h 6 015F9Ah 7 01DC95h 8 021F28h 9 025439h
[0043] Thus, the seventh track, for example, starts at 27 minutes, 6 seconds, and 505 frames: 01DC95h=122005 frames=1626.7333 seconds=27 min 6.7333 s. Of course, the track duration for each track may be computed from the track start times and the total disc time.
[0044] As noted above, the TS server 100 maintains a full track set database 110 containing information relating to a known collection of digital audio recordings, such as for example artist name, birth date, discography, album title, reviews, track listings, sound samples, etc. This database is keyed according to a unique album identifier (A_ID) associated with each recording for which information is available. The full track set database 110 also contains a set of track durations computed from the track start times provided in the original TOC data strings for each recording.
[0045] The TS server 100 also maintains a fuzzy track set database 115 of album identifiers that is generated from full track set duration data using a fuzzy algorithm. The fuzzy algorithm allows for variability in the input track durations received from the client. Such variability may arise for example due to variations in CD pressings or various means of digitization. As described in further detail below, when the TS server 100 receives an input track duration data string from a client, it first performs a lookup operation in the fuzzy track set database 115 to retrieve an A_ID and then performs a lookup in the full track set database 110 to retrieve the metadata corresponding to the A_ID.
[0046] In the preferred embodiment of the present invention, as shown in FIG. 3 , a user inserts a compact disc (step 205 ) into a client device 120 , such as a personal computer. The TOC data is read from the disc (step 210 ) using standard calls to the CD application program interface (API), which is available under most commonly used operating systems. The TOC data is then converted into a sequence of track durations and sent to the TS server 100 via the network 105 (step 215 ). Alternatively, a sequence of track durations could be derived from a collection of digital files residing on a PC or any other storage device.
[0047] The TS server 100 receives the input data from the client device 120 and rounds and/or truncates the sequence of track durations (step 220 ). For example, the track duration input data may be truncated to a particular number of tracks, e.g., five. Then the data may be rounded in a particular direction using a particular rounding factor, e.g., 100 frames. For example, the data may be rounded down, in which case each track duration is rounded to the nearest 100 frames in the downward direction. Alternatively, the data may be rounded up, in which case each track duration is rounded to the nearest 100 frames in the upward direction. As a further alternative, the data may be rounded up or down to the nearest 100 frames, in which case each track duration is rounded in the upward or downward direction depending upon which is the shortest distance. Of course, one of ordinary skill in the art would understand that rounding a track duration down to the nearest 100 frames is the same as truncating the track duration by removing the two least significant digits (the ones and tens place digits). Thus, it is to be understood that the term “rounding,” as used in this context, is the same as “truncating.”
[0048] A lookup is performed in the fuzzy track set database 115 (step 225 ) using the rounded, truncated input string to determine if there are any matching entries (step 230 ), and an A_ID is returned for each match. If there are no matches, the TS server 100 sends a response to that effect back to the client 120 (step 235 ), otherwise, the TS server 100 performs a lookup in the full track set database 110 for each A_ID. If there is more than one match, the closest match may be determined, for example, by computing the sum of the squares of the track duration differences between the input string (before rounding) and the full track duration data string associated with each A_ID in the full track set database 110 (step 240 ). The closest match, or the only match if such is the case, may be compared to a quality threshold. If the sum of the squares of the track duration differences is less than or equal to the match quality threshold, the metadata associated with the A_ID for this match is sent back to the client 120 (steps 245 and 235 ).
[0049] After receiving the response from the TS server 100 (step 235 ), the client 120 determines whether a matching A_ID has been returned (step 250 ) and then may display the returned metadata (step 255 ) or a “no matches” screen, as appropriate (step 260 ). Other actions may be taken by the client 120 as well.
[0050] To generate the fuzzy track set database 115 , a fuzzy algorithm is applied to the track duration data in the full track set database 110 , which, as described above, comprises track durations for each track (computed from the track start times in the original TOC data string). As a first step, the fuzzy algorithm truncates the track duration data to a particular number of tracks (T), e.g., T=5. The algorithm then rounds each track duration of the truncated data string in the following manner to produce a rounded, truncated substring.
[0051] FIG. 4 illustrates the manner in which the track durations are rounded. A particular rounding factor (N) is used, e.g., N=100 frames, and a particular direction is selected, e.g., the downward direction, in which case each track duration is rounded down to the near 100 frames. For example, a track duration of 11678 frames would be rounded to 11600 frames, a time of 11744 frames would be rounded to 11700 frames, and a time of 11863 frames would be rounded to 11800 frames. After rounding, only the significant digits need be retained, so these times may be expressed as 116, 116, and 118, respectively. Up to this point, the truncation and rounding are similar to that done to the track duration input data received from the client. However, the following additional steps are performed on the data stored in the fuzzy track set database.
[0052] Rounding the track durations raises the possibility that an input string that varies somewhat from the full track duration data string may round to a different result, thereby resulting in a match not being found due to a rounding boundary effect. For example, if the second pressing of a CD has a track duration of 11744 for a particular track, instead of 11678, then that time would be rounded to 117, rather than 116. This would result in a match not being found in the fuzzy track durations database for a CD from the second pressing. To avoid this problem, multiple entries may be provided in the fuzzy track set database for a particular recording, i.e., a particular album identifier.
[0053] One way of generating multiple entries for the fuzzy track set database would be to round each track duration both up and down and include every possible permutation of these multiple rounded track durations. This method, however, would be inefficient, as it would result in a database having 2 T entries (where T is the number of tracks in the truncated string) for each A_ID. Instead, a track duration will be rounded both up and down only if it is within a certain number of frames (P) of an integral multiple of the rounding factor (N). The number of frames in this rounding interval (P) is preferably chosen to be the rounding factor (N) divided by four, e.g., P=N/4=25, which is an equidistant division point between the rounding mid-point and the rounding boundary.
[0054] The division of the rounding factor by four results in a rounding interval (P) that is an optimum balance between redundancy and recognition quality. By comparison, division of the rounding factor by two results in every possible permutation being produced, because a value is always within a distance of less than half the rounding interval of the nearest rounding boundary, e.g., within 50 frames of the nearest integer multiple of 100 frames. Also, division of the rounding factor by an integer greater than four increases the possibility of missed matches, as discussed below.
[0055] For example, referring again to FIG. 4 , the value 11678 is within 25 frames of 11700, so it would be rounded both up to 117 and down to 116. Whereas, the value 11744 is not within 25 frames of a multiple of 100 frames and would therefore be rounded down to 117. Likewise, the value 11863 would be rounded down to 118. Multiple fuzzy track duration data strings are produced from the rounded values as follows.
[0056] Referring to FIG. 5 , assume a track durations data string is truncated to three tracks, with track durations of 22655, 11678, and 16628 frames, respectively (step 401 ). The value 22655 (Track 1 ) is not within 25 frames of a multiple of 100 frames (i.e., 22600 or 22700), so it is rounded down to 226 (step 402 ). The value 11678 (Track 2 ) is within 25 frames of 11700, so it is rounded to 116 and 117 (step 403 ). These two values are diagramed as separate branches of a tree structure to illustrate the multiple sequences of track durations that may be derived therefrom. The value 16628 (Track 3 ) is not within 25 frames of a multiple of 100 frames, so it rounded down to 166 (step 404 ). This value is diagramed in each of the two branches of the tree structure. This process results in the following track duration sequences, which each become entries in the fuzzy track set database:
226 116 166 226 117 166
[0059] The inclusion of multiple entries in the fuzzy track set database generated in this manner ensures a guaranteed accuracy of P frames. In other words, an input track duration string (before rounding and truncation) having track durations within P frames of corresponding track durations of the full track duration data string will result in a correct match in the fuzzy track set database. For the example above, an input string having track durations within 25 frames of the values 22655, 11678, and 16628, respectively, will result in a correct match.
[0060] The foregoing detailed description is intended to be illustrative and not limiting of the present invention, which is defined by the claims set forth below. | A system and method are provided for matching a track set from a digital audio recording to metadata relating to the recording. Track duration data is obtained for the track set, and the track duration data is rounded. A search is performed for matching records in a first database based on the rounded track duration data, each resulting matching record having an identifier. Track duration data is retrieved from a second database based on the identifiers associated with the matching records. If more than one matching record is found, the track duration data retrieved from the second database is compared to the track duration data obtained for the track set to find a best matching record of in the second database. Metadata contained in the best matching record of the second database is output. | 6 |
FIELD OF THE INVENTION
[0001] The invention is in the field of offset drive systems for utility vehicles. In particular, this invention is in the field of utility vehicles (such as Skid-Steer® and Bobcat® vehicles), fork lifts and front end loader machines.
BACKGROUND OF THE INVENTION
[0002] Traditionally, Skid-Steer® Loader Machines as made famous by manufacturers such as Bobcat® and the like have been powered almost exclusively by hydraulics. Skid-Steer® is a registered trademark of Arts-way Manufacturing Co., Inc., a Delaware Corporation. Bobcat® is a registered trademark of Clark Equipment Company of New Jersey.
[0003] These machines traditionally have gasoline or diesel internal combustion engines that drive a hydraulic pump. The pump usually provides power to two independently controlled hydraulic motors one for each side of the machine. The output of each motor drives a drive sprocket with two sets of sprocket teeth. One set of sprocket teeth drives a chain that goes to a front wheel sprocket and the other set of sprocket teeth drives a chain that goes to the rear wheel sprocket. The hydraulic pump also provides power for lifting functions and power takeoffs for implements that can be connected to the machine.
[0004] U.S. Pat. No. 4,705,449 to Christianson et al. discloses the use of two electric traction motors. FIG. 1 is a plan view of an electric drive system of U.S. Pat. No. 4,705,449 to Christianson et al. wherein battery 28 supplies electric power to two traction motors 60 , 64 which in turn are coupled 84 to a gear reducer 82 . Specifically, the '449 patent states at col. 4 line 10 et seq.: “a first traction motor 60 provides the motive force for the left-hand side of the vehicle and a second traction motor 64 provides the motive force for a right-hand side of the vehicle 66. Both the first traction motor 60 and the second traction motor 64 are powered by a battery pack 28 . . . . Similarly, the traction motor 64 is connected to a spur gear reduction assembly 82 through a coupling 84. The spur gear reduction assembly engages a chain 86 which in turn engages a right rearward gear 74 and left forward gear 90, which are respectively connected to wheels 14a and 14b through axles 92 and 94. As will be appreciated, the traction motor 60 is operated independently of the traction motor 64 thereby permitting the wheels 14c, 14d to operate at different speed than wheels 14a and 14b to create skid steering.”.
[0005] U.S. Pat. No. 4,705,449 to Christianson et al. discloses the use of two electric traction motors. The motors are not identified by type in Christianson et al as either DC or AC. However, the motors are DC electric motors as they are controlled by a device identified in the '449 patent to Christianson, namely, a General Electric EV 1 SCR Controller, which is designed to control DC motors. The General Electric EV 1 SCR Controller describes the use of rectifiers to pulse power to DC motors and has no provision for the control of AC motors.
[0006] A copy of the EV 1 SCR Controller technical literature is submitted herewith in an Information Disclosure Statement and describes the use of the controller as being for the control of DC motors. Additionally, the EV 1 SCR Controller is identified in U.S. Pat. No. 4,265,337 to Dammeyer entitled Fork Lift Truck Speed Control Upon Fork Elevation and is used to control a DC motor 92 .
[0007] Additionally, the EV 1 SCR Controller has been used in numerous automobiles (electric vehicles) in conjunction with DC series wound motors which provide high current and high torque at low rpm.
[0008] DC traction motors have been used in applications involving forklifts and similar vehicles in the past. Internal combustion engines are not favored in such applications because an internal combustion engine produces zero torque at zero engine speed (RPM) and reaches its torque peak later in its operating range. Internal combustion engines generally require a variable-ratio transmission between the engine and the wheels to match engine speed to the road speeds and loads encountered. A clutch must be provided so that the engine can be mechanically decoupled from the wheels when the vehicle stops. Additionally, some slippage of the engine with respect to the drive train occurs while starting from a stop. Direct current electric traction motors produce considerable torque at zero RPM and thus may be connected directly to the wheels. Alternating current motors, hydraulic motors and pneumatic motors also produce torque at zero RPM.
[0009] Although the term traction motor is usually referred to in the context of a direct current motor, the term is also applicable to alternating current motor applications as well. Additionally, the term traction motor is used to describe any motor of whatever type used to supply torque and power to a vehicle's wheel, tracks, etc.
[0010] In small utility vehicles and the like, space is an important consideration in the design of the vehicle. It is therefore desirable to use a small motor, electric, hydraulic, or pneumatic which is capable of supplying required torque and horsepower under all operating conditions. If an electric motor is used it may be an alternating current motor or it may be a direct current motor.
[0011] Generally, for a given power, high speed electric motors are smaller in size, lighter in weight, and less expensive than low speed motors. Generally, for a given power, alternating current motors are smaller than direct current motors.
[0012] Therefore, it is highly desirable to save space, weight and cost in the powertrain of a utility vehicle through the use of a high speed motor so that the space may be used for batteries, controls or other components.
SUMMARY OF THE INVENTION
[0013] As electric motor technology has advanced to provide more performance for less cost it makes sense to replace hydraulic systems with electric systems. Electric motors typically rotate at much higher RPM than hydraulic motors, particularly those suitable for skid-steer loaders. It is desirable to minimize the size of the drive train components so as to maximize the space available for batteries and controls. The vehicle described herein may employ Nickel Metal Hydride, Lithium Ion, Lithium Ion polymer, lead acid batteries or other battery technology.
[0014] Although one example of the invention as described herein uses high speed alternating current electric motors it is specifically contemplated that the invention may be used with high speed direct current electric motors, high speed hydraulic motors and high speed pneumatic motors.
[0015] The input to the gear box is an offset helical gear driven by a pinion. A planetary sun pinion inputs to the planetary stage. Planetary gear sets provide torque multiplication in compact packages. The output of the gear box is a carrier with a planetary gear-set reduction including a stationary ring gear. The gear box casing includes a ring gear which is a reaction gear and intermeshes with a three-gear planetary set. The carrier of the planetary gear set includes a spline which intermeshes with a splined output shaft.
[0016] The offset reduction in the gearbox is an important aspect of the invention as it enables the electric motors to be placed side to side. Use of electric motors is enabled in this application by offsetting the gear box. In this way the left and right side motors can be mounted side-by-side without interference while still maximizing available space for other components such as batteries and controls.
[0017] In another example, the offset gear box may be oriented differently (i.e., rotated 180 degrees) with the motors side by side. Although this example may result in reducing the width of the vehicle it may also result in increasing the length of the vehicle. Still alternatively, this example may be used to drive one of the wheel shafts directly.
[0018] A wheel driven utility vehicle includes a frame and two high speed alternating current electric motors arranged side by side for driving the vehicle. A variable frequency alternating current drive is utilized to control the speed of the motors and hence to control the direction and turning of the utility vehicle. Instead of high speed alternating current motors, high speed direct current motors, high speed hydraulic motors and/or high speed pneumatic motors may be used.
[0019] Each alternating current motor has an output which drives an offset planetary gear reducer. Each offset planetary gear reducer is affixed to the electric motor (or other motor type) and includes an output carrier interconnected with an output shaft. Each output shaft includes first and second chain drive sprockets which drive chains interconnected with shafts driving the front and rear wheels respectively. Each offset planetary gear reducer enables use of space saving high speed relatively low-torque alternating current electric motors (or other motors with similar performance characteristics) with attendant large speed reductions. Gear reduction enables the production of sufficient torque at the wheels of the vehicle. Applications in addition to utility vehicles are also specifically contemplated.
[0020] A utility vehicle drive system comprises two alternating current electric motors (or other high speed motors with similar performance characteristics) each having a shaft driven pinion gear. Intermediate gears engage shaft driven pinion gears which in turn drive planetary gears. Each of the planetary gear reducers include an output spline and each of the output splines are axially aligned with each other.
[0021] A method for using a high-speed electric motor (or high-speed hydraulic, pneumatic or direct current motors) in a utility vehicle includes the step of orienting the motors having shaft driven pinion gears side by side such that their shaft driven pinion gears are arranged on opposite sides of the vehicle. Next, the offset planetary gear reducers are mounted in engagement with the shaft driven pinion gears. Each of the planetary gear reducers include a gear driven by the shaft driven pinion gear. The gear driven by the shaft driven pinion gears includes a shaft portion formed as a second pinion sun gear which drives a planetary gear set and carrier. The planetary gear set reacts against a ring gear in the casing of the planetary gear reducer. The carrier of the planetary gear reducer includes a splined output. Each of the splined outputs are on the same axis of the other splined output located on the other side of the vehicle. Additionally, the method includes driving an output shaft coupled to the splined output of the carrier of the planetary gear reducer. And, finally, the method includes driving, with chains, the wheel shafts of the vehicle.
[0022] It is an object of the present invention to save motor space in a utility vehicle, recreational vehicle, and the like while providing for high torque at the vehicle wheel and tire.
[0023] It is an object of the present invention to provide a planetary gear reducer in a utility vehicle, recreational vehicle and the like which enables use of a smaller, lighter, high speed motor while providing for high torque at the vehicle wheel and tire.
[0024] It is an object of the present invention to provide a planetary gear reducer in a utility vehicle, recreational vehicle and the like which enables use of a smaller lighter high speed motor selected from the group of alternating current motors, direct current motors, hydraulic motors, and pneumatic motors.
[0025] It is an object of the present invention to provide a planetary gear reducer in a utility vehicle, recreational vehicle and the like which enables use of a smaller, lighter, high speed alternating current electric motor while providing for high torque at the vehicle wheel and tire.
[0026] It is an object of the present invention to provide for an efficient planetary gear reducer for use in a utility vehicle, recreational vehicle and the like.
[0027] It is an object of the present invention to provide for two offset electric motors in a utility vehicle, recreational vehicle, and the like by utilizing two offset planetary gear reducers.
[0028] It is an object of the present invention to utilize high speed alternating current motors in a utility vehicle, recreational vehicle or the like.
[0029] It is an object of the present invention to provide a method of using two high speed electric motors.
[0030] It is an object of the present invention to provide offset planetary gear reducers for use in combination with high speed motors for efficient use of space in a utility vehicle.
[0031] It is an object of the present invention to provide offset planetary gear reducers for use in combination with alternating current electric motors for efficient production of torque at the wheels of a utility vehicle.
[0032] These and other objects of the invention will best be understood when reference is made to the Brief Description of the Drawings, Description of the Invention and Claims which follow hereinbelow.
BRIEF DESCRIPTION OF THE DRAWINGS
[0033] FIG. 1 is a plan view of a prior art Skid-Steer vehicle powered by two DC traction motors.
[0034] FIG. 2 is a top plan view of the utility vehicle illustrating two alternating current motors oriented side by side with each having an offset planetary gear reducer driving a respective output shaft.
[0035] FIG. 2A is an enlarged portion of FIG. 2 illustrating a portion of the left side of the vehicle.
[0036] FIG. 2B is an enlarged portion of FIG. 2A illustrating the gear reducer and output shaft.
[0037] FIG. 2C is an exploded view of the input to the gear reducer, the gear reducer, and the output shaft.
[0038] FIG. 2D is a perspective view of the carrier and the output shaft.
[0039] FIG. 2E is a perspective view of the offset planetary gear speed reducer.
[0040] FIG. 3 is a block diagram of the method for using high speed alternating current electric motors with offset planetary gear reducers.
[0041] The drawings will be best understood when reference is made to the Description of the Invention and Claims below.
DESCRIPTION OF THE INVENTION
[0042] FIG. 2 is a top plan view 200 of the utility vehicle illustrating two alternating current electric motors 201 , 202 oriented side by side with each having an offset planetary gear reducer 203 , 204 driving a respective output shaft 208 , 214 . Although reference numerals 201 , 202 refer to high speed alternating current electric motors, it is specifically contemplated that other high speed motor types may be used such as direct current motors, hydraulic motors and pneumatic motors.
[0043] The utility vehicle includes a frame 205 , 206 , 250 , 251 for supporting vehicle components. As illustrated in FIG. 2 , side frame member 205 is on the left hand side of the vehicle and side frame member 206 is on the right hand side of the utility vehicle. The two side frame members 205 , 206 are shown in section in FIG. 2 , FIG. 2A , and FIG. 2B .
[0044] Frame side member 205 supports first chain driven wheel shaft 210 . Sprocket 210 S is formed as part of the wheel shaft 210 or alternatively is a separate sprocket affixed or attached to the wheel shaft 210 . Frame side member 205 also supports the output shaft 208 of the planetary gear reducer 203 .
[0045] Output shaft 208 includes two sprockets 208 S which are identical. The sprockets 208 S may be an integral part of shaft 208 or they may be separately attached to the shaft. A metal chain 210 interengages sprockets 210 S and 208 S and communicates horsepower and torque therebetween. The reduction ratio of output shaft driving sprocket 208 S to driven sprocket 210 S is approximately 2.5-5:1 such that for every rotation of the output shaft 208 the forward sprocket 210 S and wheel shaft 210 turns 0.4 to 0.2 of a turn or revolution. Reduction in speed of the driven sprocket 210 S results in a corresponding increase in torque for a given applied power.
[0046] Referring to FIGS. 2 and 2B , output shaft 208 is splined and is coupled to the splined output 230 T of the carrier 230 of the planetary gear reducer 203 . Frame side member 205 also supports the second chain driven wheel shaft 212 . Sprocket 212 S is formed as part of the wheel shaft 212 or alternatively is a separate sprocket affixed or attached to the wheel shaft 212 for driving a rearward wheel 212 A.
[0047] Metal chain 211 interengages sprockets 212 S and 208 S and communicates horsepower and torque therebetween. The reduction ratio of the output shaft driving sprocket 2085 to driven sprocket 2125 is approximately 2.5-5:1 such that for every rotation of the output shaft 208 the rearward sprocket 212 S and wheel shaft 212 rotates just 0.4 to 0.2 of a turn or revolution. The reduction in speed of the driven sprocket 212 S results in a corresponding increase in torque for a given applied power.
[0048] Similarly, the structure and operation of driven sprockets 2165 , 2175 , shafts 216 , 217 , frontward and rearward wheels 216 A, 217 A, sprockets 214 S, shaft 214 and chains 213 , 215 on the right side and within the right frame 206 are identical to the left frame side member 205 and frame 205 . The reduction ratio of the output shaft driving sprocket 214 S to driven sprockets 216 S, 217 S is the same as in connection with the left side of the vehicle, namely, approximately 2.5-5:1.
[0049] Speed reduction of approximately 2.5-5:1 just described are in addition to the speed reduction of the planetary gear reducers 203 , 204 which are described further herein. Alternating current motors 201 , 202 reside side by side and have output shafts 221 S, 222 S with pinion gears 221 , 222 thereon for driving two offset planetary gear reducers 203 , 204 to effect speed reduction and increase torque. Alternatively, a helical pinion gear 221 H and a helical driven gear 223 H. Full load electric motor torque is generally defined as follows:
[0000] Torque(ft-lbs.)=5250×horsepower/RPM
[0050] Generally, for a given power, high speed electric motors are smaller in size, lighter in weight, and less expensive than low speed motors. Generally, for a given power, alternating current motors are smaller than direct current motors. Additionally, for a given power, alternating current motors are smaller than direct current motors.
[0051] Use of planetary gear reducers 203 , 204 with alternating current motors 201 , 202 saves space. As previously stated the motors may be hydraulic, pneumatic or direct current motors. Reducers 203 , 204 are approximately 8 inches in diameter and approximately 5.5 inches deep and occupy a volume of approximately 300 cubic inches.
[0052] FIG. 2A is an enlarged portion 200 A of FIG. 2 illustrating a portion of the left side of the vehicle and FIG. 2B is a further enlargement of a portion 200 B of FIG. 2A illustrating the gear reducer 203 and pinion 221 on output shaft 221 S in more detail.
[0053] Referring to FIGS. 2A and 2B , the alternating current motors 201 , 202 are controlled by a variable frequency drive (not shown) to control the speed of the motors. Preferably the alternating current motors are three phase motors. Each of the offset planetary gear reducers 203 , 204 include a housing having a ring gear 224 affixed thereto. Ring gear 224 is trapped between housing portions 203 , 203 A of the reducer. Seals 224 S prevent leakage of lubricant from within the gear casing.
[0054] Each of the planetary gear reducers 203 , 204 includes a carrier 230 having planetary gears 225 , 226 , 229 intermeshing with the ring gear 224 and an output spline 230 T. Although the planetary gear reducer illustrated has three planetary gears, any reasonable number of planetary gears may be used. Each of the planetary gear reducers includes a gear 223 having teeth 223 T driven by the pinion gear 221 of the output shaft 221 of the alternating current motor 201 . The gear 223 driven by the pinion gear 221 of the output shaft 221 S of the alternating current motor 201 includes a shaft portion forming a sun pinion 227 with gear teeth 227 T.
[0055] Sun pinion or gear 227 intermeshes with three planet gears 225 , 226 , and 229 each of which naturally include teeth 225 T, 226 T and 229 T which intermesh with ring gear 224 . Ring gear 224 extends around the inner circumference of the gearbox. Each of the chain drive shafts 208 , 214 includes a spline 208 T thereon which intermeshes with output spline 230 T of the carrier 230 as best viewed in FIG. 2B . Planetary gear reducers 203 , 204 effect a speed reduction in the approximate range of between 20-30:1. That is for every revolution of the input pinion gears 221 , 222 , the carrier 230 will rotate 1/20 to 1/30 of a revolution. Other speed reductions are specifically contemplated. Chain drive sprockets 208 S, 214 S in combination with wheel shaft sprockets 210 S, 212 S, 216 S and 217 S effect a speed reduction in the approximate range of 2.5-5:1. That is, for every one rotation of the chain drive sprocket 208 S, the wheel sprockets 2105 , 2125 will rotate 0.4 to 0.2 of a revolution. Other speed reductions are specifically contemplated. Since torque is inversely proportional to the shaft rotational speed, torque is increased with a reduction in speed.
[0056] Other speed reductions are specifically contemplated depending on the desired torque at the wheels and traveling speed of the machine taking loads, inclines and other variables into consideration. Use of the offset speed reducer as disclosed herein enables the efficient use of space and provides the same torque to the wheel with less input torque supplied by the high speed electric motor. The efficiency of the offset speed reducer is approximately 95% at rated load.
[0057] Use of the offset speed reducer and electric motors enables use of high speed, light weight electric motors which are smaller in diameter and output less torque than slower, heavier larger motors whether they are alternating current motors or direct current motors. The savings in space, weight and money attained by use of the offset planetary gear reducers with high speed motors is considerable. Use of planetary gear reducers provides a stable transmission of power with torque amplification inversely proportional to the speed reduction. The planetary gear reducers of the instant invention weigh approximately 100 pounds but can vary in weight depending on the materials used such as steel, stainless steel or aluminum. The gears 223 , 225 , 226 , 229 and the carrier 230 are made of steel or stainless steel. Aluminum may be used for the gearbox casing 203 , 203 A if extremely light weight is desired. The low weight of the gear reducer having a volume of about 300 cubic inches (approx. 8 inches in diameter and 5.5 inches deep) in combination with a light-weight alternating current motor provides a compact low cost arrangement when placed side by side as illustrated in FIG. 2 .
[0058] Alternating current electric motors 203 , 204 are water cooled motors and run at 7,000 to 8,000 RPM. At approximately 7500 RPM the three phase electric motor outputs approximately 14.75 ft-lbs. of torque which equates to approximately 21 horsepower. The peak starting torque is about 77 ft-lbs. The motors to be used are about 14 inches long and 8 inches in diameter and have a volume of approximately 700 cubic inches.
[0059] FIG. 2C is an exploded view 200 C of the input to the gear reducer 221 T, the gear reducer 203 , and the output shaft 208 . Referring to FIGS. 2B and 2C , sun pinion 227 is supported by bearing 223 B and 227 B. Use of gear 223 enables the planetary gear reducer to be offset as it is driven by pinion 221 which is on the shaft 221 S of the electric motor. Three planet gears 225 , 226 and 229 and, more specifically, their teeth 225 T, 226 T and 229 T intermesh with sun pinion teeth 227 T and ring gear 234 and its teeth 234 T.
[0060] Planet gears 225 , 226 and 229 are supported by bearings (i.e., 235 B) and are pinned to the carrier by pins. See, for example, pin 235 in FIGS. 2A and 2B . Pin 225 P restrains pin 235 from movement within the carrier 230 and thus secures gear 225 in place. Gear 225 and the other planet gears are, of course, free to rotate but they are securely fastened to the carrier and impart rotational motion to the carrier 230 . Reference numeral 225 A indicates intermeshing between planet gear teeth 225 T and ring gear teeth 224 T. Referring to FIG. 2A , output shaft 208 is supported by bearings 208 B and 208 C and intermeshes its spline 208 T with spline 230 T of the carrier.
[0061] Planetary gear reducer 203 distributes the load evenly to three planets, 225 , 226 and 229 . As previously indicated any reasonable number of planet gears from 1 to “n” may be used. Reciting the operation of the gear reducer, torque is applied by shaft 221 S through teeth 221 T of pinion 221 which imparts rotational movement and torque to gear 223 . Gear 223 includes sun pinion 227 which by and through its teeth 227 T imparts rotational movement and torque to gears 225 , 226 and 229 via teeth 225 T, 226 T and 229 T. As previously stated planet gears 225 , 226 and 229 are free to rotate and impart rotational movement to carrier 230 effecting a speed reduction which is transmitted to output shaft 208 which is interconnected with the carrier spline 230 T. The gearbox 203 , 203 A is separable into two portions 203 and 203 A and they trap ring gear 224 when the gearbox is secured by fastener 240 A to the electric motor 201 and when the portions 203 , 203 A are secured together by fastener 240 .
[0062] FIG. 2D is a perspective view 200 D of the carrier 203 , 203 A, planet gears 229 and 225 , and output shaft 208 with a corresponding spline 208 T. FIG. 2E is a perspective view 200 E of the offset planetary gear reducer without bearing 208 B illustrated therein. The principal dimensions of the offset planetary gear reducer are approximately 8 inches in diameter and 5.5 inches deep neglecting the input housing 241 which houses pinion 221 . The offset planetary gear reducer is generally cylindrically shaped and includes a housing 241 for the shaft driven pinion gear 221 . A flange (unnumbered) is fastened to the motor 201 .
[0063] FIG. 3 is a block diagram 300 illustrating a method for using high-speed electric motors in combination with offset planetary gear reducers in a utility vehicle. The first step includes orienting two high speed electric motors having shaft driven pinion gears side by side 301 such that their shaft driven pinion gears are arranged on opposite sides of the vehicle. Next, the method includes mounting offset planetary gear reducers in engagement with the shaft driven pinion gears 302 . Each of the planetary gear reducers 203 , 204 include a gear driven by the shaft driven pinion gears 221 , 222 . The gear driven by the shaft driven pinion gears includes a shaft portion formed as a sun pinion gear 227 which drives a planetary gear set and carrier 230 reacting against a ring gear 224 in the casing of the planetary gear reducer 203 , 203 A. The carrier 230 of the planetary gear reducer includes a splined output 230 T and each of the splined outputs 230 T are on the same axis. The method further includes driving an output shaft 208 , 214 coupled to the splined output 230 T of the planetary gear reducer. Finally, the method includes driving, with chains ( 209 , 211 , 213 , 215 ), the wheel shafts ( 210 , 212 , 216 , 217 ) of the vehicle.
[0064] A list of reference numerals follows.
REFERENCE NUMERALS
[0000]
14 a - d -tires of vehicle
28 -battery
60 , 64 -motor
62 , 66 -sides of vehicle
68 , 84 -coupling
70 , 82 -spur gear reduction assembly
72 , 86 -chain
74 , 76 , 88 , 90 -gears
78 , 80 , 92 , 94 -axles
70 , 82 -spur gear reduction assembly
100 -prior art utility vehicle
200 -utility vehicle
200 A-enlarged portion of utility vehicle
200 B-further enlargement of planetary gear reducer
200 C-exploded view of powertrain
200 D-perspective exploded view of carrier and output shaft
200 E-perspective view of offset planetary gear reducer
201 , 202 -alternating current motor
203 , 203 A, 204 -gearbox
205 , 206 -vehicle side wall
208 , 214 -output shafts
208 B, 223 B, 227 B, 235 B, 208 C-bearing
208 T-spline on output shaft
209 , 211 , 213 , 215 -drive chains
210 , 212 , 216 , 217 -wheel shaft
210 A, 212 A, 216 A, 217 A-wheel tire
221 T-pinion teeth
221 , 222 -motor shaft pinion gear
221 H-helical pinion
221 S, 222 S-motor shaft
223 -gear
223 H-helical gear
223 B-bearing
223 T-teeth on gear
224 -stationary ring gear
224 T-ring gear teeth
224 S, 259 S-seal
225 , 226 , 229 -planet gear
225 A-mesh between planet gear teeth 223 T and ring gear teeth 224 T
225 P-pin
225 T, 226 T, 229 T-planet gear teeth
227 -sun pinion
227 T-sun gear teeth
230 -carrier
230 T-spline on carrier
235 -pin
240 , 240 A-bolt
241 -pinion housing
250 , 251 -frame member
300 -block diagram of method of using high speed motor and offset planetary gear reducers
301 -orienting and mounting high speed motors side by side with pinions oppositely arranged
302 -mounting offset planetary gear reducer in engagement with the shaft driven pinion gears 303 -coupling an output shaft to the spined output at a desired rate 304 -driving the wheel shifts of the vehicle
[0117] The invention has been set forth by way of example with particularity. Those skilled in the art will readily recognize that changes may be made to the invention without departing from the spirit and the scope of the claimed invention. | A wheel driven utility vehicle includes a frame and two small volume high speed alternating current electric motors arranged side by side for driving the vehicle. Alternatively high speed direct current, hydraulic or pneumatic direct current motors may be used with suitable controls. Each motor has an output shaft which drives an offset planetary gear reducer. Each offset planetary gear reducer is affixed to the electric motor and includes an output carrier interconnected with an output shaft. Each output shaft includes first and second chain drive sprockets which drive chains interconnected with shafts driving the front and rear wheels respectively. Each offset planetary gear reducer enables use of space saving high speed relatively low-torque alternating current electric motors with attendant large speed reductions. Gear reduction enables the production of sufficient torque at the wheels of the vehicle. Applications in addition to utility vehicles are also specifically contemplated. | 8 |
This application is a continuation of application Ser. No. 08/460,264 filed on Jun. 2, 1995, now abandoned, which is a divisional of application Ser. No. 08/370,709 filed on Jan. 10, 1995 abandoned.
FIELD OF THE INVENTION
The present invention relates to carbon black compositions comprising ethoxylated esters or polyethers and carbon black. The compositions may be produced by incorporating ethoxylated esters or polyethers onto fluffly carbon black in a pelletizing process to produce free flowing, low dust, attrition resistant carbon black pellets which are easily dispersible in most polymeric systems and provide enhanced rheological and mechanical properties.
The present invention also relates to polymer compositions which incorporate the carbon black compositions of the present invention.
BACKGROUND OF THE ART
Carbon blacks produced by a furnace process generally have bulk densities ranging from 0.02 to 0.1 gram/cubic centimeter (g/cc) and are generally known as fluffy carbon blacks. Fluffy carbon blacks are generally easy to disperse in liquids, and in some polymeric systems. However, fluffy carbon blacks are generally cohesive and, hence difficult to handle for purposes such as conveying and weighing.
Fluffy carbon blacks are agglomerated by various types of mechanical processes, either in the dry state, or with the aid of a liquid to produce pellets with improved handling characteristics. Common liquid pelletizing agents are oil and water. The process of agglomerating fluffy carbon blacks to form carbon black pellets is generally referred to as pelletizing.
Unfortunately, generally utilized densification or agglomeration (pelletizing) processes have detrimental effects on the dispersion characteristics of the carbon black. Therefore it is recognized in the art that in pelletizing carbon blacks there is a fine balance between acceptable handling characteristics and ease of dispersion.
A process for pelletizing carbon black is disclosed in U.S. Pat. No. 2,065,371 which describes a typical wet pelletization process whereby the fluffy carbon black and a liquid, typically water, are combined and agitated until spherical beads are formed. These beads are then dried to reduce the water content preferably to below 1% to form carbon black pellets.
Prior art patents also disclose the use of binder additives in a wet pelletization process to further improve the pellet handling characteristics.
U.S. Pat. No. 2,850,403 discloses the use of carbohydrates e.g. sugar, molasses, soluble starches, saccharides and lignin derivatives as pellet binders in the range of 0.1% to 0.4%, by weight, based on the dry carbon black. The preferred drying temperature of the wet pellet is disclosed as 150° to 425° C. which together with the residence time is sufficient to carbonize the binder.
U.S. Pat. No. 2,908,586 discloses the use of a rosin emulsion as pellet binders as an alternative to carbohydrates. The preferred level of rosin binder is in the range 0.5% to 2.0%, by weight, based on the dry carbon black.
U.S. Pat. No. 2,639,225 discloses the use of sulphonate and sulphate anionic surfactants as pellet binders at levels of 0.1% to 0.5%, by weight, based on the dry carbon black.
U.S. Pat. No. 3,565,658 discloses the use of a fatty amine ethoxylate non-ionic surfactant where the level of ethoxylation ranges from 2 to 50 moles of ethylene oxide per fatty amine group. The preferred level of surfactant in the pelletizing water is in the range 0.05% to 5%, by weight, based on the dry carbon black.
Similarly, U.S. Pat. No. 3,645,765 discloses the use of a fatty acid or rosin acid ethoxylate, non-ionic surfactant where the level of ethoxylation is 5 to 15 moles ethylene per acid group. The preferred level of addition on the carbon black is in the range 0.1% to 10%, by weight, based on the dry carbon black.
Soviet Union Patent No. 937,492 claims the benefits of using 0.1% to 5%, by weight, based on the dry carbon black, of an aqueous solution of a reaction product generated from urea and an ethoxylated alkylolamide. The preferred level of ethoxylation is 1 to 7 moles of ethylene oxide per alkylolamide molecule.
U.S. Pat. No. 3,844,809 discloses the reduction in pellet dust levels by incorporating 0.4% to 2.5%, by weight, based on the dry carbon black of an aqueous solution containing 0.001% to 0.1%, by weight, of a nonionic surfactant containing randomly repeating poly(ethylene oxide) and poly (dimethyl silicone) groups. Molasses is also included at substantially higher concentration (up to 2%, by weight) as a co-binder and nitric acid (up to 15%, by weight) as an oxidizing source.
The use of carbohydrates, rosin or surface active agents as disclosed in the above patents is focused towards improving pellet handling qualities. The patents do not disclose that the pelletizing treatments affected the performance properties of the carbon black in the final product applications, which are typically rubber orientated.
Japanese Patent No. 1,201,369 discloses the use of a carboxylic acid type amphoteric surfactant in a concentration range 0.001% to 0.1%, by weight, in the pelletizing water to produce carbon black pellets with low adhesion and excellent dispersibility.
U.S. Pat. No. 3,014,810 discloses the benefits of wet pelletizing a range of pigments, including carbon blacks, with a blend of a quaternary ammonium compound and a bis(-2-hydroxyethyl)alkyl amine. Improvements in dispersion rate, viscosity stability and antistatic properties are disclosed for the blend of surface active agents.
Pelletizing with oil, in the presence and absence of water is disclosed in U.S. Pat. No. 2,635,057, U.S. Pat. No. 3,011,902 and U.S. Pat. No. 4,102967 as beneficial in improving the handling properties of carbon black pellets.
Several patents, including U.S. Pat. No. 2,511,901, U.S. Pat. No. 2,457,962, U.S. Pat. No. 4,440,807, U.S. Pat. No. 4,569,834, U.S. Pat. No. 5,168,012 and Japanese Patent No. 77,130,481 disclose polymers in emulsion, organic solvent solutions and in molten form as means of modifying the pellet properties of carbon black.
U.S. Pat. No. 4,277,288 discloses a fluidised granulation process for producing free-flowing dustless pigment granules in the absence of water. The organic component required to produce a dustless granule consists of two components, 5-20 phr of a non-aqueous granulating aid and a non-ionic surfactant for example sorbitan oleate ethoxylate as a second component. The bulk of the disclosure relates to producing free-flowing organic and inorganic pigments, including carbon black.
U.S. Pat. No. 4,397,652 also discloses a process for producing negligible dust preparations of organic dyes and optical brighteners. The process involves the dry blending, between 30° and 80° C., of the dye, or optical brightener, with 2-10%, by weight, of an adhesive selected from the group consisting of polyhydric alcohol (e.g. sorbitol); manitol; manitose; lactose; hydrated dextrose; neopentyl glycol; and polyethylene glycol with a molar mass above 3,000. Also included in the composition is 1-10% of a dusting aid selected from the group consisting of fatty acid ethanolamide; fatty acid amide; alkyl alcohol; substituted phenol; and polyethylene glycol with a molar mass between 200 and 1000.
U.S. Pat. No. 4,230,501 discloses a pigment concentrate, dispersible in plastics, which is prepared by combining 51-85%, by weight, of a pigment and 14-49%, by weight, of a waxy component. The waxy component is disclosed as being predominantly a natural, petroleum or synthetic wax which has been blended with either polyethylene glycol or a hydrocarbon resin to reduce the melt viscosity and allow better incorporation of the pigment.
Polyethylene glycol is previously known as an additive for direct compounding into thermoplastic compositions.
U.S. Pat. No. 4,013,622 discloses the incorporation of 100 to 600 ppm of polyethylene glycol in the molar mass range of 600 to 20,000 (preferably 1300 to 7500) to reduce the breakdown of polyethylene during blown film operations which is observed as gel formation.
U.S. Pat. No. 4,812,505, U.S. Pat. No. 4,440,671 and U.S. Pat. No. 4,305,849 disclose the use of polyethylene glycols in the molar mass range 1,000 to 20,000 as beneficial for reducing the heat and water-treeing characteristics in polyolefin compositions for electrical insulation. Similarly U.S. Pat. No. 4,612,139 extends this concept of water-tree reduction to include the polyethylene glycol in semiconductive polyolefin compositions containing carbon black.
Similar compositions are claimed in German Patent DE 27 23 488 where polyethylene glycol and other mobile additives are disclosed as being beneficial to reduce the interlaminar adhesion between the insulation layer and outer conductive layer in an electric cable construction.
Polyethylene glycol and branched ethoxylate molecules are disclosed as plasticisers for ethylene-acrylic acid copolymers in U.S. Pat. No. 3,361,702.
United Kingdom Patent GB 975,847 discloses the use of polyethylene glycol, or an aliphatic derivative, in an aqueous solution as a means of producing agglomerates of organic rubber chemicals. A dough is formed as an intermediate which is then converted into pellets and dried at low temperatures.
SUMMARY OF THE INVENTION
The present invention comprises carbon black compositions that in their dry form have improved handling characteristics and that impart enhanced performance characteristics to polymer compositions. The carbon black compositions comprise:
carbon black and
0.1% to 50%, preferably 1 to 20%, by weight, of at least one binder selected from at least one of the following groups:
i) an ethoxylated polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to ethoxylation, where the total number of ethylene oxide molecules per polyhydric alcohol is at least 3; preferably the polyhydric alcohol is selected from the group consisting of triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sucrose or a polyglyceride and/or the total number of ethylene oxide molecules per polyhydric alcohol varies from 3 to 500 and more preferably varies from 5 to 100;
ii) an alkyl carboxylic acid ester of an ethoxylated polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to ethoxylation, where the alkyl carboxylic acid has from 8 to 30 carbon atoms, and may be saturated or unsaturated, and further where the mono-ester functionality is at least 80% with the remainder being a di-ester functionality, and further where the number of ethylene oxide molecules per polyhydric alcohol ester is at least 3; preferably the polyhydric alcohol is selected from the group consisting of triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sucrose or a polyglyceride and/or the total number of ethylene oxide molecules per polyhydric alcohol ester varies from 3 to 500 and more preferably varies from 5 to 100;
iii) an alkyl carboxylic acid ester of a polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to esterification, where the alkyl carboxylic acid has from 8 to 30 carbon atoms, and may be saturated or unsaturated, and further where the mono-ester functionality is at least 80% with the remainder being a di-ester functionality; preferably the polyhydric alcohol is selected from the group consisting of: triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sorbitol and a polyglyceride;
iv) an ethoxylated alkyl carboxylic acid ester of a polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to esterification, where the alkyl carboxylic acid has from 8 to 30 carbon atoms, and may be saturated or unsaturated, and further where the mono-ester functionality is at least 80% with the remainder being a di-ester functionality, and further where the number of ethylene oxide molecules per polyhydric alcohol ester is at least 3; preferably the polyhydric alcohol is selected from the group consisting of: triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sorbitol and a polyglyceride and/or the total number of ethylene oxide molecules per polyhydric alcohol ester varies from 3 to 500 and more preferably varies from 5 to 100;
v) a polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer.
It is also preferred that the binders of groups i, ii, iii, iv and v have an HLB value of 8.0 to 30.
HLB value refers to hydrophile-lipophile balance value which may be determined by the method described in Non-Ionic Surfactants Volume 23, edited by Martin Schick (Marcel Dekker Inc. (New York) 1987; ISBN 0-8247-7530-9), page 440. Non-Ionic Surfactants Volume 23 provides equations relating the structure of the surfactant molecule to HLB value. HLB value is also discussed in the following journal articles: Griffin W. C., J. Soc. Cosmetic Chemistt, Vol. 1, page 311 et seq. (1949) and Vol. 5, page 249 et seq. (1954). From data relating to the weight percentage of ethylene oxide in the molecule, saponification number of the ester linkage and acid value of the "fatty" acid, HLB value may be directly calculated from one of the following equations:
for polyhydric fatty acid esters:
HLB=20(1-S/A) where S=saponification number of the ester and A=acid number of the acid;
and
for ethoxylated polyhydric alcohols:
HLB=(E+P)/5, where E=weight of percent ethylene oxide and P=weight pigment of polyhydric alcohol.
While any carbon black may be utilized in the compositions of the present invention, preferably the carbon black component of the carbon black composition has a nitrogen surface area (N 2 SA) of 15 to 1800 m 2 /g, a fluffy dibutyl phthalate absorption value (DBP) of 50 to 350 cc/100 g and a cetyl trimethylammonium bromide absorption value (CTAB) of 15 to 1500 m 2 /g.
The carbon black compositions may be produced in any manner known in the art, such as by physically blending the components, melt mixing the components or combining the components while pelletizing the carbon black. Preferably the carbon black compositions are obtained by pretreating the carbon black with the binder.
The carbon black compositions may also be produced by a pelletizing process by:
contacting a fluffy carbon black in a pin pelletizer with an aqueous solution containing a binder selected from the foregoing groups of compounds wherein the preferred level of binder in the pelletizing water is from 0.5% to 50%; more preferably 20-40%, by weight; and
heating the wet pellets under controlled temperature and time parameters such that the water is removed from the pellets but the binder does not undergo substantial decomposition, and the final binder level on the dry carbon black is from 0.1% to 50%.
The present invention also includes new polymer compositions comprising:
a polymer component and 0.1-65%, preferably 0.1-20%, by weight, of a composition comprising a carbon black and 0.1-50%, preferably 1-20%, of at least one binder component selected from at least one of groups i, ii, iii, iv or v, set forth above. Preferably, the carbon black is pretreated with the binder component. The preferred carbon blacks, and binder components are as set forth above with respect to the carbon black compositions of the present invention. The polymer compositions may include other conventional additives such as pigments, reinforcing agents and the like.
While any polymer may be utilized in the polymer composition of the present invention, preferred polymers for use in the polymer compositions of the present invention include, but are not limited to:
a) homo or copolymers and graft polymers of ethylene where the co-monomers are selected from butene, hexene, propene, octene, vinyl acetate, acrylic acid, methacrylic acid, esters of acrylic acid, esters of methacrylic acid, maleic anhydride, half ester of maleic anhydride, and carbon monoxide;
b) elastomers selected from natural rubber, polybutadiene, polyisoprene, random styrene butadiene rubber (SBR), polychloroprene, acrylonitrile butadiene, ethylene propylene co and terpolymers;
c) homo and copolymers of styrene, including styrene-butadiene-styrene linear and radial polymer, acrylonitrile butadiene styrene (ABS) and styrene acrylonitrile (SAN);
d) linear and branched polyether or polyester polyols;
e) crystalline and amorphous polyesters and polyamides;
f) alkyd resins, rosin acids or rosin esters, hydrocarbon resins produced from thermal or Friedel Crafts polymerization of cyclic diene monomers such as dicyclopentadiene, indene, cumene; and
g) hydrocarbon oils such as parafinnic oil, naphthenic oil and hydrogenated naphthenic oil.
The polymer compositions of the present invention may be produced in any manner known to the art for combining polymers and dry or aqueous components.
The present invention further includes articles of manufacture produced from the polymer compositions of the present invention.
For use in semiconductive wire and cable applications, a typical formulation of the present invention preferably comprises:
25-55%, by weight, of a composition comprising carbon black and 0.5 to 10 parts per 100 parts of carbon black of at least one binder component selected from at least one of groups i, ii, iii, iv or v, set forth above;
0 to 2%, by weight a stabilizer or antioxidant
0 to 5%, by weight an organic peroxide, preferably dicumyl peroxide;
0 to 10%, by weight a vinyl silane;
the remainder being a polymer, or a blend of polymers, selected from the following group:
ethylene homopolymer;
ethylene copolymerized with one or more alpha olefins, such as propylene, butene, or hexene;
ethylene copolymerized with propylene and a diene monomer, preferably norbornene; and
ethylene copolymer with one or more monomers selected from vinyl acetate, acrylic acid, methacrylic acid, esters of acrylic or methacrylic acid containing 1 to 8 carbon atoms, maleic anhydride or a monoester derived from fumaric or maleic acid, vinyl chloride or vinylidene chloride.
The curable semi-conductive composition of the present invention may additionally include an additive polymer such as acrylonitrile butadiene elastomer containing 25-55%, by weight acrylonitrile.
For use as a masterbatch composition, a typical formulation of the present invention preferably comprises:
30-60%, by weight, of a composition comprising a carbon black and 0.1 to 50%, preferably 1-20%, of at least one binder component selected from at least one of groups 1, ii, iii, iv or v, set forth above; and
70-40%, by weight of an ethylene homopolymer or copolymer, where the comonomer is preferably selected from hexene, propene, butene, octene or vinyl acetate.
Preferably, the polymer composition is polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene or a polyethylene wax. The masterbatch composition may additionally include antioxidants, peroxide decomposers, hindered amine light stabilizers, substituted benzophenone UV adsorbers or process aids.
An advantage of the carbon black compositions of the present invention is that in dry form the carbon black compositions of the present invention have improved handling properties in comparison with conventional fluffy or pelleted carbon blacks.
An advantage of the polymer compositions of the present invention is that the polymer compositions exhibit enhanced rheological, processing or mechanical properties.
Further advantages of the carbon black compositions, and the polymer compositions, of the present invention will become apparent from the following detailed description.
DETAILED DESCRIPTION OF THE INVENTION
The present invention includes carbon black compositions which in dry form have improved handling characteristics and impart enhanced performance characteristics to polymer compositions.
The carbon black compositions comprise:
carbon black and
0.1% to 50%, preferably 1 to 20%, by weight, of at least one binder selected from at least one of the following groups:
i) an ethoxylated polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to ethoxylation, where the total number of ethylene oxide molecules per polyhydric alcohol is at least 3; preferably the polyhydric alcohol is selected from the group consisting of triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sucrose or a polyglyceride and/or the total number of ethylene oxide molecules per polyhydric alcohol varies from 3 to 500 and more preferably varies from 5 to 100;
ii) an alkyl carboxylic acid ester of an ethoxylated polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to ethoxylation, where the alkyl carboxylic acid has from 8 to 30 carbon atoms, and may be saturated or unsaturated, and further where the mono-ester functionality is at least 80% with the remainder being a di-ester functionality, and further where the number of ethylene oxide molecules per polyhydric alcohol ester is at least 3; preferably the polyhydric alcohol is selected from the group consisting of triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sucrose or a polyglyceride and/or the total number of ethylene oxide molecules per polyhydric alcohol ester varies from 3 to 500 and more preferably varies from 5 to 100;
iii) an alkyl carboxylic acid ester of a polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to esterification, where the alkyl carboxylic acid has from 8 to 30 carbon atoms, and may be saturated or unsaturated, and further where the mono-ester functionality is at least 80% with the remainder being a di-ester functionality; preferably the polyhydric alcohol is selected from the group consisting of: triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sorbitol and a polyglyceride;
iv) an ethoxylated alkyl carboxylic acid ester of a polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to esterification, where the alkyl carboxylic acid has from 8 to 30 carbon atoms, and may be saturated or unsaturated, and further where the mono-ester functionality is at least 80% with the remainder being a di-ester functionality, and further where the number of ethylene oxide molecules per polyhydric alcohol ester is at least 3; preferably the polyhydric alcohol is selected from the group consisting of: triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sorbitol and a polyglyceride and/or the total number of ethylene oxide molecules per polyhydric alcohol ester varies from 3 to 500 and more preferably varies from 5 to 100;
v) a polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer.
It is also preferred that the binders of groups i, ii, iii, iv and v have an HLB value of 8.0 to 30. HLB value may be determined in the manner set forth above.
While any carbon black may be utilized in the compositions of the present invention, preferably the carbon black component of the carbon black composition has a nitrogen surface area (N 2 SA) of 15 to 1800 m 2 /g, a fluffy dibutyl phthalate absorption value (DBP) of 50 to 350 cc/100 g and a cetyl triamethylammonium bromide absorption value (CTAB) of 15 to 1500 m 2 /g.
The carbon black compositions may be produced by any conventional technique for combining carbon black with dry or aqueous components. Preferably the carbon black compositions are produced by pretreating the carbon black with the binder. The carbon black compositions may be produced, in dry form, by a conventional pelletizing process. For example, the carbon black compositions of the present invention may be produced by contacting a fluffy carbon black in a pin pelletizer with an aqueous solution containing a binder selected from the foregoing groups of compounds wherein the level of binder in the pelletizing water is from 0.5% to 50%; and heating the wet pellets under controlled temperature and time parameters such that the water is removed from the pellets but the binder does not undergo substantial decomposition, and the final binder level on the dry carbon black is from 0.1% to 40%. The preparation of aqueous solutions containing the binder compositions used in the present invention is within the skill of one of ordinary skill in the art.
Pin pelletizers which may be utilized to produce the compositions of the present invention are known in the art and include the pin pelletizer described in U.S. Pat. No. 3,528,785, the disclosure of which is hereby incorporated by reference. U.S. Pat. No. 3,528,785 also describes a conventional pelletizing process which may be utilized to produce the compositions of the present invention.
The present invention also includes new polymer compositions comprising:
a polymer component and 0.1-65%, preferably 0.1-20%, by weight, of a composition comprising a carbon black and 0.1-50%, preferably 1-20%, of at least one binder selected from at least one of the following groups:
i) an ethoxylated polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to ethoxylation, where the total number of ethylene oxide molecules per polyhydric alcohol is at least 3; preferably the polyhydric alcohol is selected from the group consisting of triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sucrose or a polyglyceride and/or the total number of ethylene oxide molecules per polyhydric alcohol varies from 3 to 500 and more preferably varies from 5 to 100;
ii) an alkyl carboxylic acid ester of an ethoxylated polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to ethoxylation, where the alkyl carboxylic acid has from 8 to 30 carbon atoms, and may be saturated or unsaturated, and further where the mono-ester functionality is at least 80%lo with the remainder being a di-ester functionality, and further where the number of ethylene oxide molecules per polyhydric alcohol ester is at least 3; preferably the polyhydric alcohol is selected from the group consisting of triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sucrose or a polyglyceride and/or the total number of ethylene oxide molecules per polyhydric alcohol ester varies from 3 to 500 and more preferably varies from 5 to 100;
iii) an alkyl carboxylic acid ester of a polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to esterification, where the alkyl carboxylic acid has from 8 to 30 carbon atoms, and may be saturated or unsaturated, and further where the mono-ester functionality is at least 80% with the remainder being a di-ester functionality; preferably the polyhydric alcohol is selected from the group consisting of: triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sorbitol and a polyglyceride;
iv) an ethoxylated alkyl carboxylic acid ester of a polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to esterification, where the alkyl carboxylic acid has from 8 to 30 carbon atoms, and may be saturated or unsaturated, and further where the mono-ester functionality is at least 80% with the remainder being a di-ester functionality, and further where the number of ethylene oxide molecules per polyhydric alcohol ester is at least 3; preferably the polyhydric alcohol is selected from the group consisting of: triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sorbitol and a polyglyceride and/or the total number of ethylene oxide molecules per polyhydric alcohol ester varies from 3 to 500 and more preferably varies from 5 to 100;
v) a polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer. Preferably, the carbon black is pretreated with the binder component. The preferred carbon blacks, and binder components are as set forth above with respect to the carbon black compositions of the present invention. For example, it is preferred that the binder component have an HLB value of 8.0 to 30. The polymer compositions may include other conventional additives such as pigments, reinforcing agents and the like.
While any polymer may be utilized in the polymer composition of the present invention, preferred polymers for use in the polymer compositions of the present invention include, but are not limited to:
a) homo or copolymers and graft polymers of ethylene where the co-monomers are selected from butene, hexene, propene, octene, vinyl acetate, acrylic acid, methacrylic acid, esters of acrylic acid, esters of methacrylic acid, maleic anhydride, half ester of maleic anhydride, and carbon monoxide;
b) elastomers selected from natural rubber, polybutadiene, polyisoprene, random styrene butadiene rubber (SBR), polychloroprene, acrylonitrile butadiene, ethylene propylene co and terpolymers;
c) homo and copolymers of styrene, including styrene-butadiene-styrene linear and radial polymer, acrylonitrile butadiene styrene (ABS) and styrene acrylonitrile (SAN);
d) linear and branched polyether or polyester polyols;
e) crystalline and amorphous polyesters and polyamides;
f) alkyd resins, rosin acids or rosin esters, hydrocarbon resins produced from thermal or Friedel Crafts polymerization of cyclic diene monomers such as dicyclopentadiene, indene, cumene; and
g) hydrocarbon oils such as parafinic oil, naphthenic oil and hydrogenated naphthenic oil.
The polymer compositions of the present invention may be produced in any manner known to the art for combining polymers and dry or aqueous components.
The present invention further includes articles of manufacture produced from the polymer compositions of the present invention.
For use in semiconductive wire and cable applications, a typical formulation of the present invention comprises:
25-55%, by weight, of a composition comprising a carbon black and 0.5 to 10 parts, per 100 parts of carbon black, of at least one binder selected from at least one of the following groups:
i) an ethoxylated polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to ethoxylation, where the total number of ethylene oxide molecules per polyhydric alcohol is at least 3; preferably the polyhydric alcohol is selected from the group consisting of triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sucrose or a polyglyceride and/or the total number of ethylene oxide molecules per polyhydric alcohol varies from 3 to 500 and more preferably varies from 5 to 100;
ii) an alkyl carboxylic acid ester of an ethoxylated polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to ethoxylation, where the alkyl carboxylic acid has from 8 to 30 carbon atoms, and may be saturated or unsaturated, and further where the mono-ester functionality is at least 80% with the remainder being a di-ester functionality, and further where the number of ethylene oxide molecules per polyhydric alcohol ester is at least 3; preferably the polyhydric alcohol is selected from the group consisting of triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sucrose or a polyglyceride and/or the total number of ethylene oxide molecules per polyhydric alcohol ester varies from 3 to 500 and more preferably varies from 5 to 100;
iii) an alkyl carboxylic acid ester of a polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to esterification, where the alkyl carboxylic acid has from 8 to 30 carbon atoms, and may be saturated or unsaturated, and further where the mono-ester functionality is at least 80% with the remainder being a di-ester functionality; preferably the polyhydric alcohol is selected from the group consisting of: triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sorbitol and a polyglyceride;
iv) an ethoxylated alkyl carboxylic acid ester of a polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to esterification, where the alkyl carboxylic acid has from 8 to 30 carbon atoms, and may be saturated or unsaturated, and further where the mono-ester functionality is at least 80% with the remainder being a di-ester functionality, and further where the number of ethylene oxide molecules per polyhydric alcohol ester is at least 3; preferably the polyhydric alcohol is selected from the group consisting of: triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sorbitol and a polyglyceride and/or the total number of ethylene oxide molecules per polyhydric alcohol ester varies from 3 to 500 and more preferably varies from 5 to 100;
v) a polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer;
0 to 2%, by weight a stabilizer or antioxidant;
0 to 5%, by weight an organic peroxide, preferably dicumyl peroxide;
0 to 10%, by weight a vinyl silane;
the remainder being a polymer, or a blend of polymers, selected from the following group:
ethylene homopolymer;
ethylene copolymerized with one or more alpha olefins, such as propylene, butene, or hexene;
ethylene copolymerized with propylene and a diene monomer, preferably norbomene; and
ethylene copolymer with one or more monomers selected from vinyl acetate, acrylic acid, methacrylic acid, esters of acrylic or methacrylic acid containing 1 to 8 carbon atoms, maleic anhydride or a monoester derived from fumaric or maleic acid, vinyl chloride or vinylidene chloride.
The curable semi-conductive composition of the present invention may additionally include an additive polymer such as acrylonitrile butadiene elastomer containing 25-55%, by weight acrylonitrile.
For use as a masterbatch composition, a typical formulation of the present invention preferably comprises:
70-40%, by weight of an ethylene homopolymer or copolymer, where the comonomer is preferably selected from hexene, propene, butene, octene or vinyl acetate; and
30-60%, by weight, of a composition comprising a carbon black and 0.1 to 50%, preferably 1-20%, a binder component selected from at least one of the following groups:
i) an ethoxylated polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to ethoxylation, where the polyhydric alcohol is preferably selected from the group consisting of triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sucrose or a polyglyceride and where the total number of ethylene oxide molecules per polyhydric alcohol is at least 3, preferably varies from 3 to 500, more preferably varies from 5 to 100;
ii) an alkyl carboxylic acid ester of an ethoxylated polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to ethoxylation, where the alkyl carboxylic acid has from 8 to 30 carbon atoms, and may be saturated or unsaturated, and further where the mono-ester functionality is at least 80% with the remainder being a di-ester functionality, and further where the number of ethylene oxide molecules per polyhydric alcohol ester is at least 3, preferably varies from 3 to 500, more preferably varies from 5 to 100, and where the polyhydric alcohol is preferably selected from the group consisting of triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sucrose or a polyglyceride;
iii) an alkyl carboxylic acid ester of a polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to esterification, where the alkyl carboxylic acid has from 8 to 30 carbon atoms, and may be saturated or unsaturated, and further where the mono-ester functionality is at least 80% with the remainder being a di-ester functionality, and where the polyhydric alcohol is preferably selected from the group consisting of: triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sorbitol and a polyglyceride;
iv) an ethoxylated alkyl carboxylic acid ester of a polyhydric alcohol having at least 3 hydroxyl groups per molecule prior to esterification, where the alkyl carboxylic acid has from 8 to 30 carbon atoms, and may be saturated or unsaturated, and further where the mono-ester functionality is at least 80% with the remainder being a di-ester functionality, and further where the number of ethylene oxide molecules per polyhydric alcohol ester is at least 3, preferably varies from 3 to 500, more preferably varies from 5 to 100, and where the polyhydric alcohol is preferably selected from the group consisting of: triethanolamine, glycerol, pentaerythritol, sorbitol, sorbitan, sorbitol and a polyglyceride;
v) a polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer. Preferably, the polymer composition is polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene or a polyethylene wax. The masterbatch composition may additionally include antioxidants, peroxide decomposers, hindered amine light stabilizers, substituted benzophenone UV adsorbers or process aids.
The effectiveness and advantages of various aspects and embodiments of the present invention will be further illustrated by the following examples wherein the following testing procedures were utilized.
The following testing procedures were utilized in the determination and evaluation of the analytical properties of the carbon blacks utilized in the following examples. The DBP (dibutyl phthalate adsorption value) of the carbon blacks utilized in the examples, expressed as cubic centimeters DBP per 100 grams carbon black (cc/100 g), was determined according to the procedure set forth in ASTM D2414. The nitrogen surface area (N 2 SA) of the carbon blacks utilized in the examples, expressed as square meters per gram (m 2 /g), was determined according to ASTM test procedure D3037 Method A.
The carbon blacks pellets described in the following examples were evaluated utilizing the following testing procedures. The pellets were assessed for mass pellet strength using ASTM D 1937. Pellet attrition was evaluated using a modified version of ASTM D 4324, wherein the ASTM test procedure was modified to generate the level of dust after shaking samples for 5 minutes.
The moisture content of the pellets was determined by drying the sample to constant mass in an air circulating oven at 150° C. and then calculating moisture percentage by comparing the weight prior to drying to the weight after drying.
The polymer compositions, including the polymer masterbatch compositions, described in the following examples were evaluated utilizing the following test procedures.
Melt index was determined by ASTM D1238.
Pressure rise of the masterbatch compositions was determined by introducing a 325 mesh screen pack behind the breaker plate of a 1 inch single screw extruder fitted with a pressure transducer to measure the pressure change in the region of the screen pack.
Viscosity of the polymer compositions was measured utilizing a Carri-Med CS viscometer, produced and sold by TA Instruments of Wilmington, Del. at the temperature, and utilizing the shear rate specified in the particular example.
Triple roll mill passes were evaluated by passing the polymer compositions through a triple roll mill and recording the number of passes required to generate zero scratches on a Hegman gauge, and also recording the residual background "sand" value.
Dispersion of the diluted samples in the following examples was determed by diluting the masterbatch composition down to a loading of 2%, by weight, carbon black with the EVA resin in a Brabender mixer operating at 85° C. and 50 rpm. The mixing time was 2 minutes. Samples were then pressed between microscope slides and dispersion at 100×magnification was determined by the Cabot Corporation rating method wherein the number (1-6) refers to the size of the undispersed particles, with 1 being small and 6 being large; and the letter (A-E) refers to the number of particles per field of view, with A being 1-2 particles and E being greater than 50 particles. Lower numbers and earlier letters indicate better dispersion, with a 1A rating indicating good dispersion and a 6E rating indication poor dispersion.
In Examples 18-26, dispersion of the carbon black pellets was determined by measuring the number and size of surface imperfections in the tape formed from the compound incorporating the pellets using an optical microscope at 100×magnification and a reflected light source.
The polymer compositions were evaluated for strippability utilizing the following technique. The compositions containing 40% carbon black in the ethylene vinyl acetate resin were compounded in a Brabender mixer with 1% dicumyl peroxide while maintaining the mixing temperature below 150° C. The material was transferred to a heated hydraulic press (temperature 130° C.) and a plaque 1.2 mm thick produced. A 2 mm polyethylene plaque containing 1% dicumyl peroxide was produced in a similar manner. The two plaques were laminated together under a pressure of 100 psi and exposed to a curing cycle of 180° C. for 15 minutes. The laminate was allow to cool to ambient temperature under pressure. The delamination force under a peeling angle of 180 degrees and a separation speed of 3.94 inches/minute was recorded; the results provided are an average of 28 peel tests.
The modulus, tensile and elongation of the polymer compositions were measured by the procedure set forth in ASTM D 412.
The Shore A Hardness of the rubber compounds was determined according to the procedure set forth in ASTM D-2240-86.
The maximum torque was determined from the peak of the motor load versus time profile from the Brabender mixer.
The dump torque (Nm) was determined from the final torque value at the end of the mixing cycle.
The total energy (Nm) was determined by calculating from the area under the full mixing curve.
The MDR @ 170° C. T50 (m.m), and T90 (m.m) was determined according to the procedure set forth in ASTM 2084.
The Mooney viscosity (ML(1+4) @ 100° C. (MU)) was determined according to the procedure set forth in ASTM 1646.
The IRHD (hardness) was determined according to the procedure set forth in ASTM D1415.
The effectiveness and advantages of the present invention will be further illustrated by the following examples.
EXAMPLES 1-4
Examples 1-4 illustrate the use and advantages of carbon black compositions of the present invention, in comparison to conventional carbon black pellets, in polypropylene fiber applications.
Four carbon black pellet compositions, A, B, C and D were produced by introducing 400 grams (g) of a fluffy carbon black, identified herein as CB-1, having a DBP of 60 cc/100 g and a nitrogen surface area of 112 m 2 /g, into a batch pin pelletizer together with a solution containing 20 g of a binder and 300 g of water. The binder utilized in each pelleting composition was as shown in the Table below.
______________________________________Pellet Composition Binder______________________________________A waterB 5% sorbitan monostearate with 20 moles ethoxylateC 5% sorbitan monooleate with 5 moles ethoxylateD 5% sorbitan monooleate with 20 moles ethoxylate______________________________________
Carbon black pellet composition A was a control composition, carbon black pellet compositions B, C and D were carbon black compositions of the present invention.
The carbon black/binder mixture was agitated for 5 minutes with a rotor speed of 800 rpm. The resultant pellets were dried at 120° C. until the moisture content of the pellets was below 0.51. Pellet strength of each pellet composition was assessed qualitatively. The results are set forth in Table 1 below.
The carbon black pellets were combined with a polypropylene homopolymer of melt index 35 in a twin screw extruder to produce a masterbatch containing 35% by weight of the pelleted carbon black, the remainder being polypropylene and binder.
The polypropylene composition was introduced into a 1 inch single screw extruder until equilibrium pressure conditions. The masterbatch was introduced and the rate of pressure change recorded according to the procedure described above. The results were as shown in Table 1 below.
TABLE 1______________________________________Carbon Black Pellet pressure riseComposition pellet strength psi/g______________________________________A weak 4.86B strong 4.34C strong 4.25D strong 2.97______________________________________
These results indicate that carbon black compositions B, C and D of the present invention have improved pellet strength in comparison with the carbon black pellet composition A produced with pelletizing water only. In addition, the reduction in pressure build-up in masterbatch compositions containing carbon black compositions B, C and D of the present invention, in comparison to the masterbatch composition containing carbon black composition A, would translate to a reduction in the frequency of screen changes on a fiber production line, and therefore improved capacity and lower operating costs for the production line.
EXAMPLES 5-10
Examples 5-10 illustrate the use and advantages of carbon black compositions of the present invention, in comparison to conventional carbon black pellets, in polypropylene fiber applications.
Two carbon black pellet compositions, E and F were produced in a continuous process by combining a fluffy carbon black, identified herein as CB-2, having a DBPof 112 cc/100 g and an nitrogen surface area of 60 m 2 /g into a batch pin pelletizer together with a binder solution. The pellets were produced in a continuous pin pelletizer operating with rotor speed of 800 rpm to provide wet pellets with an average water content of 50%. The wet pellets were dried in a heated rotating drum to provide dry pellets with a moisture content below 0.6%.
The binder utilized in each pelleting composition was as shown in the Table below.
______________________________________Pellet Composition Binder______________________________________E waterF 2% sorbitan monooleate with 20 moles ethoxylate______________________________________
Four runs of carbon black pellet composition E, and two runs of carbon black pellet composition F were made. Carbon black pellet composition E was a control composition, and carbon black pellet compositions F was a carbon black composition of the present invention.
The pellets were assessed for mass pellet strength and pellet attrition using the procedures described above. In addition, the pellets were used to produce a masterbatch, as in examples 1-4, and the pressure rise determined as described above. The results are set forth in Table 2 below.
TABLE 2______________________________________ pellet pressureCarbon Black Pellet strength dust (%) riseComposition pounds 5 min. psi/g______________________________________E run 1 15 1.2 11.0E run 2 14 1.2 11.4E run 3 16 2.8 12.9E run 4 18 1.6 9.1F run 1 44 0.4 7.3F run 2 58 0.2 5.3______________________________________
These results illustrate the significant improvement in pellet strength and attrition resistance by incorporation of a binder of the type utilized in the present invention during the pelletizing process in preparing the carbon black pellet composition F of the present invention. Carbon black pellet composition F of the present invention also has improved dispersion, in comparison with a conventional water pelletized carbon black pellet composition E, as seen by the reduction in pressure build-up when extruded through a screen pack which would translate to improved output at lower operating cost.
EXAMPLES 11-14
Examples 11-14 illustrate the advantages of the carbon black pellet compositions of the present invention for use in polyurethane applications.
Two fluffy carbon blacks, identified herein as CB-3 and CB4, were pelletized to produce carbon black pellet compositions. Carbon blacks CB-3 and CB-4 had the combination of analytical properties set forth below:
______________________________________Fluffy Carbon Black DBP N.sub.2 SA______________________________________CB-3 112 cc/100 g 58 m.sup.2 /gCB-4 140 cc/100 g 68 m.sup.2 /g______________________________________
Four carbon black pellet compositions, G, H, I and J were produced in a continous process by combining the carbon blacks in a batch pin pelletizer together with a binder solution. The pellets were produced in a continuous pin pelletizer operating with rotor speed of 1000 rpm and dried in a heated rotating drum to provide dry pellets with a moisture content below 0.3%. The binder and carbon black utilized in each pelleting composition was as shown in the Table below.
______________________________________Pellet Composition Carbon Black Binder______________________________________G CB-3 waterH CB-3 2% sorbitan monooleate with 20 moles ethylene oxideI CB-4 waterJ CB-4 2% sorbitan monooleate with 20 moles ethylene oxide______________________________________
Carbon black pellet compositions G and I were control compositions, and carbon black pellet compositions H and J were carbon black compositions of the present invention.
The pellets were assessed for mass pellet strength using the procedures described above. The results were as follows:
______________________________________Pellet Composition mass pellet strength - pounds______________________________________G 14-16H 51I 10J 26______________________________________
The carbon black pellet compositions G, H, I and J were compounded into a polyether polyol, having a viscosity of 150 mPa.s at 25° C. and a hydroxyl content of 3.4%, to produce a 30% carbon black content paste. In addition, a polyether polyol compositon was produced by compounding carbon black CB4 into the polyol and adding 2% sorbitan monooleate with 20 moles ethylene oxide binder directly to the polyol. Each compounding operation involved pre-dispersion under a high shear, Dispermat, mixer for 5 minutes at a speed of 2000 rpm.
The paste was then transferred to a triple roll mill for the final size reduction process. The number of passes through the triple roll mill required to generate zero scratches on a Hegman gauge were noted together with the residual background "sand" value. The paste was then diluted with further polyol to produce a 15% carbon black loaded sample and the viscosity measured on a Carri-Med CS viscometer at a shear rate of 300 s-1. The results were as shown in Table 3:
TABLE 3______________________________________ Number viscosityCarbon Black of passes "sand" shear stressPellet Composition triple roll (microns) (dyne/cm.sup.2)______________________________________G 5 37 2800H 5 19 1900I 6 17 1860J 5 17 1400CB-4, with Binder Added 7 26 1790Directly to Polyol______________________________________
The above experiments illustrate the improved pellet strength and dispersion, and reduced compound viscosity, of the carbon black pellet compositions H and J of the present invention in comparison to use of carbon black compositions G and H pelletized with water only. The data also demonstrates the benefits of incorporating a binder directly onto the carbon black (pretreating the carbon black with a binder) in comparison to adding the binder to the polymer system.
This example is representative for polyurethane foam and sealant applications and demonstrates improvement in dispersion and rheology of the polymer compositons incorporating carbon black compositions of the present invention. The reduction in viscosity would allow use of low pressure to apply the polyurethane sealant in either automotive direct glazing or window double/triple glazing unit operations.
EXAMPLE 15-17
This example illustrates the advantages of using the carbon black compositions of the present invention in ink formulations.
Carbon black compositions G and H from Examples 11-14 were evaluated in a typical oil based gloss ink using the same process as outlined in examples 11-14. In this case the mill base and letdown system were an oil (McGee 47) and a heatset resin (Lawter Vehicle 3477) used in a ratio of 1:9 by weight. A third ink formulation was produced by adding sorbitan monooleate with 20 moles of ethylene oxide, to a composition of Carbon Black Composition G and the oil utilized in the compounding process.
The compounding operation involved pre-dispersion under a high shear, Dispermat, mixer for 5 minutes at a speed of 2000 rpm. The paste was then transferred to a triple roll mill for the final size reduction process. The number of passes through the triple roll mill required to generate zero scratches on a Hegman gauge were noted together with the residual background "sand" value. The paste was then diluted with further polyol to produce a 15% carbon black loaded sample and the viscosity measured on a Carri-Med CS viscometer at a shear rate of 300 s-1. The results were as shown in Table 4:
TABLE 4______________________________________Ink Formulation Number viscosityCarbon Black of passes "sand" shear stressPellet Composition triple roll (microns) (dyne/cm.sup.2)______________________________________G 5 18 330H 4 15 165G, with binder added to oil 4 17 240______________________________________
These results demonstrate the improved dispersion and reduced viscosity obtained when the binder composition utilized in the carbon black compositions of the present invention is either incorporated onto the carbon black or with direct addition to the ink vehicle. Incorporating the binder onto the carbon black exhibits the most significant improvement. The binder would potentially help to reduce the mixing time for the ink and the reduced viscosity and improved dispersion would help to reduce wear in the application process.
EXAMPLE 18-26
Examples 18-26 illustrate the use of carbon black compositions of the present invention in semiconductive compounds.
Three carbon black pellet compositions, K, L and M were produced by combining a fluffy carbon black, identified herein as CB-5, having a DBP of 140 cc/100 g and a nitrogen surface area of 70 m 2 /g, in a batch pin pelletizer together with a binder solution. The carbon black was combined with various binder solutions in a continuous pin pelletizer operating at 1050 rpm to provide wet pellets with levels of sorbitan monooleate with 20 moles ethylene oxide in amounts varying from 0 to 4%. The pellets were dried in a heated rotating drum to provide dry pellets with moisture content below 0.6%. The binder utilized in each pelleting composition was as shown in the Table below.
______________________________________Pellet Composition Binder______________________________________K waterL 2% sorbitan monooleate 20 moles ethylene oxideM 4% sorbitan monooleate 20 moles ethylene oxide______________________________________
The carbon blacks were compounded into ethylene vinyl acetate resin (40% vinyl acetate content, melt index 3), using a twin screw extruder, to produce a 40% carbon black loaded compound. The compound was subsequently extruded to form a tape and the level of carbon black dispersion assessed by measuring the number and size of surface imperfections using an optical microscope (magnification 100×) with a reflected light source, by the procedures described herein. The results are shown below:
______________________________________EVA CompositionCarbon Black Composition area of un-dispersed carbon black______________________________________K 0.0470%L 0.0056%M 0.0067%______________________________________
The reduction in undispersed carbon black would be seen in the final cable compound as an improvement in surface smoothness of the extruded cable. Reduction in surface imperfections of the semi-conductive insulation shield is known to reduce the frequency of electrical breakdown due to tree growth.
The EVA compositions containing carbon black compositions K and L disclosed above were evaluated for strippability onto a polyethylene substrate using the following technique: The compounds containing 40% carbon black in the ethylene vinyl acetate resin were compounded in a Brabender mixer with 1% dicumyl peroxide while maintaining the mixing temperature below 150° C. The material was transferred to a heated hydraulic press (temperature 130° C.) and a plaque 1.2 mm thick produced. A 2 mm polyethylene plaque containing 1% dicumyl peroxide was produced in a similar manner. The two plaques were laminated together under a pressure of 100 psi and exposed to a curing cycle of 180° C. for 15 minutes. The laminate was allow to cool to ambient temperature under pressure. The delamination force under a peeling angle of 180 degrees and a separation speed of 3.94 inches/minute was recorded; the results are an average of 28 peel tests:
______________________________________EVA CompositionCarbon Black Composition lb per 0.5 inch______________________________________K 6.55 +/- 0.46L 5.12 +/- 0.44______________________________________
The data shows a reduction in strip force required to remove the semi-conductive shield compound from the insulation layer. This is important in cable splicing operations or in making terminal connections. The lower strip force will result in a faster operation and minimise voids/imperfections from high strip force systems and hence reduce the potential for electrical breakdown in use.
EXAMPLES 27-37
Examples 27-37 illustrate the use of carbon black compositions in polyolefin masterbatch compositions.
Four carbon blacks were utilized to produce carbon black compositions of the present invention and control carbon black compositions. The carbon blacks utilized are designated herein as CB-6, CB-7, CB-8 and CB-9 and had the combination of analytical properties set forth below:
______________________________________ DBP N.sub.2 SACarbon Black cc/100 g m.sup.2 /g______________________________________CB-6 140 68CB-7 135 180CB-8 136 120CB-9 168 53______________________________________
The carbon blacks were were combined with either water or an aqueous solution of sorbitan monooleate with 20 moles of ethylene oxide in a continuous pelletizer operating with a rotor speed of 1000 rpm to produce wet pellets. The pellets were dried in an air circulating oven operating at 120° C. to produce dry pellets with moisture content below 0.4%. In all 11 different carbon black compositions were produced as shown below:
______________________________________Composition Carbon Black Binder______________________________________N CB-6 WaterO CB-6 0.5% sorbitan monooleate with 20 moles ethylene oxideP CB-6 1.0% sorbitan monooleate with 20 moles ethylene oxideQ CB-6 2.0% sorbitan monooleate with 20 moles ethylene oxideR CB-6 4.0% sorbitan monooleate with 20 moles ethylene oxideS CB-7 WaterT CB-7 2.0% sorbitan monooleate with 20 moles ethylene oxideU CB-8 WaterV CB-8 2.0% sorbitan monooleate with 20 moles ethylene oxideW CB-9 WaterX CB-9 2.0% sorbitan monooleate with 20 moles ethylene oxide______________________________________
The carbon black compositions were assessed for pellet strength and attrition resistance using the procedures described herein. The results are shown below in Table 5.
TABLE 5______________________________________ pellet strength dust (%)Composition (pounds) 5' 10'______________________________________N 25 4.4 5.0O 61 0.5 1.1P 49 0.6 1.5Q 55 0.2 0.4R 50 0.8 0.6S 44 3.6 15.0T 83 0.3 1.5U 62 0.8 5.2V 119 0.2 0.4W 17 2.5 4.8X 21 1.2 2.4______________________________________
Each of the carbon black compositions was identically compounded into low density polyethylene having a melt index of 26 using a Brabender mixer to produce a masterbatch containing 40% carbon black. The viscosity of the masterbatch was measured at 130° C. and a shear rate of 50 s-1. The results are set forth in Table 6 below.
TABLE 6______________________________________Composition Viscosity (Pa.s)______________________________________N 5116O 4045P 3389Q 2873R 2536S 4329T 3695U 4591V 3804W 5487X 4373______________________________________
The data in Table 6 illustrates the reduction in viscosity obtained by using a carbon black treated with a binder composition of the present invention. This reduction in viscosity would facilitate ease of dispersion of the masterbatch into further polyethylene in a typical extrusion blown film or profile extrusion application; and also improve output efficiency. One would also expect an improvement in carbon black dispersion which would also provide an improvement in pigmentary effieciency, UV protection and mechanical performance (e.g. tensile or impact strength).
EXAMPLES 38-49
This example illustrates the use of different binder compositions to produce carbon black compositions of the present invention, and the advantages of using the carbon black compositions of the present invention in ethyl vinyl acetate (EVA) applications.
Eleven carbon black compositions, HH, II, JJ, KK, LL, MM, NN, OO, PP, QQ and RR were produced by combining 400 g of a fluffy carbon black having a DBP of 128 cc /100 g and a nitrogen surface area of 68 m2/g, designated herein as CB-12, together with 8 g of binder dissolved in 500 g of water, in a batch pin pelletizer. The binder utilized in each composition was as follows:
______________________________________Composition Binder______________________________________HH waterII sucrose monoester of tallow fatty acidJJ sucrose monostearateKK sucrose distearateLL ethoxylated glycerideMM ethoxylated triglycerideNN SYNPERONIC PE/L61 surfactantOO SYNPERONIC PE/85 surfactantPP SYNPERONIC PE/F127E surfactantQQ SYNPERONIC PE/38E surfactantRR SYNPERONIC PE/108E surfactant______________________________________ *SYNPERONIC is a trade name for surfactants produced and sold by ICI Corporation and comprise ethylene oxide propylene oxide copolymers.
The mix was agitated at 800 rpm for 2 minutes to produce a pelletized carbon black. The carbon black pellets were dried at 125° C. until the moisture content was below 1%.
Mass pellet strength of the carbon black compositions was determined according to the procedures described herein. The results are set forth in Table 7 below.
Each of the carbon black compositions was combined with an ethylene vinyl acetate copolymer containing 40% vinyl acetate and a melt index of 3 in a Brabender mixer conditioned at 65° C. The compound was masticated for 6 minutes at 50 rpm to produce a fully dispersed compound containing 40% carbon black. These compounds were assessed for melt index (MI) at 190° C. using a 21.6 kg load, according to the procedures described herein. The results are also set forth in Table 9 below, which also shows the HLB of each binder.
TABLE 7______________________________________ Disp. Of MPS MI Dil.Comp Binder HLB (pounds) (g/10 m) Samples______________________________________HH water 1.6 6.58 2CII sucrose monoester 14.5 15.2 9.86 1C of tallow fatty acidJJ sucrose 15.0 15.8 6.88 1B monostearateKK sucrose distearate 12.0 22.8 9.18 1BLL ethoxylate glyceride 15.7 4.9 8.84 1CMM ethoxylated 14.4 6.7 14.00 1D triglycerideNN SYNPERONIC 16.0 9.4 10.34 1B PE/L61 surfactantOO SYNPERONIC 16.0 2.9 10.55 1C PE/85 surfactantPP SYNPERONIC 22.0 2.6 6.70 1E PE/F127E surfactantQQ SYNPERONIC 30.5 3.1 7.90 1B PE/38E surfactantRR SYNPERONIC 27.0 3.5 7.97 1E PE/108E surfactant______________________________________ Comp. = Composition; Disp. Of Dil. Samples = Dispersion of Diluted Samples.
These examples illustrate the improvement in dispersion quality and reduction in viscosity with improved pellet handling qualities, in a commercial system. These results would relate to shorter mixing cycles and improved extrusion characteristics.
EXAMPLES 50-52
These examples illustrates the production of carbon black compositions of the present invention, and the advantages of using the carbon black compositions of the present invention in ethyl vinyl acetate (EVA) applications.
Three carbon black compositions, SS, TT and UU were produced by combining a fluffy carbon black with a nitrogen surface area of 70 m2/g and a DBP of 140 cc/100 g of carbon black, designated herein as CB-13, with a binder solution containing sorbitan monooleate in a continuous pin pelletiser operating at 1050 rpm to provide wet pellets. The resulting pellets containing either 0%, 2% or 4% binder were dried in a heated rotating drum to provide dry pellets with moisture contents below 0.6%. The percentage of the binder utilized in each composition was as follows:
______________________________________Composition Binder (% by weight)______________________________________SS 0.0% sorbitan monooleate (water)TT 2% sorbitan monooleateUU 2% sorbitan monooleate______________________________________
The treated carbon blacks where compounded into various polymers using a Brabender mixer operating at 50 rpm and with an initial chamber temperature of 85° C. The mixing cycle time was 6 minutes. The compounds were assessed for melt viscosity at 130° C. and a shear rate of 50s-1.
______________________________________ Viscosity (Pa.s) percent binderpolymer 0 2 4______________________________________ethylene vinyl acetate 8155 3210 3080(40% vinyl acetate, MI 3.0)ethylene vinyl acetate 7368 3564 3498(18% vinyl acetate, MI 2.5)ethylene ethyl acrylate 7018 3170 2558(18% ethylacrylate, MI 6.0)______________________________________
The data illustrates a significant reduction in melt viscosity when using the designated binder, this would reflect in a reduction in die head pressure during the cable fabrication process. Visually this would be seen as an improvement is smoothness of the compound extrudate and also an increase in output rate.
The polymers utilized represent typical types of polymer used in wire and cable formulations used for conductor and semi-conductive shield applications. The polymers containing either 18% vinyl acetate or ethyl acrylate are typically used in conductor or bonded semi-conductive shield applications while the polymer containing 40% vinyl acetate is more suitable for a strippable semi-conductive shield type product.
It should be clearly understood that the forms of the present invention herein described are illustrative only and are not intended to limit the scope of the invention. | Carbon black compositions comprising ethoxylated esters or polyethers and carbon black. The compositions may be produced by incorporating ethoxylated esters or polyethers onto fluffy carbon black in a pelletizing process to produce free flowing, low dust, attrition resistant carbon black pellets which are easily dispersible in most polymeric systems and impart to polymer compositions enhanced rheological and mechanical properties. The polymeric compositions have particular utility as semiconductive compositions or masterbatch compositions. | 8 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The invention relates to a rotatable apparatus, and more particularly to a rotatable apparatus which utilizes a gear to cooperate with a rack, so as to prevent a main body of the rotatable apparatus from colliding with a base during the rotation.
[0003] 2. Description of the Prior Art
[0004] The horizontal length of the conventional liquid crystal display (LCD) is usually longer than the vertical length, such that the user can obtain a broader view in horizontal direction. Recently, as technology has been developed gradually, the personal computer (PC) has more and more functions. Consequently, rotatable LCD has been developed for the user to operate these various functions. In other words, the user may rotate the LCD by 90 degrees based on individual needs, so as to obtain a broader view in the vertical direction.
[0005] In the prior art, when the user wants to rotate an LCD from horizontal to vertical, he/she needs to lift the LCD by a specific distance to prevent the LCD from colliding with a plane or a base during the rotation. Afterward, the LCD is rotated to a fixed position. According to the aforesaid mechanism of the convention LCD, it is not very convenient for the user to operate, and the design is also more complicated.
[0006] Therefore, the scope of the present invention is to provide a rotatable apparatus to solve the aforesaid problem.
SUMMARY OF THE INVENTION
[0007] A scope of the invention is to provide a rotatable apparatus which utilizes a gear to cooperate with a rack, such that a main body of the rotatable apparatus is capable of moving upward and downward along the rack during the rotation, so as to prevent the main body from colliding with a base.
[0008] According to a preferred embodiment, the rotatable apparatus of the invention comprises a base, a holder, a rack, an auxiliary fastening member, a gear and a main body. The holder has a first end and a second end, and the holder is mounted onto the base via the first end. The rack is mounted onto the second end of the holder; it has a front side and a back side, wherein a plurality of teeth are provided on the front side, and a guide rail is provided on the back side. The auxiliary fastening member has a guide groove cooperating with the guide rail of the rack, such that the auxiliary fastening member is capable of moving upward and downward along the rack. The auxiliary fastening member also has a protrusion which protrudes from the guide groove. The gear has a first side and a second side. The first side of the gear is rotatably attached to the protrusion of the auxiliary fastening member, and the gear is meshed with the teeth of the rack. The main body is attached to the second side of the gear.
[0009] In the aforesaid preferred embodiment, the rotation of the main body together with the gear is actuated by applying an external force on the main body to make the gear rotate relative to the teeth of the rack; at the same time, the guide groove of the auxiliary fastening member moves relative to the guide rail of the rack. Consequently, the main body rotates and moves relative to the base. In other words, when the user wants to rotate the main body of the rotatable apparatus by a specific angle, the main body is capable of moving upward and downward along the rack due to the cooperation between the gear and the rack. When the base of the rotatable apparatus is placed on a plane, and the horizontal length of the main body is longer than the vertical length, the main body is capable of rotating and moving upward along the rack, such that the user can rotate the main body by a specific angle, and the invention can prevent the main body from colliding with the base.
[0010] The advantage and spirit of the invention may be understood by the following recitations together with the appended drawings.
BRIEF DESCRIPTION OF THE APPENDED DRAWINGS
[0011] FIG. 1A is a back perspective view illustrating the rotatable apparatus according to a first preferred embodiment of the invention.
[0012] FIG. 1B is a back perspective view illustrating the main body (shown in FIG. 1A ) being rotated by 90 degrees.
[0013] FIG. 2 is a schematic diagram illustrating the rotation of the rotatable apparatus shown in FIG. 1A .
DETAILED DESCRIPTION OF THE INVENTION
[0014] Referring to FIGS. 1A and 1B , FIG. 1A is a back perspective view illustrating the rotatable apparatus 10 according to a first preferred embodiment of the invention. FIG. 1B is a back perspective view illustrating the main body 22 (shown in FIG. 1A ) being rotated by 90 degrees. As shown in FIG. 1A , the rotatable apparatus 10 comprises a base 12 , a holder 14 , a rack 16 , an auxiliary fastening member 18 , a gear 20 , and a main body 22 . The main body 22 may be a display device. In this embodiment, the main body 22 is an LCD. The holder 14 has a first end 140 and a second end 142 . The holder 14 is mounted onto the base 12 via the first end 140 . The rack 16 is mounted onto the second end 142 of the holder 14 and has a front side 160 and a back side 162 . A plurality of teeth are provided on the front side 160 , and a guide rail is provided on the back side 162 . In another preferred embodiment, the holder 14 and the rack 16 are monolithically formed.
[0015] As shown in FIG. 1B , the auxiliary fastening member 18 has a guide groove 180 cooperating with the guide rail 162 of the rack 16 , such that the auxiliary fastening member 18 is capable of moving upward and downward along the rack 16 . The auxiliary fastening member 18 also has a protrusion 182 which protrudes from the guide groove 180 . The gear 20 has a first side and a second side. The first side of the gear is rotatably attached to the protrusion 182 of the auxiliary fastening member 18 , and the gear 20 is meshed with the teeth of the rack 16 . The main body 22 is attached to the second side of the gear 20 .
[0016] In the aforesaid embodiment, the rotation of the main body 22 together with the gear 20 is actuated by applying an external force on the main body 22 to make the gear 20 rotate relative to the teeth of the rack 16 ; at the same time, the guide groove 180 of the auxiliary fastening member 18 moves relative to the guide rail 162 of the rack 16 . In other words, when the user wants to rotate the main body 22 of the rotatable apparatus 10 by a specific angle, the main body 22 is capable of moving upward and downward along the rack 16 due to the cooperation between the gear 20 and the rack 16 , as shown in FIGS. 1A and 1B . When the main body 22 rotates from the state shown in FIG. 1A to the state shown in FIG. 1B , the main body 22 moves upward along the rack 16 , so as to prevent the main body 22 from colliding with the base 12 or the plane where the base 12 is placed. When the main body 22 rotates from the state shown in FIG. 1B to the state shown in FIG. 1A , the main body 22 moves downward along the rack 16 . Furthermore, the gear 20 is rotatably attached to the protrusion 182 of the auxiliary fastening member 18 by a hinge (not shown in the figures), such that the main body 22 can be rotataed by a specific angle and be fixed at the specific angle.
[0017] In the aforesaid embodiment, the rotatable apparatus 10 further comprises a resilient member 24 , as shown in FIG. 1A . The resilient member 24 is positioned between the rack 16 and the auxiliary fastening member 18 , so as to assist the gear 20 in rotating relative to the rack 16 . Accordingly, it is easier for the user to rotate the main body 22 . The resilient member 24 may be a line spring or the like.
[0018] Referring to FIG. 2 , FIG. 2 is a schematic diagram illustrating the rotation of the rotatable apparatus 10 shown in FIG. 1A . As shown in FIG. 2 , to prevent the main body 22 from colliding with the base 12 or the plane where the base 12 is placed, the rotatable apparatus 10 can be further designed to satisfy an inequality (equation 1) as follows:
[0000] R ×θ>√{square root over (L 2 +W 2 )} −W. Equation 1
[0019] In equation 1, L represents half of the length of the main body 22 , W represents half of the width of the main body 22 , R represents the radius of the gear 20 , and θ represents a desired angle with which the main body 22 is rotated. Furthermore, R×θ represents the distance which the main body 22 moves up while the main body 22 is rotated by the angle θ.
[0020] Compared to the prior art, when the user wants to rotate the main body 22 of the rotatable apparatus 10 by a specific angle θ, the main body 22 is capable of moving upward along the rack 16 due to the cooperation between the gear 20 and the rack 16 , so as to prevent the main body 22 from colliding with the base 12 or the plane where the base 12 is placed. Accordingly, the invention simplifies the complicated structure of the prior art, and it is more convenient and practical for the user.
[0021] With the example and explanations above, the features and spirits of the invention will be hopefully well described. Those skilled in the art will readily observe that numerous modifications and alterations of the device may be made while retaining the teaching of the invention. Accordingly, the above disclosure should be construed as limited only by the metes and bounds of the appended claims. | The invention discloses a rotatable apparatus including a base and a main body attached thereon. The rotatable apparatus utilizes a gear cooperating with a rack to make the main body rotate and further move along the rack during the rotation of the main body, so as to prevent the main body from colliding with the base. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a method for monitoring a hearing device comprising an electro-acoustic output transducer worn at a user's ear or in a user's ear canal. The invention also relates to such a hearing device having self-monitoring function. According to another aspect, the invention relates to a method for adjusting a behind-the-ear hearing device and also to such an adjustable behind-the-ear hearing device.
2. Description of Related Art
Ear-worn hearing devices, such as hearing aids (which have an integrated microphone system) or wireless systems (which comprise a remote audio signal source, such as a remote microphone, and an ear-piece receiver) usually comprise an electro-acoustic output transducer (loudspeaker) which is located in or at least close to the ear canal. This applies particularly to in-the-ear (ITE) or completely in-the-canal (CIC) systems. However, also behind-the-ear (BTE) systems have a tubing extending from the loudspeaker (which in this case is located behind the ear) into the ear canal. A frequent problem of such ear-worn hearing devices is that the performance of the loudspeaker may be significantly deteriorated due to blocking with ear wax (cerumen) from the ear canal.
It is known to use special wax filters in order to protect the loudspeaker for preventing the loudspeaker from getting blocked by wax. However, none of these wax filters is capable of providing for a full protection from wax blocking.
If the loudspeaker performance is deteriorated by wax blocking, the user may not immediately notice this. This may be particularly true for systems used by children, since they usually have much more difficulty in noticing and communicating problems regarding the hearing device.
EP 1 276 349 B1 relates to a hearing aid with a self-test capability, wherein the hearing-aid automatically undergoes a self-test procedure for determining whether the hearing aid comprises a defect. The hearing aid is capable to indicate the presence and the type of defect to the user, for example, on the display of a programming device connected to the hearing aid for service purposes. During the self-test procedure it is checked whether each of the hearing aid microphones produces a signal. From the absence of such signal it is concluded that the input port to the respective microphone has been occluded by ear wax.
It is one object of the invention to provide for a method for monitoring a hearing device comprising an electio-acoustic output transducer worn at a user's ear or in a user's ear canal, by which method it should be enabled to monitor the acoustic performance of the output transducer in a simple and efficient manner. In addition, such hearing device having a monitoring function should be provided.
It is a further object of the invention to provide for a method for adjusting a behind-the-ear hearing device comprising an electroacoustic output transducer connected to a tubing ( 26 ) extending into a user's ear canal. In addition, such a hearing device should be provided.
SUMMARY OF THE INVENTION
According to a first aspect of the invention there is provided a method comprising the steps of measuring an electrical impedance of said output transducer; analyzing the measured electrical impedance of the output transducer in order to evaluate a status of the output transducer and/or an acoustical system cooperating with the output transducer; and outputting a status signal representative of the status of the output transducer and/or the acoustical system cooperating with said output transducer. Also, in accordance with first aspect, a hearing device is provided with self-monitoring function, comprising an electroacoustic output transducer to be worn at or in a user's ear canal, means for measuring an electrical impedance of said output transducer, means for analyzing said measured electrical impedance of said output transducer in order to evaluate the status of the output transducer and/or an acoustical system cooperating with the output transducer, and means for outputting a status signal representative of the status of the output transducer and/or the acoustical system cooperating with said output transducer.
According to a second aspect of the invention there is provided a method for adjusting a behind-the-ear hearing device having an electroacoustic output transducer connected to a tubing extending into a user's ear canal, involving the steps of measuring an electrical impedance of said output transducer, analyzing the measured electrical impedance of the output transducer to determine at least one parameter selected from a length of the tubing and a diameter of the tubing, and adjusting operation parameters of the hearing device according to the at least one parameter determined to optimize an acoustical performance of said hearing device. Also, in accordance with second aspect, a hearing device is provided having an electroacoustic output transducer connected to a tubing adapted for extending into a user's ear canal, means for measuring an electrical impedance of the output transducer, means for analyzing the measured electrical impedance of the output transducer in order to determine at least one parameter selected from a length of said tubing and a diameter of said tubing, and means for providing a signal representative of the at least one parameter for adjusting operation parameters of the hearing device to optimize acoustical performance of the hearing device.
The invention is generally beneficial in that, by measuring and analyzing the electrical impedance of the output transducer, the status of the output transducer and/or of an acoustical system cooperating with the output transducer, such as a tubing of a BTE hearing device, may be evaluated in a simple and efficient manner. According to one aspect, thereby it is enabled to automatically and immediately recognize when the output transducer or an acoustical system cooperating with the output transducer is blocked by ear wax or when the output transducer is damaged. According to another aspect, thereby the length and/or diameter of the tubing of a BTE hearing device can be automatically determined in a simple manner, and the thus determined length and/or diameter of the tubing can be used to optimize the operation parameters of the hearing device according the determined length and/or diameter of the tubing in order to optimize the acoustical performance of the hearing device.
These and further objects, features and advantages of the present invention will become apparent from the following description when taken in connection with the accompanying drawings which, for purposes of illustration only, show several embodiments in accordance with the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram of a first embodiment of a hearing device according to the invention;
FIG. 2 is a block diagram of a second embodiment of a hearing device according to the invention;
FIG. 3 is an example of how the electrical impedance of the output transducer of a hearing device according to the invention may be measured;
FIG. 4 shows schematically the set-up for the test measurements of FIGS. 5 and 6 ;
FIG. 5 is a plot of the voltage measured at the resistor of FIG. 4 as a function of frequency obtained in test measurements with the set-up of FIG. 4 for different obstruction levels of the loudspeaker; and
FIG. 6 is a plot of the acoustic output level curve of the loudspeaker measured with the set-up of FIG. 4 in a 1.4 cc coupler for different loudspeaker obstruction levels.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is a block diagram of a first example of a hearing device for which the invention can be used, wherein the hearing device is a hearing aid 10 which comprises a microphone arrangement 12 (which may consist of two spaced-apart microphones for enabling acoustic beam forming capability), a central processing unit 14 for processing the audio signals produced by the microphone arrangement 12 , a power amplifier 16 for amplifying the processed audio signals from the central processing unit 14 , and a loudspeaker 18 for stimulating the user's hearing with the processed amplified audio signals from the microphone arrangement 12 . The hearing aid 10 could be of the ITE or CIC type, in which cases the loudspeaker 18 would be located in the ear canal of the user.
The loudspeaker 18 may cooperate with an acoustical system 20 located downstream of the loudspeaker 18 , which may comprise, for example, a wax filter 22 , acoustical filters 24 and some kind of tubing 26 . Such tubing 26 will have a significant length if the hearing aid 10 is of the BTE type, in which case the loudspeaker, together with the hearing aid 10 , will be located behind the ear, while the tubing 26 extends into the ear canal.
FIG. 2 is a block diagram of an alternative embodiment of a hearing device, wherein the hearing device is a wireless ear-piece 110 which represents the receiver unit of a wireless audio system and which receives audio signals from a remote transmission unit 143 via a wireless audio link 145 .
The transmission unit comprises a microphone arrangement 144 (which may consist of two or more spaced-apart microphones for enabling acoustic beam forming capability), an audio signal processing unit 146 for processing the audio signals from the microphone arrangement 144 , a transmitter 148 and an antenna 150 . Usually the audio link 145 will be an FM link.
The receiver unit 110 comprises an antenna 152 , a receiver 154 for recovering the audio signals from the signal received at the antenna 152 , a central processing unit 114 for processing the received audio signals, a power amplifier 116 for amplifying the processed audio signals, and a loudspeaker 118 . As in the example of FIG. 1 , the loudspeaker 118 may cooperate with an acoustical system located downstream of the loudspeaker 118 , for example, a wax filter 22 . As in the case of FIG. 1 , the loudspeaker 118 will be located in or at the ear canal. The loudspeaker 118 may be integrated into the receiver unit 110 , as shown in FIG. 2 , or it may be mechanically and electrically connected thereto.
Both in the embodiment of FIG. 1 and the embodiment of FIG. 2 an analyzer unit 30 is provided which may be activated by the central processing unit 14 , 114 and which serves to measure the electrical impedance as a function of frequency of the loudspeaker 18 , 118 and to provide the corresponding measurement result to the central processing unit 14 , 114 in order to enable the central processing 14 , 114 to produce a status signal representative of the status of the loudspeaker 18 , 118 and/or the acoustical system 20 , 120 cooperating with the loudspeaker 18 , 118 . The measured electrical impedance as a function of frequency of the loudspeaker 18 , 118 provided by the analyzer unit 30 is evaluated in the central processing unit 14 , 114 in order to generate the respective status signal.
According to one embodiment, an acoustic alarm signal may be produced by the central processing unit 14 , 114 with the help of the loudspeaker 18 , 118 in order to provide the user with an acoustic alarm. Such acoustic alarm may comprise an alarm tone and/or a voice message.
According to an alternative embodiment, the status signal may be transmitted from the central processing unit 14 , 114 to a remote device 32 via a wireless link 34 which possibly is an inductive link utilizing an inductive antenna 38 included in the remote device 32 and an inductive antenna 36 connected to the central processing unit 14 , 114 . The remote device 32 further includes a signal processing unit 40 for processing the signals received by the antenna 38 and a display 40 for displaying the alarm signal received via the inductive link 34 , which in this embodiment will be an optical alarm signal rather than an acoustic alarm signal.
The remote device 32 could be used by the user of the hearing device 10 , 110 , or, in particular in the case of FIG. 2 , it could be used by the person using the transmission unit 143 , for example, the teacher in a classroom of pupils using the receiver unit 110 . In this case, the remote device 32 could be functionally integrated within the transmission unit 143 .
The inductive link 34 may be bidirectional link. In this case, transmission of the status signal from the hearing device 10 , 110 may be initiated by receipt of a polling command at the hearing device 10 , 110 transmitted from the remote device 32 . Thereby, for example, the teacher in the classroom may check whether the loudspeaker 118 used by each pupil works properly. In addition, the bidirectional link 34 may serve to monitor also other components of the system, such as battery status, status of the audio link 145 , etc.
According to an alternative embodiment, rather than being initiated by receipt of a polling signal, measurement of the electrical impedance of the loudspeaker 18 , 118 and the subsequent analysis of the measured electrical impedance will be repeated in regular intervals.
Preferably, the measured electrical impedance as a function of frequency will be analyzed by comparing the measured electrical impedance to reference data stored in the hearing device 10 , 110 . Such reference data may be generated in the manufacturing process of the hearing device 10 , 110 . Preferably the resonance frequency and/or the quality factor of the loudspeaker 18 , 118 are analyzed by measuring the electrical impedance as a function of frequency. Preferably the status signal will be provided as all alarm signal if the difference between the actually measured electrical impedance data and the stored reference data exceeds a predetermined threshold, wherein the magnitude of the difference between the measured data and the stored reference data may be taken as a measure of the degree of disturbance of the loudspeaker 18 , 118 , for example of the degree of the mechanical obstruction of the loudspeaker 18 , 118 by ear wax.
The evaluation of the status of loudspeaker 18 , 118 and/or the acoustical system 20 , 120 cooperating with the loudspeaker 18 , 118 may include an evaluation of whether the loudspeaker 18 , 118 is working according to specification.
Preferably such evaluation will include a check of whether the loudspeaker is still working properly or whether it is out of order.
In the case of a BTE hearing aid the system will include a tubing 26 extending from the loudspeaker 18 into the user's ear canal. The length and/or the diameter of such tubing 26 can be selected individually by the fitter. If the length/diameter of the tubing 26 is known, the acoustical performance of the BTE hearing aid can be optimized. Due to the acoustical coupling of the tubing 26 to the loudspeaker 18 it is possible to estimate from the measured electrical impedance of the loudspeaker 18 the length/diameter of the tubing 26 used for each BTE hearing aid 10 . With this knowledge, it is possible to optimize the acoustical performance of the hearing device automatically by optimizing the setting the operation parameters of the hearing aid according to the determined length/diameter of the tubing 26 , eliminating therefore the need for the fitter to enter the length/diameter data into the computer (not shown) for a fine tuning procedure, thus saving time and avoiding possible errors. To this end, the central processing unit 14 of the hearing aid 10 may provide for a signal representative of the determined length/diameter of the tubing 26 , which signal is supplied to the fitting computer.
In addition to evaluating the length/diameter of the tubing 26 from the measured electrical impedance of the loudspeaker 18 it is also possible to evaluate whether the end of the tubing 26 suffers from a mechanical obstruction, for example by ear wax.
An example of how the measurement of the electrical impedance of the loudspeaker 18 , 118 can be done by the analyzer unit 30 as given in FIG. 3 . According to FIG. 3 , the voltage on a serial resistor 60 located between the ground and the loudspeaker 18 is measured by voltmeter 62 . For such an arrangement the voltage curve (i.e. the voltage as a function of frequency) on the resistor 60 becomes the image of the impedance curve of the loudspeaker 18 . The electric impedance—and hence the voltage measured by the voltmeter 62 —will be different depending on whether the loudspeaker is open or blocked. Even if the loudspeaker 18 is only partly blocked (resulting in a relatively small acoustic attenuation), a change in voltage will be observed.
Test measurements have been performed with the set-up of FIG. 4 , wherein the resistor 60 had a resistance of 22 Ohms, the loudspeaker 18 had a resistance of 260 Ohms and the acoustic output level measurements were performed in a 1.4 cc coupler with perfect sealing.
FIG. 5 shows the voltage measured at the resistor 60 as a function of frequency for different levels of obstruction, namely for totally closed filter (close acoustic output, labeled “close”), different intermediate levels of obstruction (partly closed acoustic output, labeled “Half 1 ” to “Half 4 ”, measurement without filter (open acoustic output, labeled “Nofilter”) and measurement with filter (open acoustic output, labeled “Wsfilter”). The loudspeaker 18 was fluid damped.
According to FIG. 5 , different voltage levels are obtained for different obstruction levels of the loudspeaker 18 , 118 . The voltage difference is obviously the largest at the resonance frequency of the loudspeaker 18 , 118 (in the present case about 3,200 Hz). In the case of small obstruction the quality factor decreases due to the parasitic acoustical resistance. For a totally blocked filter, the air volume between the loudspeaker 18 and the “stopper” creates a compliance (acoustic capacitor) in parallel with the standard compliance of the loudspeaker diaphragm. If the acoustic resistor is replaced by a compliance, the quality factor increases, but the resonance frequency also increase to about 4,000 Hz.
FIG. 6 shows the acoustic output level of the loudspeaker 18 measured in a 1.4 cc coupler as a function of frequency for the various obstruction levels of FIG. 5 .
According to one embodiment, the resonance frequency of the loudspeaker in free space is stored in the hearing device 10 , 110 during the manufacturing process. Later, when the hearing device 10 , 110 is operated, the analyzer unit 30 generates the stored resonance frequency and measures the voltage on the resistor 60 at this frequency. If the measurement shows too much of a difference, an alarm signal is created, as already explained above, for example, telling the user that the loudspeaker is blocked and should be cleaned.
While various embodiments in accordance with the present invention have been shown and described, it is understood that the invention is not limited thereto, and is susceptible to numerous changes and modifications as known to those skilled in the art. Therefore, this invention is not limited to the details shown and described herein, and includes all such changes and modifications as encompassed by the scope of the appended claims. | There is provided a method for monitoring a hearing device having an electroacoustic output transducer worn at a user's ear or in a user's ear canal, the method includes the steps of measuring the electrical impedance of the output transducer; analyzing the measured electrical impedance of the output transducer in order to evaluate the status of the output transducer and/or of an acoustical system cooperating with the output transducer; and outputting a status signal representative of the status of the output transducer and/or of the acoustical system cooperating with the output transducer. | 7 |
BACKGROUND OF THE INVENTION
This invention in one aspect relates to tuneable bandpass filters and, more particularly, to filters for use in a variety of equipments including spectrum analyzers and sine wave oscillators, but principally flow rate signal processors. In other aspects, my invention relates to unique trigger circuits for use in such processors.
In order to measure the flow rate of fluid in a conduit, it is common to utilize a Rodely bluff body to generate vortex shedding as described in U.S. Pat. No. 3,572,117 issued on Mar. 23, 1971, and assigned to the assignee hereof. The vortex shedding, which is oscillatory in nature, is in turn detected by a suitable sensor such as a thermistor, a shuttle or a diaphragm. The detector converts a parameter (e.g., temperature, pressure) variation of the fluid into an electrical signal. Typically, this signal is a composite of a low amplitude, high frequency fluid flow signal superimposed on a higher amplitude, random noise signal of lower frequency. The noise signal is generally not of interest.
Various types of electronic equipment have been proposed by the prior art to process the composite electrical signal and thereby measure flow rate. In many applications the flowmeter has been highly constrained by the high cost of such equipment. One system employs a series combination of a pre-amplifier, a filter and a schmitt trigger. The pre-amplifier incorporates frequency compensation which modifies the effective gain at various frequencies. The gain contouring is specific and is experimentally derived to get the best accuracy from the trigger circuit. Likewise, the signal passes through a fixed bandpass filter, one which has to be specifically designed for each application (e.g., each type of fluid or range of possible flow rates). In this type of equipment the filter bandwidth (f max :f min ) typically has to be less than 30:1 even for a bluff body-sensor arrangement (meter) which produces high signal quality; and, of course, has to be much narrower for poor signal quality meters. In addition, the equipment has to be adjusted, sometimes critically, to achieve adequate accuracy.
To avoid having to redesign the filter for each different frequency (flow rate) range, the prior art has suggested that a tracking filter be substituted for the fixed bandpass filter. These filters fall into two categories: electrically and mechanically tuneable. Electrically tuneable filters depend on electrically variable components such as light sensitive resistors, FETs (Field Effect Transistors) and voltage variable capacitors as tuning elements. All of these electrical components are notoriously nonlinear and temperature sensitive. In addition, a tuneable filter employing FETs, for example, has two other disadvantages: it is very slow and hence cannot be utilized in most applications which require response to dynamic flow rate changes; and it is very expensive due to the need for matched FETs. A mechanically tuneable filter, on the other hand, is cumbersome, complex and requires sophisticated electronics to interface with the mechanics.
Another development in fluid flow detection is generally referred to as a signal processor and typically has two models, one for measuring liquid flow rates and the other for gas flow. This inherently causes a problem in measuring the flow rate of high pressure gas which has a signal quality between liquid and gas. The basic processor solves the tuning range problem by switching whole sections of circuitry on or off, according to flowrate, but is a precision system, quite complex and difficult to repair.
It is therefore one object of my invention to provide flowmetering equipment which operates over a relatively wide range of signal quality, frequency, signal amplitude and noise conditions.
It is another object of my invention to provide such equipment utilizing a building block approach to circuitry which is simple to repair and modify, and which employs low-cost, non-precision components.
It is yet another object of my invention to provide a unique tuneable bandpass filter for use in such equipment, as well as in other equipments not necessarily related to flowmetering.
It is still another object of my invention to provide a unique trigger circuit for detecting the filter output, especially in flowmetering applications.
SUMMARY OF THE INVENTION
In accordance with one aspect of my invention, a tuneable bandpass filter comprises an input terminal connected to a non-inverting input of a balancing operational amplifier which rejects signal components outside the filter bandpass, a first variable rate integrator connected between the output of the balancing amplifier and an output terminal, Q and gain determining means connected between the output terminal and the non-inverting input of the balancing amplifier, a second variable rate integrator connected between the output terminal and the inverting input of the balancing amplifier and means for varying the rate of integration of the integrators.
In one embodiment of my filter, the variable rate integrators each comprise an operational transconductance amplifier in series with an operational amplifier integrator (i.e., an operational amplifier with a capacitor connected between its output and input). The rate varying means is a current bias applied to the transconductance amplifier.
In another embodiment of my filter, the variable rate integrator comprises an operational transconductance amplifier, a capacitor connected between its output and ground, and a high input impedance follower circuit connected between the output of the transconductance amplifier and the output terminal. Again, the rate varying means is a current bias applied to the transconductance amplifier.
Both of these embodiments possess a number of important advantages: (1) a broad range of frequency tuneability (e.g., 10,000:1), with the relationship between bias current and frequency being linear over the entire range; (2) constant Q over the tuneable range; and (3) self-balancing of the frequency determining components or matching between components.
In a second aspect, my invention is a signal processor for measuring the flow rate of fluid from a composite electronic signal characterized by a high frequency, low amplitude fluid flow signal riding on lower frequency, higher amplitude noise and other medium amplitude random frequency noise. The processor in one embodiment comprises the series combination of a gain controllable pre-amplifier, a tuneable filter as described above, an a.c. coupled summing amplifier and a transitional trigger circuit (to be described hereinafter). Two connections are made between the filter and summing amplifier: one, the bandpass output, to a multiple gain input of the summing amplifier, and the other, a highpass output (at the output of the balancing amplifier of the filter), to a unity gain input of the summing amplifier. The output of the summing amplifier is passed through an a.c. level detector and integrator to the gain controllable pre-amplifier. On the other hand, the output of the transistional trigger, which is also the processor output, is passed through a frequency-to-current converter to the filter (i.e., to the bias control of the variable rate integrators).
In another embodiment of my signal processor, the composite electronic signal is coupled to the series combination of a gain controllable pre-amplifier and a tuneable filter as described above. The bandpass signal of the filter passes through an auto-trigger circuit (to be described hereinafter) to the processor output, and is fed back through an a.c. level detector and integrator to the pre-amplifier; whereas the high pass output of the filter passes through a transitional trigger circuit and a frequency-to-current converter back to the filter (i.e., to the bias control as above).
Third aspects of my invention, therefore, are unique trigger circuits which can be utilized in the foregoing processors. The auto trigger functionally differs from a Schmitt trigger in that the latter switches whenever the input voltage exceeds fixed trigger voltages whereas the former switches whenever the high frequency signal (riding on low frequency noise) changes slope. Structurally, a Schmitt trigger is simply a bistable operational amplifier having a resistor connected between its output and its non-inverting input, which is also resistively coupled to the source of the signal to be processed. A resistor connects the inverting input of the amplifier to ground. In contrast, in an auto-trigger the latter resistor is replaced by a capacitor and a pair of oppositely poled, parallel connected diodes are coupled between the inverting input and the signal source. In comparison, the transistional trigger functions as a Schmitt trigger at low frequencies and as an auto-trigger at high frequencies. It is structurally identical to the auto trigger but for the addition of a resistor in parallel with the capacitor.
A fourth aspect of my invention incorporates the above-described tuneable filter into a low cost, low frequency spectrum analyzer in which the signal to be analyzed is coupled to a pre-amplifier, the output of which passes through the filter to an AC/DC converter. The filter frequency range is swept by a ramp generator and the converter output is displayed on suitable means such as a chart recorder or an x-y recorder.
In accordance with a fifth aspect of my invention, an oscillator comprises a closed loop including the series combination of an automatic level controller, a tuneable filter as above and an inverting, unity gain amplifier. The oscillator is tuned by the current bias applied to the variable rate integrators (range up to 10,000:1). The bandpass output of the filter supplies an osciallator signal at zero degrees phase whereas the amplifier output is at +180 degrees. Signals are also available from the filter at -90° (high pass signal at the output of the balancing amplifier) and at +90° (low pass signal at the inverting input of the balancing amplifier).
BRIEF DESCRIPTION OF THE DRAWING
These and other objects of my invention, together with its various aspects, features and advantages, can be readily understood from the following description taken in conjunction with the accompanying drawing in which:
FIG. 1 is a schematic of a tuneable bandpass filter in accordance with one aspect of my invention;
FIG. 2 is a schematic of another embodiment of my tuneable bandpass filter.
FIG. 3 is a schematic of an alternative Q and gain determining means for use with the filter of either FIG. 1 or FIG. 2;
FIG. 4 is a block-diagram of a signal processor in accordance with another aspect of my invention;
FIG. 5 is a block-diagramatic view of another embodiment of my invention;
FIG. 6 is a schematic of a prior art Schmitt trigger circuit;
FIG. 7 is a schematic of an auto-trigger circuit in accordance with a third aspect of my invention. This trigger is utilized, for example, in the processor of FIG. 4;
FIG. 8 is a schematic of a transistional trigger circuit in accordance with an alternative embodiment of the auto-trigger of FIG. 7. The transistional trigger is employed in the processors of both FIGS. 4 and 5;
FIG. 9 is a schematic of an alternative embodiment of the transistional trigger of FIG. 8
FIG. 9A is a modified form of FIG. 9 adapted to compensate for the base-emitter voltage drop of transistors Q1 and Q2;
FIG. 10 is a block-diagram of a spectrum analyzer incorporating my tuneable filter in accordance with a fourth aspect of my invention; and
FIG. 11 is a block-diagramatic view of an osciallator incorporating my tuneable filter in accordance with a fifth aspect of my invention.
DETAILED DESCRIPTION
Tuneable Bandpass Filter (FIGS. 1-3)
With reference now to FIG. 1, there is shown a tuneable bandpass filter 10 comprising input and output terminals 12 and 14, respectively, a balancing (differential) operational amplifier 16 having its non-inverting input 16.1 coupled to input terminal 12, and a first variable rate integrator 18 connected between the output 16.3 of amplifier 16 and output terminal 14. Q and gain determining means 20 is connected between output terminal 14 and the non-inverting input 16.1 of amplifier 16. A second variable rate integrator 22 is connected between output terminal 14 and the inverting input 16.2 of amplifier 16.
More specifically, the signal to be filtered (typically a fluid flow composite electrical signal 13) is coupled through resistor R1 to the input of balancing amplifier 16, i.e., to the non-inverting input 16.1 of operational amplifier A1. Feedback resistor R2 is connected between the inverting input 16.2 and the output 16.3 of A1. The output 16.3 of A1 is coupled to the input of integrator 18; i.e., through resistor R4 to the non-inverting input 18.1 of operational transconductance amplifier A5, which in turn is coupled through resistor R5 to ground. The inverting input 18.2 of A5 is also connected through a resistor R6 to ground. Bias current is supplied to A5 on lead 18.3 to vary the rate of integration of integrator 18. The output 18.4 of A5 is connected to the inverting input 18.5 of operational amplifier A3 whose non-inverting input 18.6 is grounded. Tuning capacitor C2 is connected between the inverting input 18.5 and the output 18.7 of A3, which is itself connected to the filter output terminal 14.
Output terminal 14 is also connected to the input of integrator 22, i.e., through resistor R7 to the non-inverting input 22.1 of operational transconductance amplifier A4, which in turn is coupled through resistor R8 to ground. The inverting input 22.2 of A4 is also connected through resistor R9 to ground. Bias current is supplied to A4 on lead 22.3 to vary the rate of integration of integrator 22. The output of 22.4 of A4 is connected to the inverting input 22.5 of operational amplifier A2 whose non-inverting input 22.6 is grounded. Tuning capacitor C1 is connected between the inverting input 22.5 and the output 22.7 of A2, which is itself connected through resistor R3 to the input of balancing amplifier 16, i.e., to the inverting input 16.2 of A1.
Q and gain determining means 20, illustratively resistor R13, is connected between output terminal 14 and the input of balancing amplifier 16; i.e., to the non-inverting input 16.1 of A1.
From a functional standpoint, A1 is a balancing amplifier which rejects frequency components of the input signal which are outside the bandpass of the filter. To better understand this function, assume that the input frequency f in =f c , is the center frequency of the filter. Then variable rate integrators 18 and 22 pass f c at a "gain" of -1. The highpass output at 16.3 and the lowpass output at 22.8 have equal amplitudes and, if R2=R3, then lead 16.2 is at zero volts (i.e., ground). Because lead 16.2 is grounded, A1 acts as an inverting amplifier in conjunction with integrator 18 yielding a filter gain of -R13/R1 at the bandpass peak point. On the other hand, if f in <f c , the integrators 18 and 22 each have "gain" greater than -1. Because the signal amplitude at the lowpass point 22.8 is greater than that at the output whereas the signal amplitude at highpass point 16.3 is less than that at the output, a non-zero signal occurs on lead 16.2. A1 subtracts this signal at 16.2 from the input signal at terminal 12. Therefore, a smaller voltage drop occurs across R1 which in turn means a smaller drop across R13 and hence a smaller output signal than at the bandpass peak point. Conversely, if f in >f c , the integrators 18 and 22 have "gain" less than -1. Therefore, the signal amplitude at 16.3 is greater than at the output which in turn is less than that at 22.8. Again, a signal appears at 16.2 which, as above, is subtracted from the input signal by A1.
A2 and A3 are integrators, the rate of integration being the determining factor of the bandpass frequency. The integrating capacitors C1 and C2 are, therefore, tuning elements. Preferably these capacitors are identical in value but the circuit will operate with mismatched values as well.
A4 and A5 determine the current supplied to integrators A2 and A3, respectively. That is, the bias current to A4 and A4, along with the voltage difference of their inputs, determines the current to A2 and A3. Since this relationship is linear, the filter operation is linear over the entire tuning range.
Resistor R1 determines the filter input resistance, and, together with R13, determines both filter Q and gain at the center frequency. More specifically, at the center frequency junction 16.4 equals zero impedance. R1 therefore determines the input impedance at center frequency. But, the impedance of junction 16.4 increases rapidly above and below the center frequency. Therefore, the filter input impedance is variable, R1 determining the lowest value. In addition, in accordance with the well known inverting amplifier gain equation, the gain at center frequency is equal to the ratio R13/R1. Empirically, I have found that the Q of the circuit to a first approximation is given by 20 log (R13/R1).
Resistors R2 and R3, on the other hand, are center frequency determining components. One resistor may be used as a variable component to match filters in production. Thus, as with C1 and C2, R2 and R3 are preferably equal, but operation is entirely feasible with mismatched values. A similar comment applies to mismatches between A4 and A5, including their associated resistors. R2 and R3 determine the center frequency f c by establishing the ratio of the highpass and lowpass voltages at f c . For example, as mentioned previously, with R2=R3, highpass and lowpass voltages are equal at f c . But, if R2=2R3 then the highpass voltage at 16.3 must be one-half of the lowpass voltage at 22.8 to cause zero volts at f c . Unequal values of R2 and R3 must therefore change f c and the integrators 18 and 22 must have different gains (i.e., other than -1) to accommodate the different voltages at the highpass and lowpass outputs. That is, f c is lowered to cause a "gain" of +2 through both integrators in cascase, thereby causing the highpass voltage to be one-half the lowpass voltage at f c . Assuming identical integrators and R2=2R3, each integrator must have a gain of √2 at the new center frequency f c '. All else being constant it can be shown that f c =f c ' √ R3/R2 where F c ' is the new center frequency and f c is the center frequency when R2=R3.
Resistive dividers R4-R5 and R7-R8 reduce the signal levels to the linear range of A5 and A4, respectively (typically these amplifiers are linear only for a ±10 mV swing at their inputs). R6 and R9 are input impedance matching resistors.
An alternative embodiment of my tuneable filter is shown in FIG. 2 in which components corresponding to those of FIG. 1 have been given identical reference numbers to facilitate comparison. The basic difference between the two filters resides in variable rate integrators 18' and 22'. In 18', for example, the inputs of A5 are reversed, the output of A5 is connected to the non-inverting input 18.6 of A3' (rather than to the inverting input as in FIG. 1) and C2' is connected between the output 18.4 and ground (rather than between the input and output of A3 as in FIG. 1); and the inverting input 18.5 and output 18.7 of A3' are directly connected (rather than capacitively coupled through C2 as in FIG. 1). In a similar fashion 22' can be related to 22 of FIG. 1.
Functionally, A4 and A5 act as variable rate integrators which integrate voltages onto C1' and C2', respectively. A2' and A3' remove loading effects on the integrators A4 and A5, and can be transistor emitter followers, FET source followers, operational amplifier followers (as shown in FIG. 2), or any other high input impedance follower circuit configuration. The input impedance of the follower determines the quality of the filtering to some extent because of non-ideal integration by A4 and A5.
In applications where variable gain or Q is desired, R13 is replaced, as shown in FIG. 3, with operational transconductance amplifier A6 and input resistors R10, R11, and R12. These resistors are used for the same functions as R4, R5 and R6, i.e., to lower the signal level and to balance the input impedances. As with A4 and A5, the output current of A6 is linearly determined by the differential input voltage times the bias current. The gain is inversely proportional to the bias current and is quite nonlinear, being based on R1 divided by the resistance R(A6) of the circuit of FIG. 3. Since R(A6) is variable, the bias current has a nonlinear control of gain.
By way of example, the following resistor, capacitor and amplifier component values have been found suitable for use in the filter of FIG. 2:
______________________________________TABLE OF COMPONENT VALUESComponent Value Comment______________________________________R1 560K Ohms 10K - 10M Ohm suitable.R2,R3 100K Ohms Need not be equal. Range 2:1 to 1:2 suitable.R4,R7 20K Ohms Typical for 2V peak output at filter center frequency. 0- 1M Ohm dependent of operating voltage range. -R5,R6,R8,R9 60 Ohms Chosen to reduce voltage at inputs of A4 and A5 to 10 mV peak-to-peak.R12 3M Ohms 10K- 100M Ohms suitable.C1',C2" .01 Micro 10pf-- 100 micro F typically; F (low leakage capacitors).A1,A2',A3' CA3140AT Manufactured by RCA. CA3130 (RCA) or LM122, 222, 3232 (National Semiconductor Corp., Santa Clara, Calif.) also suitable.A4,A5 CA3080E Manufactured by RCA. CA3080A, CA3060 (RCA) also suitable.Circuit Q 14.5 Flow signal had frequency jitter, necessitating low Q. Range of 0-60 possible.Gain 5.3 Range of 1- 1000 possible.______________________________________
The tuneable bandpass filters described above have the following notable characteristics (1) wide range tuneability up to 10,000:1, (2) linear tuneability over the entire range with only about 1% deviation; (3) constant Q and gain over the entire tuning range; (4) a direct bandpass output (at terminal 14), a highpass output (at the output of A1, i.e., at 16.3 of FIGS. 1 and 2), a lowpass output (at the output of A2, i.e., at 22.7 of FIGS. 1 and 2), and a band reject output equal to the sum of the highpass and lowpass outputs, all simultaneously tuned to the identical frequency. This feature is employed in the signal processor described hereinafter; (5) for any of the above outputs, low phase distortion of ±90 degrees reference to the phase angle at the center frequency; (6) intrinsically self-balanced circuitry--there is no need for matching or balancing components in production in order to achieve proper Q or gain peak point. More specifically, the frequency-determining components (FIG. 1: A4, A5, C1, C2, R4, R5, R7, R8) are portions of variable integrators. Variations in these components affect the rate of integration but not the quality of integration. That is, because these components affect the center frequency of the filter but not the Q, their total effect can be readily nullified by varying the bias current to A4 and A5. Self-balancing, therefore, means that all frequency-determining components can be lumped together and treated as a net effect on the ratio of the bias current to center frequency of the filter, but no such component need be matched to obtain proper Q; (7) variable gain and Q which follow simple mathematical formulae and can be adjusted via R13 or A6; (8) low cost components; and (9) duplication of components to reduce stock and increase quantity discounts.
Before discussing the several processors which incorporate my tuneable filter, it will be helpful to first describe two trigger circuits which are also utilized in those processors.
Trigger Circuits (FIGS. 6-9)
In FIG. 6, a prior art Schmitt trigger circuit is depicted as comprising a bistable operational amplifier A7, a resistor 3R connected between its inverting input and ground, a resistor 2R connected between its non-inverting input and its output, and a resistor 1R connected between its non-inverting input and a source of signals (INPUT). This Schmitt trigger has a fixed baseline and fixed upper and lower threshold (trigger) voltages. Whenever the signal crosses the trigger levels, amplifier A7 toggles and a pulse is produced at the output. But, because the Schmitt trigger ignores signals which do not cross the trigger levels, it would give an erroneous output for a typical composite fluid flow signal, i.e., a high frequency low amplitude fluid flow signal riding on lower frequency, high amplitude noise.
This problem is solved in accordance with another aspect of my invention, the provision of an auto-trigger circuit which has a variable baseline and provides an output pulse whenever the signal changes slope. An auto-trigger which can remove a fluid flow signal from noise greater than the signal itself, is illustratively shown in FIG. 7. It differs from the Schmitt trigger of FIG. 6 in that resistor 3R has been replaced by capacitor 1C, and a pair of oppositely poled parallel connected P-N junction devices (e.g., diodes) CR1 and CR2 are connected in series with resistor 4R and the series combination is connected between the inverting input of A7 and the INPUT. In operation, the baseline is controlled by the voltage on capacitor 1C and follows the signal (less the voltage across the diodes) when the signal is increasing and follows the signal (plus the voltage across the diodes) when the signal is decreasing.
A further modification of the auto-trigger circuit is the transitional trigger circuit shown in FIG. 8. It is a Schmitt trigger at low frequencies and an auto-trigger at high frequencies, with the transition between the two regimes of operation being controlled by an RC time constant. More specifically, the transitional trigger differs from the auto-trigger by the addition of resistor 3R in parallel with capacitor 1C. The transition frequency between Schmitt trigger and auto-trigger operation occurs at approximately (2 R3C1) -1 , although there is (desirably) considerable overlap of the two modes of trigger operation in the transitional range.
In both the auto and transitional trigger circuits, the circuit components advantageously have the following characteristics. A7 is a bistable operational amplifier. It should have low bias currents to reduce drift on 1C, and be able to stand a differential input voltage without damage or leakage. 1C is a storage capacitor sufficient to reduce drift due the bias current of A7 to a tolerable level. Resistor 1R and 2R determine the hysteresis of A7. The hysteresis voltage must be less than the diode forward voltage drops. 3R and 1C determine the baseline drift and 4R limits the diode current to safe levels. CR1 and CR2 are illustratively low level signal diodes with low reverse leakage currents.
Alternatively, diodes CR1 and CR2 can be replaced with transistors which, owing to their gain, reduce input loading. As shown in FIG. 9, transistors Q1 and Q2 are complementary and have their emitters connected to the inverting input of A7 and their bases connected to 4R. The collector of Q1 is connected through 5R to a B+ voltage source and the collector of Q2 is connected through 6R to a B- voltage source. Another advantage to using transistors relates to the diminished effect of emitter-base leakage current on the voltage across capacitor 1C because (1) the base currents are smaller than the diode currents and (2) leakage through one base-emitter junction is partially cancelled by emitter to collector leakage in the other transistors.
In the transitional trigger embodiment of FIG. 9, the Schmitt trigger mode has greater sensitivity than the auto-trigger mode because of the base-emitter voltage drops of Q1 and Q2. However, another embodiment of my transitional trigger shown in FIG. 9A compensates for these voltage drops by the addition of a diode current steering bridge 100 and an operational amplifier A8 between the input and resistor 1R and the bases of Q1 and Q2.
More specifically, the bridge 100 comprises two pairs of opposite terminals 101-102 and 103-104. Terminals 103-104 are connected together by resistor 12R and are connected through resistors 11R and 13R to voltage sources B+ and B-, respectively, and through resistors 4RB and 4RA to the bases Q1 and Q2, respectively. Terminals 101-102 are connected respectively to the output of A8 and to resistor 1R. The diodes are configured as follows: diode D1 connects terminals 103 and 101, D3 connects 101 and 104, D2 connects 103 and 102 and D4 connects 102 and 104, with D1 and D3 being oppositely poled with respect to terminal 101 and D2 and D9 being oppositely poled with respect to terminal 102.
Amplifier A8, on the other hand, has the feedback resistor 8R connected between its output and inverting input. The input to the trigger circuit is applied to the non-inverting input of A8. The inverting input is also connected through resistor 10R to ground and through resistor 9R to terminal 102.
Resistor 11R, 12R and 13R provide a small reverse bias to the emitter-base junctions of Q1 and Q2 to reduce leakage currents. Resistor 8R stabilizes A8 by providing a feedback path around the diode bridge 100. 9R and 10R set the gain of this noninverting configuration. A similar circuit functions in the inverting configuration.
The embodiment of FIG. 9A differs from that of FIG. 9 as follows: (1) the bases of Q1 and Q2 are not connected together and through a single resistor 4R to the input. Instead, the bases are coupled through separate resistors 4RA and 4RB to the resistively connected opposite terminals 103-104 of bridge 100; and (2) resistor 1R is connected to the input through the other pair of terminals 102-101 and A8 instead of directly to the input. Otherwise, Q1-Q2, C1-R3 and A7 function as in the embodiment of FIG. 9.
The implementation of the foregoing trigger circuits and tuneable filters in signal processor arrangements will now be described in accordance with yet another aspect of my invention.
Signal Processors (FIGS. 4-5)
One embodiment of my invention, the signal processor of FIG. 4, incorporates both an auto and transitional trigger circuit as well as my tuneable bandpass filter. In particular, a composite fluid flow signal 30 is applied to input terminal 32 and passed through a gain controllable pre-amplifier 34 to tuneable bandpass filter 36 of the type depicted in FIGS. 1 and 2. The bandpass output of filter 36 (i.e., the signal at terminal 14 of FIGS. 1 and 2) is applied to the input of auto trigger 38 (see FIG. 7) which provides a square wave output 40 at output terminal 42. The bandpass output of the filter 36 is also passed through gain controller (GC) 44 back to preamplifier 34. Typically, GC 44 comprises a rectifier 44.1 in series with an AC level detector-integrator 44.2. The output of detector-integrator 44.1 is connected to the gain control input of pre-amplifier 34 and the input of rectifier 44.1 is connected to the bandpass output of filter 36. In addition, the highpass output of filter 36 (i.e., the signal at terminal 16.3 of FIGS. 1 and 2) is applied to the input of transitional trigger 46 (see FIGS. 8 and 9), the square wave output of which is applied to converter 48. The latter converts the frequency of the square wave to a current which is coupled back to tuneable filter 36 (i.e., to bias inputs 18.3 and 22.3 of FIGS. 1 and 2).
In operation, with no signal at input terminal 32, the gain control of pre-amplifier 34 is set at maximum gain by means of controller 44, and filter 36 is tuned to minimum frequency. When signal 30 is applied to input terminal 32, it is amplified by pre-amplifier 34 and fed through the highpass output of filter 36 to transitional trigger 46. The trigger has some "filtering" properties itself, and triggers on the signal being fed into it. The square wave output of the trigger 46 is frequency-to-current converted by converter 48 to generate bias current which controls the center frequency of filter 36.
The highpass output of filter 36 is initially an all pass output because the filter is initially set at its minimum frequency. As filter 36 is tuned upward in frequency, low frequencies are removed from the highpass output, yielding a cleaner signal and, therefore, more accurate tuning.
When the center frequency of filter 36 approaches the actual frequency of signal 30 (i.e., its high frequency component), an output begins to be generated at its bandpass output. This is true flow signal. It is passed through gain controller 44 to provide a gain control current to pre-amplifier 34. More specifically, the AC signal at the bandpass output of filter 36 is full-wave rectified by rectifier 44.1 and fed to the inverting input of integrator-detector 44.2, typically an operational amplifier having a capacitor connected between its output and its inverting input and a reference voltage applied to its non-inverting input. The integrator integrates up and down according to the level of its input signal in relation to the reference voltage. Thus, if the average level of the input signal is below reference, up-integration occurs and conversely. The output voltage of the integrator is converted to a current (via a resistor) which controls the gain of the pre-amplifier 34 (e.g., this current is used as the bias current to an operational transconductance amplifier (not shown) within preamplifier 34).
The flow signal at the bandpass output of filter 36 is also applied to the input of auto-trigger circuit 38 which generates square wave output 40 corresponding to the high frequency fluid flow component of input signal 30. Counting these pulses provides a measure of fluid flow rate.
One comment is in order regarding the use of both types of trigger circuits in the processor of FIG. 4. First, the auto-trigger 38 is used as shown because a DC offset voltage appearing at the bandpass output of filter 36 would render a transitional trigger useless for its Schmitt trigger characteristics. Second, the transitional trigger 46 is used for its Schmitt trigger characteristics at low frequencies (e.g., low flow water) where high frequency noise appears on the basic signal. Under these circumstances, an auto-trigger would trigger on both low frequency signal (e.g. 10 Hz for water flow) and higher frequency noise (e.g., 20 Hz for water flow) and would therefore generate erroneous tuning of the filter 36. In contrast, transitional trigger 46 ignores the higher frequency noise on low frequency signals.
The signal processor of FIG. 4 has a number of unique features: (1) the gain control feedback is derived from the final filtered signal output. Therefore, poor signal quality at input terminal 32 (as might be generated by a poor or defective flowmeter sensor) has virtually no effect upon the output signal level because the gain of pre-amplifier 34 is adjusted to bring the signal of interest to the proper level regardless of noise associated with the flowmeter signal 30: (2) the tuning signal of filter 36 is derived from a partially filtered point (i.e., the high pass output) of filter 36, which improves the tuning signal enough to provide highly accurate filter tuning; and (3) the filter 36 is linearly tuned thereby allowing inexpensive and fast tuning. This feature is especially significant because it eliminates a closed feedback gain control tuning loop configuration dependent on signal amplitude. Instead, the signal processor is essentially independent of signal amplitude. It is basically a measure and set situation, i.e., the frequency is measured and the tuning current is set. In addition, the improved signal quality which occurs after tuning enhanced the measurement of frequency. Consequently, the setting of the filter center frequency is further improved (positive feedback in the tuning loop).
An alternative and somewhat simpler embodiment of my signal processor is shown in FIG. 5. It is simpler in that it incorporates only my tuneable filter and transitional trigger circuit, but no auto trigger circuit. More specifically, a composite fluid flow signal 50 is applied to input terminal 52 and passed through a gain controllable pre-amplifier 54 to tuneable bandpass filter 56 of the type depicted in FIGS. 1 or 2. The bandpass output of filter 56 (i.e., the signal at terminal 14 of FIGS. 1 and 2) as well as its high pass output (i.e., the signal at terminal 16.3 of FIGS. 1 and 2) are applied to the input of a weighted summing amplifier 58. Typically, the high pass signal is connected to a unity gain input of amplifier 58 whereas the bandpass signal is connected to a multiple gain (e.g., 3×) input. The output of summing amplifier 58 is applied to the input of transitional trigger circuit 60 (see FIGS. 8 or 9) which generates square wave signal 62 at output terminal 64. Terminal 64 is also coupled through a frequency-to-current converter 66 to produce a tuning current which varies the center frequency of tuneable filter 56 (i.e., the tuning current is applied to bias inputs 18.3 and 22.3 of FIGS. 1 and 2). In addition, the output of summing amplifier 58 is coupled through gain controller 68 to provide gain control current to pre-amplifier 54.
As with the embodiment of FIG. 4, initially the gain control of pre-amplifier 54 is set at maximum gain by means of controller 68, and filter 56 is tuned to minimum frequency. When flow signal 50 is applied to input terminal 52, it feeds through pre-amplifier 54, the high pass output of filter 56 and the summing amplifier 58 (at unity gain) to the transitional trigger circuit 60. As the trigger circuit 60 responds to the signal and generates square wave 62, it tunes filter 56 upward in frequency (via converter 66). The signal quality improves which enhances tuning accuracy. As the center frequency of filter 56 approaches the actual input frequency of signal 50 (i.e., its high frequency fluid flow component), the input signal starts to emanate from the bandpass output of filter 56. Because the bandpass output has a summed gain of, say, three (3×), the gain controller 68 lowers the bias to pre-amplifier 54 (in response to a larger signal), lowering the output signal level from filter 56 and thereby reducing the effect of the high pass signal.
It is to be understood that the hereinbefore described arrangements are illustrative of the application of the principles of this invention. In light of this teaching, it is apparent that numerous other arrangements may be devised by those skilled in the art without departing from the spirit and scope of my invention. In particular, many functional systems are possible using the four outputs of my tuneable filter: bandpass at terminal 14 of FIGS. 1 or 2, high pass at terminal 16.3, low pass at terminal 22.8, and band reject by summing the highpass and lowpass outputs. In addition, my analysis indicates that at gain less than unity at f c the bandpass output of my filter should become a band reject output with high Q as the gain at f c is reduced.
Spectrum Analyzer
One such system shown in FIG. 10 is a low frequency, low cost system analyzer which depends directly on my tuneable bandpass filter for its implementation.
The signal 70 to be analyzed is applied to input terminal 72 and fed through pre-amplifier 74 to the input of tuneable filter 76 of the type depicted in FIGS. 1 and 2. Filter 76 is set at maximum Q and its bandpass output is coupled to an AC-to-DC converter 78. The latter drives a suitable display device such as chart recorder 80 or an x-y recorder (not shown). In order to sweep the input signal, the center frequency of filter 76 is linearly varied by ramp generator 82 which supplies tuning current (i.e., to bias inputs 18.3 and 22.3 of FIGS. 1 and 2). Start-stop means 84 controls both ramp generator 82 and recorder 80 (via its motor, not shown). With filter 76 set at maximum Q, the display on recorder 80 consists of a series of spikes at each frequency corresponding to a frequency component of the input signal. The height of each spike corresponds to the amplitude of the corresponding frequency component. The resolution of the analyzer is determined by the Q of the filter 76, the higher the Q the better the resolution.
Oscillator
My tuneable bandpass filter has a 180 degree phase shift at its center frequency. Consequently, another 180 degree shift can be provided by an inverting amplifier to bring the input into phase with the output and thereby lend my filter to oscillator applications. One such embodiment is shown in FIG. 11.
An automatic level (gain) controller 90, a tuneable bandpass filter 92 of the type shown in FIGS. 1 and 2 and an inverting, unity gain amplifier 94 are connected in series in a closed loop; i.e., the output of controller 90 is coupled to filter 92, the bandpass output of filter 92 drives amplifier 94, and the output of amplifier 94 is fed back to the input of controller 90. Filter 92 is set at maximum Q and tuned by current source 96 (applied to bias inputs 18.3 and 22.3 of FIGS. 1 and 2). Gain controller 90 is an automatic level controlling device which keeps the loop gain at exact unity while oscillating, and increases the loop gain to initiate oscillation.
Sinusoidal signals of the following phases are generated: zero degrees at the bandpass output of filter 92; -90 degrees at its high pass output; +90 degrees at its lowpass output; and -180 degrees at the output of inverting amplifier 94. Source 96 varies the frequency of the sinusoids. | Described are several signal processors for measuring the flow rate of fluid. These processors incorporate various combinations of a unique tuneable bandpass filter, which rely on variable rate integration, and unique trigger circuits which trigger on the change of signal slope. Also described are a spectrum analyzer and oscillators which employ the tuneable bandpass filter. | 7 |
BACKGROUND AND SUMMARY OF THE INVENTION
This invention relates generally to sewing machine gauges and, more particularly, to a gauge having provisions incorporated therein to enable an individual to continuously monitor the condition of the thread contained on a bobbin disposed below the gauge.
In conventional sewing machines, two supplies of thread must necessarily be provided. One of these is the thread supplying the needle itself which is usually in the form of a spool located on the upper portion of the machine and in plain view of the operator, thus allowing the operator to continuously monitor the amount of thread remaining, as well as the condition of the thread as it passes through various tensioning and other feed control devices. Thus, should this thread become snagged upon a portion of the machine or should the supply become exhausted, the operator will be immediately aware of the problem which may then be easily corrected.
The second supply of thread required on such machines is generally located in a bobbin case disposed in the lower portion of the machine, normally immediately adjacent to and below the needle. In normal operation, this bobbin case is concealed from view by a cover member or throat plate. Thus, the operator of the machine must either guess as to the condition and amount of thread remaining on the bobbin or go through the time consuming process of periodically removing the throat plate thereby exposing the bobbin for a visual inspection. This arrangement is particularly undesirable on machines being used for commercial operations, as it will likely result in bobbins being replaced before the thread supply is exhausted thus wasting materials in addition to reducing the output available from the machine and operator thereof as the operator must periodically cease production to inspect the condition of the bobbin thread supply. Should the operator continue sewing after the thread supply from the bobbin has been exhausted or otherwise interrupted, the stitches will not hold and thus it will be necessary to spend additional time removing the unsecured stitches and restitching the entire article thus consuming substantial time, reducing the machine and operator's output and otherwise delaying production. Additionally, when sewing certain types of materials, it will be impossible to go back and restitch the material should the bobbin thread become broken or the supply be exhausted during a stitching operation, as the initial needle punctures will remain visible thus incurring additional costs in the form of wasted material.
While such problems may be annoying to the homemaker doing only occasional sewing, they are extremely significant in high volume production work. It is estimated that a single production line seamstress will completely exhaust 50 bobbins during an 8 hour shift. That means that a single operator will be using approximately 6 bobbins an hour. When this figure is multiplied by numerous operators, it is apparent that substantial amounts of time, money, and materials may be wasted due to the inability to continuously monitor the bobbin thread supply and condition.
Various attempts have been made to provide a solution to this problem by providing assorted arrangements of apertures, lights, mirrors, and other devices designed to inform the operator of the bobbin thread condition. However, none of these arrangements have been totally acceptable.
In one arrangement, transparent plexiglass throat plates were designed to replace the typical metal plates. This arrangement worked quite well initially, but as material was continuously moved across the throat plate, the plexiglass became scratched and clouded thereby requiring frequent machine down time in order to replace them and rendering their usefulness over an extended time period uneconomical. Also when a stitch depth gauge was installed on the machine, it concealed the view of the bobbin. As such stitch depth gauges are commonly used in producting sewing, this device proved totally unsuitable for such applications.
Another arrangement provides a remotely located opening in combination with mirrors to enable the operator to view the bobbin. While this arrangement eliminates the problems associated with the transparent throat plate, it is expensive to install and requires the mirrors be readjusted for different operators thus making them costly to use on a production line basis. Additionally, the mirrors require cleaning periodically and are subject to breakage.
Accordingly, the present invention offers a unique solution to this problem in providing means by which the machine operator may easily continuously visually inspect the condition of the bobbin thread, the supply remaining on the bobbin, as well as observing the operation of bobbin stitching mechanisms. The present invention provides a stitching gauge which is specially adapted to include a window portion therein which cooperates with an opening provided in the throat plate to afford the operator an unobstructed view of the bobbin thread and associated feed mechanism. The device thus provided may be easily adapted to fit most any conventional home or industrial sewing machine and is extremely durable while still affording means for easily adjusting the stitch gauge for any particular job. As the material being sewn does not pass across the window, the device is extremely rugged and may be inexpensively fabricated the problems associated with these prior arrangements are effectively overcome. Further, the window may be adapted to be easily and quickly cleaned and/or replaced should it become damaged or broken thus minimizing machine down time while affording substantial savings in material costs and increasing operator productivity.
Additional features and advantages of the present invention will become apparent from the subsequent description and the appended claims taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the invention shown in operative relationship to a portion of a sewing machine;
FIG. 2 is a perspective view of the see-through sewing gauge of the present invention;
FIG. 3 is a bottom view of the throat plate in accordance with the present invention;
FIG. 4 is a sectional view of the present invention taken along line 4--4 of FIG. 2;
FIG. 5 is a top view of another embodiment of the present invention; and
FIG. 6 is a view of the embodiment of FIG. 5 shown in section taken along line 6--6 of FIG. 5.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 1, there is shown a conventional sewing machine indicated generally at 10 and including a presser foot 12, needle 14 and needle bar 16 adapted to reciprocate the needle into and out of an aperture provided in plate 18 located directly therebelow. Base plate 18 is provided with additional apertures adapted to accommodate feed dogs which project upward above the surface of the base plate and reciprocate so as to advance the material as the needle provides the stitching action thereto. Immediately adjacent and below these feed dogs and housed within the base portion 20 of the machine is a bobbin case and associated feed mechanism. The bobbin case has associated therewith a bobbin carrying a supply of thread and associated thread feeding mechanism. Access to this case is afforded through a generally rectangular opening 22 in the base plate 18 which is covered by a base or throat plate 24 during operation thereof. As these portions of the machine are well-known within the art, further description thereof is believed unnecessary.
In FIG. 1, base or throat plate 24 is modified in accordance with the present invention having a stitch gauge 26 with a transparent window 64 provided therein secured thereto all of which will be described in greater detail below.
Referring now to FIGS. 2 through 4, there is shown a see-through sewing gauge in accordance with the present invention indicated generally at 30. The gauge 30 includes a base plate 24 having a generally rectangular shape adapted to fit within opening 22 of sewing machine 10 and is provided an aperture 32. Base plate 24 will generally be fabricated of metal and of a thickness so as to insure the top surface thereof will fit flush with base plate 18 of sewing machine 10. Aperture 32 will be of a generous size and positioned within base plate 24 so as to afford a clear unobstructed view of the bobbin thread supply and associated feed mechanism.
A gauge member 26 is adjustably secured to base plate 24 and is comprised of a pair of substantially parallel legs 34 and 36 extending outward from opposite ends of a cross member 38 so as to form a generally "U" shaped structure. Each of legs 34 and 36 has a longitudinally elongated slot 40 and 42 respectively extending therethrough adapted to allow gauge member 26 to be adjustably secured to base plate 24 as described below. Cross member 38 will generally be of a slightly greater thickness than legs 34 and 36 so as to insure a generous vertical wall 44 against which the material will travel. The outer wall portions 46 and 47 at the intersection of respective leg members 34 and 36 with cross member 38 are rounded so as to insure against the possibility of the material becoming snagged and to otherwise insure the smooth advancement of the material.
Threaded screw fasteners 48 are disposed in respective slots 40 and 42 each threadingly engaging apertures provided in base plate 24 and have an enlarged diameter cylindrically shaped top portion 50 provided with serrations around the circumference thereof which are adapted to allow finger tightening and loosening thereof. Top portion 50 forms a shoulder 52 which engages surfaces 54 and 56 of leg 34 and surfaces 58 and 60 of leg 36 so as to clamp legs 34 and 36 to base plate 24 once vertical wall portion 44 has been properly positioned with respect to the needle of the sewing machine so as to provide a guide to insure a constant distance between the edge of the material being sewn and the line of stitching. Also screw fasteners 48 are each provided with a hexagonal indentation 62 at the top of enlarged diameter portion 50 suitable for insertion of an allen wrench should additional tightening torque be desired. Additionally, should it be desirable, each of these screw fasteners 48 may be provided with a washer 63 so as to insure complete engagement with and secure clamping of respective portions 54, 56, 58 and 60 of leg members 34 and 36.
A transparent window member 64 is disposed between the leg members 34 and 36 and the cross member 38. This window is of a size to fit snuggly therebetween so as to be frictionally retained in position. As illustrated in FIG. 2, aperture 32 provided in base plate 64 has a width slightly less than the distance between leg members 34 and 36 thereby providing a shoulder portion 65 adjacent each of leg members 34 and 36 for supporting window member 64. Also window member 64 will be longer than aperture 32 so as to allow it to be supported at least one and possibly two additional sides thereof depending upon the position at which gauge member 26 is secured. In any event it is apparent that the three sided support in addition to the frictional fit with leg members 34 and 36 will positively prevent window member from dropping down into the bobbin case. If desired this window member may be of a slightly greater thickness than the leg portions 34 and 36 so as to allow the upper surface thereof to be engaged by washers 63 provided on screw fasteners 48 thereby clamping window member 64 to base plate 24 or should it be desirable, shoulder portion 52 may be sized to slightly overlap window member 64 so as to eliminate the need for washers 63 while still allowing window member 64 to be clamped in position. This arrangement thus insures that the window member 64 will be securely held in place during use of the device but yet still affords easy removal and replacement should window member 64 become scratched, broken or otherwise damaged. Alternatively, window member 64 may be secured in position by a suitable adhesive such as indicated at 67 of FIG. 4 should this be found desirable. While plexiglass is particularly well suited for this application, any other transparent material may be easily substituted therefore such as, for example, a polycarbonate composition or even glass.
Referring now to FIGS. 3 and 4, base plate 24 has a reduced thickness portion 68 shaped generally as shown on the bottom thereof which is provided to insure adequate clearance for the bobbin and associated feed mechanism. Also, three pairs of spaced apart threaded apertures 70, 72 and 74 are provided in the base plate for receiving the threaded portion of the screw fasteners 48 previously described. While a single pair of such apertures 72 would be sufficient, greater flexibility in adjustment of the gauge member is provided by the additional apertures 70 and 74 which allow the position of screw fasteners 48 to be selectively positioned for any particular job. These additional threaded apertures in combination with slots 40 and 42 afford a wide degree of movement of gauge member 26 with respect to base plate 24.
In order to utilize the above described see-through gauge, the operator need merely remove the existing bobbin cover plate from the machine and place the present invention in its place. Next, the operator will adjust the gauge to be desired stitch depth as measured between surface 44 and needle, secure the screw fasteners and then proceed in a normal fashion. The material to be sewn will be placed in the machine in a conventional manner with the edges adjacent the portion to be seamed abutting vertical wall 44 of gauge 26 thereby providing means by which the operator can insure a constant distance between the edge of the material and the seam. Also as will be noted, the main portion of the material will extend away from the gauge thereby leaving the window member 64 unobstructed and allowing the operator to easily view the condition of the bobbin thread. Should the supply of thread on the bobbin become exhausted, the operator will be immediately aware of this fact and be able to replace the bobbin.
Referring now to FIGS. 5 and 6 another embodiment of the present invention is illustrated therein being generally indicated at 76. See-through sewing gauge 76 is similar to gauge 26 having a base plate 78 with an aperture 80 disposed therein, a gauge member 82 movably mounted thereon through the agency of screws 84 and 86 passing through elongated slots 88 and 90 respectively and a transparent window member 92 secured to gauge member 82. In this embodiment gauge member 82 is generally rectangular in shape and has an aperture 94 provided therein into which transparent window member 92 is secured. Gauge member 82 is provided with a pair of shoulder portions 96 and 98 projecting into aperture 94 from opposite side walls thereof which are adapted to provide support for window member 92. Shoulder portions 96 and 98 will generally be of a thickness approximately one half the total thickness of side portions 100 and 102. This support arrangement not only enables the gauge to be fabricated with a substantially reduced thickness window member but in that window 92 is spaced away from base plate 78 it will not become scratched by dust or dirt as it is moved during the adjustment of gauge member 82. Also, greater latitude in the size of aperture 80 in base plate 78 is afforded as only gauge member 82 is supported on base plate 78. As aperture 92 is enclosed on four sides by portions of the gauge member 82, window member 92 is prevented from any possibility of vibrating or otherwise slipping out of the gauge member. Further, the edges of the gauge member serve to afford the window member with increased protection. Window member 92 may be secured within aperture 94 in the same manner as described with reference to the embodiment of FIG. 2. Also similar to that of the embodiment of FIG. 2, gauge member 82 is provided with a substantially thicker wall surface portion 104 along which the edge of the material to be sewn is passed and an arcuate outer edge 106 at the junction of surface 104 with side portion 100 so as to insure smooth snag-free advancement of the material.
It is therefore apparent that the present invention provides a sewing gauge which may be manufactured very inexpensively and can easily be adapted to fit most any sewing machine so as to enable an operator thereof to substantially increase their productivity in that the device eliminates the time consuming need to periodically check the bobbin thread supply as well as reducing the amount of thread wasted in early bobbin replacement. Further, as the present invention allows continual visual monitoring this feed mechanism the operator will be immediately aware of any mechanical failure or other malfunctioning of this portion of the machine thereby enabling repairs to be made before additional damage is caused as well as preventing the production of faulty seams.
While it is apparent that the preferred embodiments of the invention disclosed provide a substantially improved sewing machine gauge, it will be appreciated that the invention is susceptible to modification, variation and change without departing from the proper scope of fair meaning of the subjoined claims. | There is disclosed herein an improved see-through sewing gauge comprising a gauge means for controlling the depth of a stitch during a sewing operation and having a window portion disposed therein adapted to cooperate with an opening provided in an associated throat plate so as to enable an operator to continuously monitor the condition of the bobbin thread supply disposed below said gauge. The gauge and window combination is movably secured to the throat plate of the sewing machine in such a manner as to be easily adjustable thereby enabling an operator to conveniently set the gauge to any desired depth of stitch. | 3 |
BACKGROUND OF THE INVENTION
The present invention relates to the measurement of unidirectional current, and more particularly, to measurement of unidirectional output currents of multiphase power rectifiers.
Many circuits for measuring unidirectional current are known. Among such circuits are those disclosed in U.S. Pat. Nos. 3,281,642, issued Oct. 25, 1966 to Dortort, and 3,944,919, issued Mar. 16, 1976 to Jewell et al, the Jewell et al patent being assigned to the assignee of the present application.
Briefly, the Dortort patent discloses circuits for reducing measurement error due to a 30° power circuit phase shift, as in a simple wye-delta or delta-wye three phase power circuit connection. In one such circuit, Dortort discloses delta connection of the current transformer secondaries associated with the primary line conductors and connection of these secondaries to a dc measuring instrument through a multiphase instrument rectifier. The Jewell et al patent discloses circuits for reducing the measurement error due to power circuit phase shift of 30° as well as other magnitudes of phase shift. In one such circuit, Jewell et al provide current transformers in the input circuit of the power transformer with the current transformer secondary windings connected in wye circuit relation to a three phase instrument rectifier through a phase shifting current transformer. In one form of the Jewell et al circuit, the phase shifting transformer comprises an autotransformer.
Although the circuits disclosed in the Jewell et al patent are successful in many applications, for some applications, these circuits present some problems. One such problem is that the asymmetrical arrangement of the current autotransformers shown in FIGS. 6 and 7 of Jewell et al provide a non-unity magnitude transformation in addition to providing the desired phase transformation. This non-unity current magnitude transformation is undesirable as its presence requires additional current transformation circuitry in order to provide accurate measurement. More particularly, such additional current transformation circuitry must be provided in order that identical magnitude transformation is associated with groups of 6 pulse arrangements that are phase shifted with respect to each other. This allows the accurate summation (or comparison) and the determination of the total group current. Another problem with the circuits disclosed by Jewell et al is that, in some power systems, the power transformer primary circuit may involve a zero sequence current component. In such systems, the presence of the zero sequence component may be due to the distributed capacitance of a power transformer winding neutral to ground. In the Jewell et al circuit, no means are provided for handling the presence of the zero sequence current component. As a result, the presence of the zero sequence current may cause inaccurate measurement due to damage to the measurement circuitry. One means employed to provide zero sequence current capability is to connect the neutral connection of the wye connected current transformer secondaries to the ac terminal of a fourth bridge leg of the multiphase instrument rectifier. This provides zero sequence current protection but causes measurement error in the event that zero sequence current exists. Another problem with the Jewell et al circuit and with the Dortort circuit is that no means are provided for indicating the blowing of a fuse associated with the power rectifier circuit. This means that additional circuitry must be provided to indicate such a condition.
Thus, it is a general object of our invention to provide improved means for utilizing alternating input circuit current to measure dc output current in power rectifier apparatus without introducing error due to power transformer phase shift.
Another object of our invention is to provide such an improved measuring means which further includes means for rendering the current transformation substantially unity without the necessity of providing current transformation circuitry in addition to a phase shifting autotransformer.
Another object of our invention is to provide such an improved measuring means which includes means for handling the presence of zero sequence current without causing measurement error or circuit damage.
Another object of our invention is to provide such an improved measuring means which includes means for indicating a blowing of a fuse associated with the power rectifier circuit.
SUMMARY OF THE INVENTION
In carrying out our invention in one form, we provide a system for measuring the magnitude of direct output current from a multiphase power rectifier having an input circuit including a multiphase power transformer. The power transformer has primary and secondary phase windings connected to provide a phase shift between the multiphase primary and secondary line currents coupled by the power transformer. The system includes line current transformers for measuring each of the primary line currents. A phase shifting current autotransformer includes multiple phase windings coupled by separate magnetizable core members in each phase. The core members are designed for normal operation below saturation. Means are provided for connecting the line current transformer secondary windings to the primary windings of the phase shifting current autotransformer. The phase shifting current autotransformer provides a phase shift which, when combined with the phase shift of the line current transformers, is vectorially equal to the phase shift of the power transformer. A multiphase instrument rectifier is connected to the secondary windings of the phase shifting current autotransformer and a direct current measuring instrument is connected to the output terminals of the instrument rectifier.
In accordance with the present invention, the system further includes means for rendering the transformation ratio of the phase shifting autotransformer substantially unity. In another form of the present invention, the system further includes means for providing system capability for the presence of zero sequence current. In another form of the invention, fuse failure detector means are provided for indicating blowing of a fuse associated with the power rectifier circuit.
BRIEF DESCRIPTION OF THE DRAWINGS
Our invention will be more fully understood and its various objects and advantages further appreciated by referring now to the following specification, taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a schematic representation of one form of the present invention showing a power rectifier apparatus including a direct current measuring system.
FIG. 2 is an exemplary connection diagram for use in the direct current measuring system of FIG. 1.
FIG. 3 is a schematic representation of another form of the present invention showing a power rectifier apparatus including a direct current measuring system.
FIG. 4 is a schematic representation of another form of the present invention showing a power rectifier apparatus including a direct current measuring system.
DETAILED DESCRIPTION OF THE INVENTION
Referring initially to FIG. 1, one form of power rectifier circuit and direct current measuring circuit of the present invention for a three phase power system is generally designated 10. Line conductors 12, 14, 16 carry the three phase current between a source (not shown) and a rectifier power transformer 18. The rectifier power transformer 18 includes primary windings P1, P2, P3 connected in extended wye circuit relation. The power transformer 18 also includes secondary phase windings S1, S2, S3 connected in delta circuit relation and also connected through secondary line conductors 20, 22, 24 to a three phase bridge type power rectifier 26 having direct current output terminals T1, T2, coupled to a load 27. The power rectifier 26 is of any conventional type and may, for example, include appropriately poled thyristors 28 in series and/or parallel relation. Each current path includes a current fuse 30. It is to be appreciated that each of the three legs of the rectifier 26 may comprise a plurality of parallel paths, each of the paths including appropriately poled thyristors and fuses corresponding to 28 and 30.
The direct current measuring circuit is generally designated 32 and includes a phase shifting autotransformer 34 which receives the outputs of the primary line current transformers 36, 38 and 40. The secondaries of the primary line current transformers 36, 38, 40 are wye connected. It is to be noted that the phase shifting autotransformer 34 is similar to the one disclosed in the previously mentioned Jewell et al patent but includes several modifications thereto which will be discussed in detail following a general description of the circuit 10. The phase shifting autotransformer 34 is provided with tertiary windings 42 in order to provide system capability for the presence of zero sequence current. The output of the phase shifting autotransformer 34 is connected to an instrument rectifier 44 and to a dc measuring instrument, designated A. The instrument rectifier 44 also includes a fuse failure detector 46 which is connected across a resistor R o which is in series circuit relation with the measuring instrument A.
Referring more particularly now to the phase shifting autotransformer 34, it is to be noted that the phase shifting autotransformer 34 is in double extended wye form and coupled to the tertiary windings 42. More specifically, in a preferred form, each phase employs a separate magnetizable core member, or core. Each core is encompassed by four windings. For purposes of clarity, an exemplary connection diagram for such an autotransformer 34 is depicted in FIG. 2. Each core includes a main (M), or wye winding, with these windings being connected to a common or neutral terminal (N). Two extension windings (E) and (F) are provided, these windings are appropriately connected to the current transformer connection terminals 1, 2, 3 and to the connection terminals A1, A2, A3 for the instrument rectifier 44. The fourth winding comprises the tertiary winding (T). The tertiary windings (T) for the three cores are connected together in closed delta form. For reference information on transformer and rectifier applications, and symbols therefor, see ANSI Standard C34-2-1968 (R1973), entitled, "Practices and Requirements for Semiconductor Power Rectifiers." This reference depicts various vector diagrams of the type employed in FIG. 1 of this application, see especially, Table 6, beginning on page 49 of this reference. More particularly, items 11 and 12 on page 49 appear to disclose a secondary arrangement, "fork," which is somewhat related to the double extended wye autotransformer 34 of FIG. 1 of this application.
The fuse failure detector 46 comprises means for detecting a condition in which the transformed current I D ' through the resistor R o exceeds a predetermined threshold value which is greater than the value at normal rated current. For example, at a typical normal rated load current, I D =36,000 amps, I D '=4.3 amps. Under these conditions, the threshold value will be set at about 110% to 120% of normal rated current, i.e., 4.8 to 5.2 amps. More particularly, the failure detector 46 is actuated by voltage R o ×I D ', where I D ' is the transformed current representing a value in excess of the predetermined value. The detector 46 also includes means for indicating such a condition. Exemplary indicating means may comprise seal in lights and/or alarms.
The operation of the circuit 10 of FIG. 1 will now be more fully discussed. The extended wye to delta arrangement of the power transformer 18 is, for purpose of illustration, assumed to provide a phase shift between the primary voltage e p vector and the secondary e s vector of an angle φ of other than 30°. The wye connected primary current tranformers 36, 38, 40 provide no compensation for this phase shift. The appropriate adjustable phase shift compensation is provided by the double extended phase shifting autotransformer 34. More particularly, as shown vectorially in FIG. 1, the extension windings of the phase shifting autotransformer 34 are so proportioned that the phase shift relationship of the output vector i A to input vector i l is substantially identical to the phase shift relationship of the power transformer voltage vectors e s to e p , and, the magnitudes of vectors i A and i l are substantially equal. This means that the currents flowing between the phase shifting autotransformer 34 and the instrument rectifier 44 are substantially identical to the currents flowing between the power transformer secondary and the power rectifier 26 except for the current transformer and power transformer magnitude transformation ratio. Thus, not only is the appropriate phase shift compensation provided by the double extended phase shifting autotransformer 34, but the phase shifting autotransformer 34 also provides unity current transformation. It should be noted that, the magnitude of phase shift provided by the autotransformer 34 can be made to be adjustable simply by providing symmetrical taps along the extension windings (not shown). With such tap points, the magnitude of phase shift can be varied while maintaining unity current transformation. This is to be contrasted with the operation of the autotransformer in the Jewell et al patent in which varying the phase shift varies the current transformation through values other than unity.
Zero sequence line current from lines 1, 2, 3, to the power transformer 18 requires equivalent transformed currents flowing from the current transformer secondary wye ends to the phase shifting autotransformer input terminals 1, 2, 3, and, to return from the phase shifting autotransformer neutral (N) to the secondary wye neutral of the current transformers 36, 38, 40. In order to ensure that this zero sequence current does not cause ampere turn unbalance on the phase shifting autotransformer 34, the closed tertiary 42 is provided. The closed tertiary 42 allows the necessary compensating current to flow in the windings thereof, thereby providing ampere turn balance on the phase shifting autotransformer. This makes the phase shifting autotransformer 34 a very low impedance to the flow of the zero sequence current. As a result, the zero sequence current is diverted from disturbing the measurements made within the instrument rectifier 44.
Referring now to the operation of the fuse failure detector 46, fuse failure may involve only one of a number of parallel paths which include a fuse 30 in series with a thyristor 28. That is, each of the three current paths shown in FIG. 1 typically comprises about twelve such paths, each including a fuse. Typically, if one fuse blows, the remaining paths will continue to operate. Nonetheless, the fuse interruption current (blown fuse current) will generally be very substantial as compared to normal current. Hence, the transformed current I D ' through the resistor R o of the instrument rectifier 44 will, in many applications, exceed its normal current level, thereby producing operation of detector 46. This relationship can be calculated for a given application such that the detector 46 is actuated by a voltage R o ×I D ' which is above the threshold level. It is to be noted that the fuse blowing event is generally transient as the blowing of the fuse clears the fault from the circuit. This means that subsequent circuit operation is again normal unless additional faults occur. Depending upon the particular power system parameters, fault clearing times may be of the order of hundreds of microseconds to several milliseconds. In any event, it is preferable to provide the detector 46 with seal in gate means which are actuated by the threshold voltage level. These seal in gate means then actuate an annunciator, e.g., light/alarm, to signal the fuse failure. Then, an operator can replace the blown fuse at a time following its failure.
Another power rectifier and dc measuring circuit of the present invention is shown in FIG. 3 and is generally designated 50. The power rectifier and measuring circuit 50 is similar to the circuit 10 of FIG. 1 so that, where possible, like reference numerals have been employed to designate like elements.
The power transformer 18 is shown, for purposes of illustration, as having a delta primary and a wye connected secondary which provide a current angle phase shift φ of 30°. The secondary winding of the primary line current transformers 36, 38, 40 are connected to a phase shifting autotransformer 134 and to a zig-zag autotransformer 52. The purpose of the zig-zag autotransformers 52 will be discussed later in connection with the operation of the circuit 50. The zig-zag autotransformer 52 is a true zig-zag arrangement, preferably employing a separate magnetizable core member, or core, for each phase. Each of the three cores is encompassed by two identical windings, thus, the zig-zag autotransformer 52 involves a total of six identical windings. The two identical windings on each core are preferably wound with low leakage flux therebetween. (This true zig-zag is to be contrasted with an extended wye arrangement in which three windings are of different turns than the three remaining windings). The phase shifting autotransformer 134 is of the type known as a truncated delta arrangement. By this it is meant that each of three separate magnetizable core members, or cores, is encompassed by two windings. One of these windings is a main, or greater turns winding, and the other is a minor, or lesser turns winding. (If the phase shift required is 60°, all the windings are of equal turns). All the main windings, and all the minor windings are respectively substantially identical. The windings of the three separate cores are interconnected in closed truncated delta form, as shown in FIG. 3. By constructing the vectors from the neutral or center of the truncated delta, the phase shift and the unity current transformation is depicted. The relative windings of the major and minor windings are chosen such that the angle φ of vector i A to vector i l is substantially identical to the angle of vector e s to vector e p .
In the operation of the dc measuring circuit 50, the truncated delta arrangement 134 functions in substantially the same manner as the double extended arrangement 34 of the measuring circuit 10 of FIG. 1. More particularly, it exhibits the identical phase shift that is associated with the power transformer 18 as well as unity current transformation. However, the truncated delta arrangement 134 does not provide for zero sequence current flow. To provide capability for such flow, the neutral (N) of the zig-zag autotransformer 52 is connected to the neutral of the wye formed by the secondary windings of the line current transformers 36, 38, 40. Under these circumstances, zero sequence current can flow as follows: out of the ends of the wye connected line current transformers 36, 38, 40; into the associated terminals 1, 2, 3, of the zig-zag autotransformer 52; through the zig-zag autotransformer 52 windings to its neutral (N); and return to the line current transformer secondary neutral. The zig-zag autotransformer 52 provides a low impedance to the zero sequence current flow, and hence, provides a suitable path therefor. The fuse detector 46 will not be discussed in connection with the circuit 50 as its operation is substantially the same as that described in connection with the circuit 10 of FIG. 1.
Another dc measuring system of the present invention is shown in FIG. 4 and is generally designated 60. The measuring system 60 is similar to the measuring systems 10 and 50 of FIGS. 1 and 3 so that, where possible, like reference numerals have been employed to designate like elements.
The measuring system 60 is shown in connection with two power transformers 118, hereinafter also designated A and B. As is known in the art, six pulse systems, such as those hereinbefore in FIGS. 1 and 3, can be improved by going to a higher pulse system. For example, problems due to harmonics in a six pulse system can be minimized by going to a twelve or twenty four pulse system. The twelve and twenty four pulse systems are typically obtained by combining a number of six pulse systems at a predetermined phase angle therebetween. For example, in FIG. 4, the power transformers A and B are combined to the load 27 through multiphase rectifiers 26A, 26B. The angle of -30° between the secondaries of the two transformers A and B causes the combined system to function as a twelve pulse system. A twenty four pulse system (not shown) can be obtained by combining two such twelve pulse systems with an angle of 15° displacement therebetween.
In the measuring system 60, the power transformer A includes an extended wye primary and a delta secondary exhibiting -37.5° phase shift. Power transformer B includes a truncated delta primary and a delta secondary exhibiting a -7.5° phase shift. As mentioned previously, this system may comprise a portion of a twenty-four pulse system. The power transformers A and B supply three phase double way bridges 26A, 26B which are connected in parallel to supply a common load 27.
The primary line current transformer secondaries 62A, 64A, 66A and 62B, 64B, 66B are respectively cconnected in delta to each exhibit a -30° phase shift. (Note they could also be connected in delta to exhibit a +30° phase shift). The delta connection provides a circulating path for the induced zero sequence components of the primary line currents, if such exist. The unity gain phase shifting current transformers, designated 234A, 234B, illustrated in truncated delta form, provide respectively -7.5° and +22.5° phase shift for the primary currents associated with the power transformers A and B. The instrument rectifier 144 is similar to the instrument rectifiers of the six pulse systems of FIGS. 1, 3, but includes several modifications thereto. The instrument rectifier 144 preferably includes three dc measuring instruments, designated A A , A B , A A+B .Instrument A A measures the dc load current I DA provided by the transformer A; instrument A B meausres the dc load current I DB provided by transformer B; and instrument A A+B measures the total dc load current I D provided to the load 27. It is to be noted that, the unity current transformation of the phase shifting current autotransformers 234A, 234B is particularly desirable for this system. More particularly, the phase shifting operation introduces no additional error into the measurement process.
The power rectifier and direct current measuring circuit of the present invention has hereinbefore been described in connection with embodiments which preferably included the following: means for providing substantially unity current transformation in the phase shifting autotransformer; means for handling zero sequence current; and fuse detector means. However, it is to be noted that these three features need not all be present at the same time. For example, if zero sequence capability is not needed, the tertiary windings 42 of the circuit 10 in FIG. 1 and the zig-zag autotransformer 52 of the circuit 50 of FIGS. 2 may be omitted. Also, although the embodiments hereinbefore described have included a power rectifier circuit employing thyristors, other arrangements may be substituted therefore. For example, such arrangements may include diodes or a combination of diodes with saturating reactors.
It is to be appreciated that the phase shifting autotransformer employed in the present invention to provide the proper phase angle compensation and unity current transformation need not be adjustable but may instead comprise a fixed phase shift, e.g., 30° . Also, although it is generally preferable to provide three separate magnetizable cores, one for each phase (in a three phase system), a single magnetizable core member having three separate core legs may also be provided. Further, although the present invention has been described in connection with a three phase power system, it is to be appreciated that the present invention is generally applicable to multiphase power systems including 6 phase, 12 phase or 36 phase circuits used in very high power rectifiers.
While we have illustrated preferred embodiments of our invention, many modifications will occur to those skilled in the art and we therefore wish to have it understood that we intend in the appended claims to cover all such modifications as fall within the true spirit and scope of our invention. | A dc measuring circuit for power rectifiers is described wherein primary line current is utilized to measure direct current output. In the measuring circuit, line current transformers are connected to a multiphase instrument rectifier through a phase shifting current transformer which is adjustable to compensate for differences between the primary and secondary line current phase shift characteristics of the power transformer and any phase shift in the line current transformer. By such compensation, the average value of rectified primary line current in the measuring circuit is maintained independent of the commutating angle of the rectified power current. The dc measuring circuit includes means for providing unity current transformation through the phase shifting current transformer. The dc measuring circuit also includes means for handling the presence of zero sequence current without causing measurement error or circuit damage. The dc measuring circuit also includes means for indicating the blowing of a fuse associated with the power rectifier circuit. In one embodiment, the phase shifting current transformer comprises a double extended wye connected autotransformer. In another embodiment, the phase shifting current transformer comprises a truncated delta autotransformer. | 6 |
SUMMARY OF THE INVENTION
This invention relates generally to wrapping machines of the type particularly adapted to handle sticks of gum individually, and collectively in a stack for wrapping purposes. More particularly, this invention relates to a stacking station within such a machine for accumulating a predetermined number of sticks in a stack for purposes of applying an outer wrapper thereto. Machines for feeding sticks of gum either wrapped or unwrapped to a stacking station are well known in the art, and the reader is referred to the Smith et al U.S. Pat. No. 2,276,744 for a complete disclosure of one possible system for feeding sticks of gum individually to a stacking station. In more recent machines capable of higher speeds than that of the type disclosed in the Smith patent, the sticks of gum are individually fed into the stacking station by an indexing wheel, but it is a feature of the present invention that the stacking mechanism to be described is suitable for use with any of these types of stick infeed mechanisms.
Still with reference to the prior art generally, the Smith U.S. Pat. No. 2,276,744 also shows means for handling the stack of gum sticks whereby the stack is fed generally at right angles to a web of material and into one of several openings provided for this purpose in a tumble box or the like where the stack of gum sticks is further handled, usually being wrapped in the outer wrapper prior to being discharged from the machine.
The present invention relates to the mechanism for forming the stack of gum sticks fed individually to the stacking station so that they can be conveniently moved out of the stacking station in a downstream direction for further handling. More particularly, the present invention relates to means for elevating each stick fed to the stacking station, and said means may comprise a rotating stacker wheel with lobes suitable for indexing the sticks fed to recesses provided for this purpose in the wheel and for elevating each of these sticks in its turn at the stacking station. Side guides are provided at either end of the stack for guiding the ends of the sticks so elevated, and these side guides are mounted for limited lateral movement toward and away from one another in order to center the stack at the stacking station. Biasing means in the form of coiled compression springs are provided for urging these side guides inwardly toward one another to keep the stack oriented in centered relationship, and it is a further feature of the present invention that abutments are provided on the downstream edges of these side guides in order to further assist in supporting the stack as succeeding sticks are fed into the bottom of the stack at this stacking station.
Thus, the general aim of the present invention is to provide an improved stacking mechanism whereby the sticks of gum are positively handled throughout the stacking process, including that portion of the cycle when these stacked sticks of gum are pushed out of the stacking station into the web of outer wrapper material to be wrapped in a tumble box or the like.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a vertical elevational and partial sectional view illustrating the stacking station with reference to the stick infeed mechanism for the sticks of gum, and also with reference to the tumble box in which the stack is wrapped, these latter portions of the drawings being illustrated in schematic fashion only to provide a frame of reference for the stacking mechanism to be described.
FIG. 2 is a vertical sectional view looking upstream being taken generally on the line 2--2 of FIG. 1, but through the side guide supporting structure at the stacking station.
FIG. 3 is a plan view of the stacking mechanism illustrated in FIGS. 1 and 2.
FIG. 4 is a sectional view taken generally on the line 4--4 of FIG. 3.
DETAILED DESCRIPTION
Turning now to the drawings in greater detail, FIG. 1 shows a series of gum sticks S, S fed by the pocket P of an index wheel 11 through a track defining structure 10 in the direction of the arrow 12 generally toward a stacking station to be described. While these gum sticks may be prewrapped, the actual process for wrapping these sticks and feeding them to the stacking station forms no part of the present invention and any conventional mechanism might be adapted for feeding these sticks S, S either by an index wheel as shown at 11, or by means of a walking beam of the type described in the above mentioned U.S. Pat. No. 2,276,744 to Smith et al, or by other means.
A stacker wheel 14 rotates on a fixed axis in the machine, and more particularly on the shaft 16 driven in the direction of the arrow 18 by suitable means (not shown) and preferably in timed relationship with the operation of other components of the machine, such as the index wheel 11, in a well known manner. As shown in FIG. 1 the foremost stick S in the stream of incoming gum sticks will move into one of the recesses defined by the stacker wheel 14 and be fed by the rotating index wheel 11 toward the surface 22 at the stacking station. When the stick S has reached the stacking station the lobe 24 on the stacker wheel 14 will cause that stick S to be raised upwardly between two side guides, one of which is shown at 26 in FIG. 1. The next stick of gum among those fed to the stacking station by the infeed or index wheel 11 will be received in the next pocket of the stacker wheel 14, with the result that it will be fed in under the first stick at the stacking station between the side guides 26 and 28, best shown in FIG. 2.
As a predetermined number of sticks are being stacked between the side guides 26 and 28 a stack pusher 30 will have travelled from the position shown in FIG. 1 generally rearwardly and upwardly in the direction of the arrow 32 and thence downwardly behind the stack, as suggested by the portion of the path indicated generally at 34 in FIG. 1, with the result that the pusher 30 is in position for moving the stack downstream. The side guides 26 and 28 remain at the stacking station and the stack is pushed toward the viewer in FIG. 2 through a passageway 36, defined for this purpose in the machine, to ultimately engage a web of wrapper material W such that the web and the stack of gum sticks can be received in a conventional tumble box structure as indicated generally at 38. The reader is referred to the above mentioned U.S. Pat. No. 2,276,744 issued to Smith et al for a more complete description of the portion of the machine downstream of the stacking station, that is for a more complete description of the pusher means 30 for moving the stack out of the stacking station and the associated mechanism for imparting the path of movement to the pusher as illustrated schematically in FIG. 1 by the path of the arrows 32, 34. The tumble box structure and the means for timing the rotation of the tumble box with the rotation of the index wheel 11 is also described in detail in said U.S. Pat. No. 2,276,744.
As described in the above mentioned patent, the pusher 30 is adapted to move downstream in the direction indicated schematically for it in FIG. 1, and the pusher itself more particularly comprises a pair of pusher members 30a and 30b which pusher members are adapted to move downwardly at the rearward limit of travel so as to be received in slots such as those indicated generally at 36a and 36b in FIG. 2. It is an important feature of the present invention that the pusher elements 30a and 30b must free the stack of sticks from the side guides, 26 and 28, and more particularly must supply sufficient force to cause the side guides to pivot away from one another so that the ends of the stack will be forced between the abutments 26a and 28a best shown in FIG. 3. The direction of movement of the stack in response to the above described motion of the pusher members 30a and 30b is illustrated generally by the arrow in FIG. 3, and although the pusher 30 itself is not illustrated in FIG. 3 it will be apparent that the pusher elements 30a and 30b will clear the stacker wheels 14 and 14a as best shown in FIG. 2.
Referring now more particularly to the construction of the side guides 26 and 28, and the means for supporting these side guides for limited movement toward and away from one another, FIG. 2 shows each of these side guides 26 and 28 as being supported for limited pivotal movement on an associated rock shaft 40 and 42 respectively. The location for these rock shafts is below the path of travel of the stack as it moves out of the stacking station, and these rock shafts are supported in fixed brackets 68 mounted to the machine frame 62 so as to permit the limited pivotal movement of the side guides 26 and 28 as described above. Each of these guides is biased inwardly toward the other by an associated spring, 44 and 46 respectively, said springs acting between the fixed brackets in the machine and the upwardly extending side guides as best shown in FIG. 2. Still with reference to the side guides 26 and 28, each of these can be seen from FIG. 2 to be of generally L-shape, the upwardly extending leg of the L defining the side guide portion, 26a and 28a respectively, thereof and the horizontally extending leg thereof defining an arm, 26b and 28b respectively, which can be engaged by a stop screw 48 and 50 respectively. The stop screws 48 and 50 can be preadjusted to limit the inner travel of the side guides, 26 and 28 respectively, until the first stick in the stack of gum sticks has reached the stacking station. Adjustable nuts, 52 and 54, are provided on these stop screws, 48 and 50 respectively, in order to lock the associated screws in the desired position for determining the inner limit of movement of the associated side guide 26 and 28 absent the gum sticks. As the gum sticks are accumulated at the stacking station, the stack moves up and the side guides move out slightly with the addition of each stick. The guides continue to keep end pressure on the sticks under the influence of the springs 44 and 46.
Means is provided above the stack of gum sticks being formed at the stacking station for urging the stack into a compacted condition prior to feeding of the stack through the passageway 36 described above. As best shown in FIG. 1, said means preferably comprises at least one presser foot 56 mounted in a structure 58, which structure is adapted for preadjustment to accommodate stacks of different height. The presser foot 56 is mounted, through a pin and slot connection, to the structure 58 and is spring biased downwardly as illustrated by the coiled compression spring 60 in FIG. 1. Thus, the presser foot 56 is adapted to urge the stack downwardly in order to hold it in a compressed condition at the stacking station, and thereby facilitate feeding of the stack in a downstream direction out of the stacking station through the passageway 36 and into an associated receptacle provided for this purpose in the rotating tumble box 38.
In accordance with conventional gum wrapping machine practice, the various components described above are mounted from a vertically extending plate or frame, such plate or frame being indicated generally at 62 in FIG. 1. As illustrated generally at 64, additional fixed frame structure is provided for mounting the passageway defining structure 66 in the path of movement of the stack as the stack is fed by the pusher 30 from the stacking station. The shaft 16 associated with each of the two stacker wheels 14 and 14a is split, having a portion 16a best shown in FIG. 2 associated with the right hand stacker wheel 14a. The fixed passageway defining structure 66 is also supported from the frame 62 and carries the bracket super-structure 68 for supporting the rock shaft 40 associated with the side guide 26. The other rock shaft 42 is similarly supported and the overall details of the supporting structure for the various components of a machine incorporating the present invention have been omitted herein for the purpose of clarifying the disclosure of the stacking mechanism to which the present invention is directed, as defined in the following claims. | Sticks of gum are fed individually to the bottom of a stack where each stick is raised by an elevator wheel to form the stack between side guides pivotally mounted, and biased toward one another. Each side guide has an abutment to keep the stack aligned vertically, and a presser foot resiliently holds the stack from above so that a pusher can move the stack out of the stacking station, into a wrapper, and thence into a tumble box for further handling. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an apparatus, such as a camera, which is adapted to use a shape memory member.
2. Description of the Related Art
A proposal regarding an apparatus adapted to use a shape memory alloy as a shape memory member has been made in Japanese Patent Application No. Hei 7-19175. According to the proposal, such an apparatus includes a first cover provided with a shape memory alloy wire and a second cover provided with a solar battery, and the function of the apparatus is such that when the temperature of the shape memory alloy wire reaches a predetermined temperature, the shape memory alloy wire recovers its shape (shrinkage) and hence the engagement of a latch claw connected to the wire is released, whereby the first and second covers are made to move integrally in a direction away from the body of the apparatus by the force of a spring, thereby producing a space between the body of the apparatus and the first and second covers to prevent overheating of the body of the apparatus.
However, the construction of the above-described proposal presupposes that the shape memory alloy is used at a suppressed strain of 1% or less in the state of small hysteresis (an elasticity area) (if the hysteresis becomes large, the shape memory alloy becomes unable to recover its original shape even if a temperature fall occurs). Accordingly, the shape memory alloy can only provide a small amount of displacement with respect to a variation in the temperature of the shape memory alloy.
For this reason, in the case of a wire-shaped shape memory alloy which can be disposed within a small space in an apparatus, as shown in FIG. 12, the amount of displacement (B) of such shape memory alloy, which is obtainable from the temperature variation thereof, is extremely small the obtainable amount of displacement of a wire of approximately 80 mm long is approximately 0.3 mm, inclusive of a safety margin which ensures that the wire can always be used in the state of small hysteresis). As a result, in the case of the apparatus having the above-described construction, since the amount of engagement of a latch claw cannot be made large at normal temperatures, the first cover may open by a vibration or by a shock due to a fall.
SUMMARY OF THE INVENTION
In accordance with one aspect of the present invention, there is provided an apparatus which comprises a shape memory member, a deforming device which deforms the shape memory member into a predetermined state, an operating device which performs a predetermined movement in response to a movement in which the shape memory member restores itself from the predetermined state to a memorized state, and a restraining device which restrains an operation of the deforming device at least when the shape memory member performs the movement of restoring itself from the predetermined state to the memorized state, so that the shape memory member can correctly restore itself to the memorized state an d the operating device can correctly perform a desired movement.
The above and other objects, features and. advantages of the present invention will become apparent from the following detailed description of preferred embodiments of the present invention, taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an exploded perspective view showing an essential portion of a camera which is an apparatus according to a first embodiment of the present invention;
FIG. 2 is an exploded perspective view showing an essential portion of the camera shown in FIG. 1;
FIGS. 3(a), 3(b) and 3(c) are diagrammatic side elevational views showing the operation of the camera shown in FIG. 1, FIG. 3(a) representing a state in which a grip cover 4 provided with a shape memory alloy wire 15 is rotated forwardly from a camera body 1, FIG. 3(b) representing a state in which the grip cover 4 is being returned toward the camera body 1, and FIG. 3(c) representing a state in which the grip cover 4 is engaged with the camera body 1;
FIGS. 4(a) to 4(c) are schematic side elevational views showing different positions which are taken by a solar cover 2 provided on the camera of FIG. 1 during the movement of the solar cover 2, FIG. 4(a) representing a state in which the camera is not in use, FIG. 4(b) representing a state in which the solar cover 2 is located away from the camera body 1 to prevent overheating of the camera body 1, and FIG. 4(c) representing a state in which photography is possible;
FIG. 5 is a schematic view aiding in explaining the relationship of the relative movement between a cam and a cam follower 7 which allow the grip cover 4 and the solar cover 2 of the camera shown in FIG. 1 to be independently movably joined to each other;
FIG. 6 is a circuit diagram showing one example of a power source circuit portion provided in the camera of FIG. 1;
FIG. 7 is a graph showing the relationships among the hysteresis of the shape memory alloy wire 15 of the camera of FIG. 1 before and after the deformation of the shape memory alloy wire 15, the strain of the shape memory alloy wire 15 and the load thereof;
FIG. 8 is a perspective view of an essential portion of a camera according to a second embodiment of the present invention having a driving arrangement for both giving strain to the shape memory alloy wire 15 by power driving and power-driving the grip cover 4 in a closing direction;
FIG. 9 is a circuit diagram of one example of a power source circuit portion of the camera shown in FIG. 8;
FIG. 10 is a flowchart of a microcomputer 33 of FIG. 9;
FIG. 11 is a circuit diagram showing a third embodiment of the present invention which is a partial modification of the circuit shown in FIG. 9; and
FIG. 12 is a graph showing the strain-load characteristics of the shape memory alloy wire used in a previously proposed apparatus.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Preferred embodiments of the present invention will be described below in detail with reference to the accompanying drawings.
FIGS. 1 to 6 show a first embodiment of the present invention. The first embodiment relates to an example of a camera to which the present invention is applied, but the range of application of the present invention is not limited to only the camera and encompasses various other apparatuses such as portable telephones, radios and portable computers.
FIG. 1 is an exploded perspective view of the camera according to the first embodiment of the present invention, and mainly shows the internal mechanism of a grip cover (first cover). In FIG. 1, the grip cover is represented by two-dot chain lines and the camera is shown in partly transparent form for convenience sake. FIG. 2 is an exploded perspective view of the camera, and mainly shows an arrangement for urging a solar cover (second cover) in a closing direction with respect to the grip cover (first cover). FIGS. 3(a) to 3(c) are side elevational views showing the internal portion of the grip cover in partly transparent form, similarly to FIG. 1. FIG. 3(a) shows a state in which the grip cover is opened as the camera is heated to a high temperature by exposure to the direct rays of the sun. FIG. 3(b) shows a state in which the grip cover is manually being closed after the camera has been air-cooled owing to the opening of the grip cover. FIG. 3(c) shows a state in which the grip cover is completely closed.
FIGS. 4(a) to 4(c) are schematic side elevational views of the camera. FIG. 4(a) shows a state in which the solar cover is closed so that the user can normally carry the camera. FIG. 4(b) shows a state in which the grip cover is opened as the temperature of the camera rises and the solar cover is also opened in accordance with the opening of the grip cover. FIG. 4(c) shows a photography-enabled state in which the solar cover is independently opened.
FIG. 5 is an explanatory view of a cam for urging the solar cover (second cover). FIG. 6 is a circuit diagram of the power source portion of the camera. FIG. 7 is a graph showing the strain-load characteristics of a shape memory alloy applied to the camera, and the hysteresis characteristics of expansion and shrinkage at 60° C. are represented by solid lines, while the hysteresis characteristics of expansion and shrinkage at 25° C. are represented by dashed lines. The force with which a wire made of a shape memory alloy is pulled by the action of a tension spring 20 is represented by alternate short and long dash lines.
Referring to FIGS. 1 to 7, a camera body 1 includes a lithium-ion secondary battery 1a provided in built-in form at the position shown in part by solid lines and in part by dashed lines in FIG. 1, and a photographing lens barrel 1b.
Five solar battery cells 3 each of which is made from amorphous material are attached to a solar cover 2 in such a manner as to extend thereon in parallel with one another. The solar cover 2 also has the function of a protection cover for covering a photographing optical system and a viewfinder optical system. As shown in FIG. 6, the solar battery cells 3 are connected in series, and are arranged to supply electrical power to the lithium-ion secondary battery 1a when illuminated with light.
The camera body 1 also includes a grip cover 4 and a bottom cover 5 having hinge portions 5a, 5b and 5c. The solar cover 2, the grip cover 4 and the bottom cover 5 are joined by a hinge shaft 6 fitted in these three components, whereby the solar cover 2 and the grip cover 4 are supported for rotation about the hinge shaft 6. The bottom cover 5 on which the solar cover 2 and the grip cover 4 are supported for rotation about the hinge shaft 6 is fixed to the bottom of the camera body 1 by means of screws. A cam follower 7 is fitted in a hole 2a provided in the solar cover 2, and a key 7a is engaged with a key groove 2b of the solar cover 2 to prevent rotation of the cam follower 7. The cam follower 7 has a through-hole 7b through which the hinge shaft 6 is inserted in such a manner that the cam follower 7 can rotate and axially slide with respect to the hinge shaft 6. A compression spring 8 has an urging force which acts to press a cam abutment portion 7c of the cam follower 7 against cam faces 4a to 4c integrally provided on the grip cover 4. The compression spring 8 is accommodated in the hole 2a of the solar cover 2 together with the cam follower 7. When the solar cover 2 is placed in its closed position (the state shown FIG. 4(a)), the cam abutment portion 7c of the cam follower 7 is pressed against the cam face 4a, whereby the solar cover 2 is urged in a closing direction (the direction indicated by an arrow A in FIG. 2) with respect to the grip cover 4 and an oblique face 2c of the solar cover 2 is maintained in abutment with an oblique face 4d of the grip cover 4. A switch actuating member 9 is axially slidably fitted on the hinge shaft 6 similarly to the cam follower 7. A compression spring 10 has an urging force which acts to press a cam abutment portion 9a of the switch actuating member 9 against a cam face (not shown) integrally provided on the solar cover 2. The switch actuating member 9 is arranged to move toward the right as viewed in FIG. 2 in accordance with the opening movement of the solar cover 2 and toward the left by the spring force of the compression spring 10 in accordance with the closing movement of the solar cover 2. A switch plate 11 has contacts 12 and 13 retained by heat caulking, and is arranged to move toward the right and the left integrally with the switch actuating member 9 with an engagement portion 11a being engaged with a recess portion 9b of the switch actuating member 9. The contacts 12 and 13 are in contact with the pattern of a printed wiring board (not shown), and are operative to turn on or off a power source according to the rightward or leftward movement of the switch plate 11. The contacts 12 and 13 constitute a microcomputer activating switch 34 and a main switch 35, both of which are shown in FIG. 6.
A mechanism which is disposed inside the grip cover 4 will be described below. The mechanism includes a grip base plate 14 and a shape memory alloy wire 15 made of Ni--Ti, and the shape memory alloy wire 15 is fastened at one end to an adjustment plate 16 by caulking and at the other end to a cylindrical collar 17 by caulking. A latch claw 18 is supported for rotation about a shaft 14a of the grip base plate 14, and is retained by a grip ring 19 so as not to come off the shaft 14a.
The collar 17 to which the shape memory alloy wire 15 is fastened at one end is engaged with a recess provided in an arm 18a of the latch claw 18, and the shape memory alloy wire 15 is passed along an arc-shaped rib 14d of the grip base plate 14 in the vicinity of the inside face of the grip cover 4. The adjustment plate 16 to which the shape memory alloy wire 15 is fastened at the other end by caulking is supported for rotation about a shaft 14b of the grip base plate 14. The adjustment plate 16 is fixed to the grip base plate 14 by a screw after the tension of the shape memory alloy wire 15 has been adjusted. The tension spring 20 is disposed between an arm 18b of the latch claw 18 and a dowel 14c of the grip base plate 14 to urge the latch claw 18 in the counterclockwise direction.
The grip base plate 14 having the above-described mechanism is held on the back and side faces of the grip cover 4 by screws (not shown). A torsion spring 21 serves to urge the grip cover 4 to open in a direction away from the camera body 1. Normally, a user carries the camera with a claw portion 18c of the latch claw 18 being held in engagement with a claw engagement portion 1d of the camera body 1 by the charged urging force of the torsion spring 21, i.e., with the grip cover 4 being closed in the state shown in FIG. 3(c). If the camera is exposed to intense sunlight, the temperatures of the solar battery cells 3 and the grip cover 4 become higher, so that the shape memory alloy wire 15 is deformed and shrinks to its memorized length. Thus, the latch claw 18 is made to turn in the clockwise direction against the spring force of the tension spring 20, whereby the claw portion 18c disengages from the claw engagement portion 1d of the camera body 1. When the claw portion 18c disengages from the claw engagement portion 1d, the grip cover 4 opens by the spring force of the torsion spring 21, and is made to stop when a rib 4e integrally provided on the inside of the grip cover 4 comes into abutment with a dowel 1c of the camera body 1 and the opening angle of the grip cover 4 reaches approximately 25° (the state shown in FIG. 3(a)).
A manual release knob 22 is provided on the side face of the grip cover 4 in such a manner as to be slidable upward and downward. When the user slides the manual release knob 22 downward against the urging force of a compression spring 23, an arm 18e of the latch claw 18 rotates by being pressed by a shaft 22a of the manual release knob 22, so that the claw portion 18c can be disengaged from the claw engagement portion 1a of the camera body 1.
A pulling mechanism for the shape memory alloy wire 15 which constitutes one feature of the present apparatus will be described below. A V-shaped lever 24 is supported for rotation about a shaft 1e provided on a side of the camera body 1. The V-shaped lever 24 is prevented from coming off the shaft 1e, by a lever pressing tongue 25a of a battery cover 25 which covers the lithium-ion secondary battery 1a. The battery cover 25 is attached to the side of the camera body 1 by a screw (not shown). The torsion spring 26 serves to urge the V-shaped lever 24 in the counterclockwise direction, and when the grip cover 4 is opened, one arm end 24a of the V-shaped lever 24 is positioned in abutment with a projection 1f of the camera body 1 (the state shown in FIG. 3(a)).
FIG. 6 is a block diagram showing the power source portion of a circuit suited to the present apparatus (the camera). The power source portion includes a solar battery 30, the lithium-ion secondary battery 1a, a diode 31 for preventing a reverse current, a known overcharging preventing circuit 32, a microcomputer 33 for controlling the camera body 1, the microcomputer activating switch 34 which is turned on when the solar cover 2 is made open, and the main switch 35 which is arranged to be turned on immediately after the main switch 34 has been turned on. Specifically, in the power source portion, a power-saving circuit construction is realized in that even the supply of electrical power to the microcomputer 33 is shut off when the apparatus (the camera) is not in use.
The operation of the camera having the above-described construction will be described below. Normally, the user carries the camera with the solar cover 2 and the grip cover 4 being closed as shown in FIGS. 3(c) and 4(a), so that the solar battery cells 3 are exposed to external light to charge the lithium-ion secondary battery 1a with electricity. When the solar cover 2 and the grip cover 4 are in their closed states, the shape memory alloy wire 15 is expanded by the pulling mechanism for the shape memory alloy wire 15 which will be described later, and the latch claw 18 is engaged with the claw engagement portion 1d of the camera body 1. In addition, the cam abutment portion 7c of the cam follower 7 fitted in the solar cover 2 is pressed by the cam face 4a of the grip cover 4, whereby the solar cover 2 is urged in the closing direction.
As the solar cover 2 urged in this manner is opened by hand for the purpose of photography, the cam abutment portion 7c climbs up the cam face 4a while charging the compression spring 8, as shown in FIG. 5. When the cam abutment portion 7c is located in an area "a" of FIG. 5, an urging force is applied to the solar cover 2 in the closing direction. When the cam abutment portion 7c is located in an area "b", no urging force is applied to the solar cover 2 in either of the opening and closing directions (the state shown by dashed lines in FIG. 4(c)). When the cam abutment portion 7c enters an area "c", a force which urges the solar cover 2 in the opening direction is produced. Accordingly, the fluctuation of the solar cover 2 is suppressed even when the solar cover 2 is located at a photographing position where it is fully opened. As the solar cover 2 is opened, the switch actuating member 9 climbs up a cam face (not shown) integrally provided on the solar cover 2 while charging the compression spring 10, and travels toward the right as viewed in FIG. 2 and turns on the microcomputer activating switch 34 and then the main switch 35 in accordance with a switching pattern of the printed wiring board which is in contact with the contact 12. When the main switch 35 is turned on, the photographing lens barrel 1b moves forward from its barrel-retracted state to its photography standby position, as shown in FIG. 4(c), so that photography becomes possible. Contrarily, as the solar cover 2 is closed, the switch actuating member 9 travels toward the left by the spring force of the compression spring 10 and the main switch 35 is turned off, whereby the photographing lens barrel 1b is retracted. Even during the aforesaid movement of the solar cover 2 for the purpose of photography, the grip cover 4 is maintained in the closed state with respect to the camera body 1.
The following description is made in connection with the operation of the aforesaid camera which is capable of coping with a temperature rise which may occur while the user is charging the secondary battery of the camera in direct sunshine.
According to the experiment made by the present inventor, it has been found out that the temperature of the interior of a vehicle which is parked in fine weather in an area near to the equator (for example, Malaysia) reaches approximately 90° at or near the dashboard and the average air temperature of the interior reaches as high as 52° C.
If the camera is placed in such an environment in the state shown in FIG. 4(a), the temperature of the solar battery cells 3 of the solar cover 2 will rise above 90° C. in approximately one hour, and the temperature of the air layer between the solar cover 2 and the camera body 1 and that of the front face of the camera body 1 will rise to an excessively high temperature of approximately 85° C. (Since the thickness of the air layer can only be made as large as approximately several millimeters in terms of portability, the speed at which a convection current of fresh air flows in the air layer is restricted to only several millimeters per second owing to the viscous resistance of air to the back face of the solar cover 2 and the front face of the camera body 1. For this reason, when the camera is in the state of FIG. 4(a), the effect of cooling the back face of the solar cover 2 is low.) As a result, not only will the components of the camera body 1 be damaged, but also the temperature of the aforesaid lithium-ion secondary battery 1a will rise above 65° C., and the temperature of film may also rise above 60° C.
The present apparatus has a function which is capable of preventing occurrence of the above-described overheated state.
If the camera is placed in direct sunshine in the states shown in FIGS. 3(c) and 4(a), the temperatures of the solar cover 2 and the grip cover 4 as well as the temperature of the solar battery cells 3 rise. Particularly when the camera is exposed to a severe environment such as the aforementioned one, the temperature of the grip cover 4 becomes equal to or higher than 60° C. in approximately twenty minutes. Then, the shape memory alloy wire 15 made of Ni--Ti is deformed and shrinks to cause the latch claw 18 to turn in the clockwise direction against the spring force of the tension spring 20, thereby disengaging the claw portion 18c from the claw engagement portion 1d of the camera body 1. Then, the grip cover 4 is opened by an opening angle of approximately 25° by the spring force of the torsion spring 21, so that the rib 4e of the grip cover 4 comes into abutment with the dowel 1c (the state shown in FIG. 3(a)). With the opening movement of the grip cover 4, the oblique face 4d of the grip cover 4 presses the oblique face 2c of the solar cover 2 upwardly, so that the solar cover, 2 is also opened by an opening angle equal to that of the grip cover 4 (the state shown in FIG. 4(b)). Since the solar cover 2 is urged via the cam follower 7 in the closing direction with respect to the grip cover 4, the torsion spring 21 needs only have a sufficient force to press the grip cover 4 and the solar cover 2 upwardly. When the camera is in the state shown in FIGS. 3(a) and 4(b), the air layer between the solar cover 2 and the camera body 1 becomes not less than 15 mm thick (with respect to the original several millimeters), so that the solar cover 2 and the front face of the camera body 1 are cooled by the convection current of fresh air (a maximum of 52° C.). In particular, the temperature of the front face of the camera body 1, which is covered with the shades of the solar cover 2 and the grip cover 4 which have been popped up, falls to a temperature approximately equal to the air temperature of the interior of the vehicle. In addition, since the solar battery cells 3 continue to absorb the energy of the sunshine, the temperature of the solar cover 2 rises to a further extent, but does not exceed the aforementioned 90° C., because the back face of the solar cover 2 is cooled by fresh air.
In addition, the lithium-ion secondary battery 1a which is easily affected by high temperatures is disposed in the camera body 1 in an area thereof which can be covered with the shade of the grip cover 4, so that even if the user erroneously places the camera under the light of the sun with the solar cover 2 being fully open, the outside portion of the camera body 1 which is adjacent to the lithium-ion secondary battery 1a built therein is prevented from being exposed to the direct rays of the sun. Accordingly, the lithium-ion secondary battery 1a behind that outside portion is prevented from being heated to a high temperature. In addition, since film is laid in a back portion of the camera body 1, the temperature of the film only rises to a practically allowable temperature (experimentally, approximately 45° C.), so that the film practically does not suffer any problem.
Even after the camera has been left in the above-described environment for several days, if the user does not forget to carry the camera out of the vehicle, fresh air (in many cases, 40° C. or less) flows into the space between the camera body 1 and the solar cover 2 which is located away from the camera body 1 in the popped-up state, and rapidly cools the shape memory alloy wire 15.
When the temperature of the shape memory alloy wire 15 falls below 55° C., the shape memory alloy wire 15 is restored to the original state and the tension of the shape memory alloy wire 15 lowers.
As shown in the graph of FIG. 7, even if the temperature falls to 25° C. (normal temperature) and the tension of the shape memory alloy wire 15 lowers, since the acting force of the tension spring 20 hooked on the latch claw 18 is set to be lower than a yield force F25 of the shape memory alloy wire 15 at 25° C., the shape memory alloy wire 15 cannot be pulled to a great extent by the force of the tension spring 20, with the result that the shape memory alloy wire 15 cannot be expanded up to a yield area in which the amount of engagement of the latch claw 18 with the claw engagement portion 1d can be made large.
In contrast, if the force of the tension spring 20 is designed to be stronger than the yield force F25, the tension spring 20 may produce a spring force stronger than a recovery force f60 at 60° C., with the result that the latch claw 18 cannot be actuated at 60° C. and the engagement of the latch claw 18 is not released before the temperature of the shape memory alloy wire 15 reaches a higher temperature (for example, 80° C.). In other words, if the difference between the normal temperature (25° C.) and an operating temperature (in the present embodiment, 60° C.) is small, the above-described problem will occur. To solve the problem, the present embodiment is arranged so that the force of the tension spring 20 is set to be lower than the yield force F25 and the shape memory alloy wire 15 can be pulled and deformed to a great extent by the pulling mechanism for the shape memory alloy wire 15 which is interlocked with the closing movement of the grip cover 4.
In use, if heat radiation is completed during the opened state of the grip cover 4, the grip cover 4 is necessarily closed by the user so that the camera is changed into a portable form or a form suited to photography. Specifically, the camera is used in accordance with the sequence of battery charging due to sunlight→temperature rise of camera→opening of grip cover→temperature fall of camera closing of grip cover→carrying of camera or execution of photography→battery charging due to sunlight. By incorporating the operation of pulling (deforming) the shape memory alloy wire into the aforesaid use sequence of the camera, it is possible to solve the above-described problem.
The following description is made in connection with the operation of closing the grip cover 4 which is in the opened state as shown in FIG. 3(a). First, when the grip cover 4 is rotated about the hinge shaft 6 in the closing direction against the opening force of the torsion spring 21 by hand, an arm 18d of the latch claw 18 comes into abutment with the arm end 24a of the V-shaped lever 24. When the grip cover 4 is rotated to a further extent, since the V-shaped lever 24 is maintained in abutment with the projection 1f of the camera body 1, the latch claw 18 is rotated in the counterclockwise direction by the rotation of the grip cover 4 in the closing direction. Accordingly, the shape memory alloy wire 15 is pulled and expanded up to the yield area. When the grip cover 4 continues to be rotated in the closing direction, an end face 14e of the grip base plate 14 comes into abutment with an arm 24b of the V-shaped lever 24 and the V-shaped lever 24 starts to rotate in the clockwise direction against the urging force of the torsion spring 26. The amount of pulling of the shape memory alloy wire 15 reaches a maximum when the arm 18d of the latch claw 18 and the arm end 24a of the V-shaped lever 24 are brought into abutment with each other at right angles (as shown in FIG. 3(b)). After that state, the arm end 24a of the V-shaped lever 24 moves away from the arm 18d of the latch claw 18 in accordance with the rotation of the grip cover 4. As shown in FIG. 3(c), when the grip cover 4 is fully closed, the claw portion 18c of the latch claw 18 is engaged with the claw engagement portion 1d of the camera body 1 and the arm end 24a of the V-shaped lever 24 is located at a position where it does not interfere with the unlatching movement of the latch claw 18 (i.e., the clockwise rotating movement of the latch claw 18 when the temperature of the shape memory alloy wire 15 rises to a high temperature). The above-described operation will be described with reference to the graph of FIG. 7. The process through which the latch claw 18 rotates in the counterclockwise direction and pulls and expands the shape memory alloy wire 15 corresponds to the portion from a point (i) at which the shape memory alloy wire 15 balances the acting force of the tension spring 20 to a point (ii) at which the shape memory alloy wire 15 is expanded by the 25° C. yield force F25. "X" represents the maximum strain of the shape memory alloy wire 15 and corresponds to the state shown in FIG. 3(b). As the V-shaped lever 24 moves away from the latch claw 18, the shape memory alloy wire 15 naturally shrinks until it balances the acting force of the tension spring 20 (the portion from the point (ii) to a point (iii)). At this time, the grip cover 4 is fully closed and the latch claw 18 is brought into engagement with the claw engagement portion 1d of the camera body 1 (FIG. 3(c)). If a temperature rise occurs at the point (iii) and the shape memory alloy wire 15 passes through an engagement release position Y relative to the latch claw 18 and performs recovery of its shape (reduction of the strain), the grip cover 4 opens. A remarkable variation of the strain appears in the vicinity of a transformation point (55° C.), so that the shrinkage of the shape memory alloy wire 15 at temperatures of 25° C. to 50° C. is extremely small. If the temperature of the shape memory alloy wire 15 rises to 60° C., the latch claw 18 is rotated in the clockwise direction in accordance with the shrinkage of the shape memory alloy wire 15, thereby pulling the tension spring 20 (the point (iii)→a point (iv)→a point (v)).
After that, when the shape memory alloy wire 15 cools to 25° C., it returns to the point (i) at which the shape memory alloy wire 15 balances the tensile load of the tension spring 20. Accordingly, even if the shape memory alloy wire 15 is pulled to a great extent up to the yield area and is deformed so that the amount of engagement of the latch claw 18 with the claw engagement portion 1d can be made large, the force required for such deformation does not act on the shape memory alloy wire 15 during the recovery of the shape thereof, so that the engagement of the latch claw 18 can be released.
Although the above description of the present embodiment has referred to a wire-shaped shape memory alloy which can be incorporated into a small space, it is a matter of course that the present invention can also be applied to a coil spring-shaped shape memory alloy capable of providing a far larger amount of displacement.
The following description is made in connection with a second embodiment of the present invention which is arranged to deform a shape memory alloy wire by pulling it while closing a grip cover by the action of a motor. The construction of the second embodiment is substantially identical to that of the first embodiment, and only different constituent elements of the second embodiment are shown in FIG. 8. FIG. 8 is a schematic view showing a speed reduction mechanism which closes the grip cover 4 by using a motor built in the camera body 1 as a driving source. FIG. 9 is a circuit diagram of a circuit suited to the second embodiment. The speed reduction mechanism shown in FIG. 8 includes a motor 40 which serves as a driving source, a gear train 41 for transmitting the rotation of the motor 40, gears 42 and 43 which are separate constituent elements each of which contains part of a known one-way clutch mechanism, a gear 44 integrally fixed to a driving shaft 45 and meshed with the gear 43. The grip cover 4 and the driving shaft 45 are integrally fixed to each other so that they are prevented from producing a relative rotation. In operation, when the rotation of the motor 40 is transmitted as shown by solid arrows in FIG. 8 with the grip cover 4 opened, the grip cover 4 rotates in the closing direction (in the direction indicated by an arrow B). At this time, the pulling action described previously in connection with the first embodiment is applied to the shape memory alloy wire 15, and after a large tensile deformation has been imparted to the shape memory alloy wire 15, the claw portion 18c of the latch claw 18 engages with the claw engagement portion 1d of the camera body 1. Contrarily, when the shape memory alloy wire 15 shrinks by being heated to a high temperature similarly to the case of the first embodiment and the engagement of the latch claw 18 with the claw engagement portion 1d is released, the grip cover 4 opens by the force of the torsion spring 21. Then, the gear 44 and the driving shaft 45 integrally fixed to the grip cover 4 rotate in the direction of the arrow shown on the gear 44 by a dashed line in FIG. 8, and the gear 43 also rotates. The gear 42, which is directly coupled to the motor 40, does not rotate, while the gear 43 rotates while slipping on the gear 42 by the action of the one-way clutch mechanism (not shown). In other words, the rotation opposite to the rotation of the motor 40 indicated by the solid-line arrow can be used also as a driving source for driving another mechanism of the camera (for example, zooming or film transport).
FIG. 9 is a block diagram of a circuit suited to the present embodiment. In FIG. 9, identical reference numerals are used to denote constituent elements identical to those shown in FIG. 6, and the description thereof is omitted. In FIG. 9, reference numeral 50 denotes a solar battery current detector, and reference numeral 51 denotes an analog switch which performs a switching operation according to the current value detected by the solar battery current detector 50. Although the system described previously as the first embodiment is arranged so that only when the solar cover 2 is opened, the microcomputer activating switch 34 is turned on to perform control of the function of each part of the camera, the second embodiment is arranged so that the analog switch 51 is automatically turned on even when the current value detected by the solar battery current detector 50 exceeds a predetermined value. Specifically, if the camera is placed in sunlight of high illumination intensity, the microcomputer 33 is activated. A temperature detector 52 and a motor driving circuit 53 are controlled by the microcomputer 33. A cover switch 56 is provided for detecting the closed state of the grip cover 4, and the on/off state of the cover switch 56 is detected by the microcomputer 33.
The operation of the above-described construction and arrangement will be described below with reference to FIG. 10 which shows a flowchart of the microcomputer 33.
First of all, the solar battery 30 generates electrical power by exposure to light irrespective of whether the grip cover 4 is opened, thereby charging the lithium-ion secondary battery 1a with electricity.
Even if the microcomputer 33 is not in operation, the current value of the electrical power generated by the solar battery 30 is detected by the solar battery current detector 50. If the solar battery current detector 50 detects a current value I greater than a predetermined current value I 0 , the solar battery current detector 50 turns on the analog switch 51 and activates the microcomputer 33. Thus, the microcomputer 33 starts its operation with Step S1 to be described below. In other words, if the camera is placed in such intense light that the grip cover 4 is heated to a high temperature and is popped up, the solar battery 30 generates electrical power because of the high illumination intensity, and the solar battery current detector 50 detects the current of the solar battery 30, turns on the analog switch 51 and activates the microcomputer 33.
[Step S1] It is determined whether the cover switch 56 is on (the grip cover 4 is closed) or off (the grip cover 4 is opened). If the cover switch 56 is on, the process proceeds to Step S8; otherwise, the process proceeds to Step S2.
[Step S8] After a predetermined time is counted, the process proceeds to Step S9.
[Step S9] The number of times by which this routine has been repeated is counted.
[Step S10] If the off state of the cover switch 56 is detected five times, the process proceeds to Step S7. If the off state of the cover switch 56 has not yet been detected up to five times, the process returns to Step S1, in which the state of the cover switch 56 is detected. Specifically, after the opened state of the grip cover 4 has been detected, the process proceeds to a flow for a closing operation.
[Step S2] A temperature "t" at a predetermined location of the camera is detected by the temperature detector 52, and the process proceeds to Step S3. [Step S3] A preset temperature t0 and the detected temperature "t" are compared. If the detected temperature "t" is lower than the set temperature t0, the process proceeds to Step S4. If the detected temperature "t" is equal to or higher than the set temperature t0, the process returns to Step S2, in which the detection of the temperature "t" is repeated.
[Step S4] The motor 40 is energized to rotationally drive the speed reduction gears 41 to 44, thereby executing the closing operation of the grip cover 4.
[Step S5] It is determined whether the cover switch 56 is on or off. If the on state of the cover switch 56 is detected (the grip cover 4 is closed), the process proceeds to Step S6, whereas if the off state of the cover switch 56 is detected, the energization of the motor 40 of Step S4 is continued.
[Step S6] When the closing operation of the grip cover 4 is completed, the motor 40 is deenergized.
[Step S7] The microcomputer 33 stops the operation and brings this flow to an end.
Specifically, after the grip cover 4 is heated to a high temperature and is popped up, if the temperature of the camera lowers owing to heat radiation, a fall in outside air temperature, interruption of illumination with sunlight or the like and it is detected through the temperature detector 52 that the temperature of the camera has become a temperature lower than a predetermined temperature, the microcomputer 33 causes the motor driving circuit 53 to energize the motor 40 and closes the grip cover 4 via the gear train shown in FIG. 8.
FIG. 11 is a circuit diagram showing a third embodiment which is suited to an apparatus in which a shape memory alloy spring is used as a power source in place of the motor used in the second embodiment described above. In FIG. 11, identical reference numerals are used to denote constituent elements identical to those shown in FIG. 9, and the description thereof is omitted.
Similarly to the second embodiment, after the grip cover 4 is popped up, if the camera cools and the temperature detector 52 detects a temperature lower than a predetermined temperature, the microcomputer 33 causes a shape memory alloy driving circuit 54 to energize a shape memory alloy spring 55. The shape memory alloy spring 55 is deformed and shrinks by self-heating due to the energization, thereby closing the grip cover 4.
The shape memory alloy spring 55 is hooked between the grip cover 4 and the camera body 1. When the shape memory alloy spring 55 is energized, a tension (the shape recovery force of the shape memory alloy spring 55) works as a force stronger than the force of the torsion spring 21 for opening the grip cover 4. The transformation temperature of the shape memory alloy spring 55 is set higher than that of the shape memory alloy wire 15 which is used for releasing the engagement of the latch claw 18 with the claw engagement portion 1d. Accordingly, if the temperature of the camera rises during battery charging and the shape memory alloy wire 15 performs recovery of the shape, the recovery of the shape of the shape memory alloy spring 55 does not occur during that of the shape memory alloy wire 15.
Incidentally, the operation flow of the third embodiment may be realized by partly modifying the flowchart of FIG. 10 of the second embodiment so as to energize and deenergize not the motor 40 but the shape memory alloy spring 55. Specifically, Step S4 may be assigned "ENERGIZE SHAPE MEMORY ALLOY SPRING 55 BY SHAPE MEMORY ALLOY DRIVING CIRCUIT 54" in place of "ENERGIZE MOTOR", and Step S5 may be assigned "DEENERGIZE SHAPE MEMORY ALLOY SPRING 55 BY SHAPE MEMORY ALLOY DRIVING CIRCUIT 54" in place of "DEENERGIZE MOTOR".
Although each of the above-described embodiments is arranged to pull and expand the shape memory alloy wire 15 up to the yield area, the present invention can also be applied to the case in which the shape memory alloy wire 15 is deformed within its elasticity area.
Although each of the above-described embodiments employs the V-shaped lever 24, the present invention can also be applied to another example in which the shape memory alloy wire 15 is expanded not by using the V-shaped lever 24 but by being directly pulled by the shape recovery force of the shape memory alloy spring 55 used in the third embodiment and, while the shape memory alloy wire 15 is recovering its shape, the shape recovery force of the shape memory alloy spring 55 does not work but the spring force thereof works, i.e., an arrangement which does not completely cancel but lessens the action of pulling and expanding the shape memory alloy wire 15 during the recovery of the shape of the shape memory alloy wire 15.
In addition, the present invention can also be applied to an arrangement which employs an illumination intensity detector or other similar devices capable of indirectly identifying the state of temperature, in place of the aforementioned temperature detector used in each of the second and third embodiments.
While the present invention has been described with respect to what is presently considered to be the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. To the contrary, the invention is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.
The individual components shown in schematic or block form in the drawings are all well-known in the camera arts and their specific construction and operation are not critical to the operation or best mode for carrying out the invention.
The present invention can also be carried out by combining the above-described embodiments or technical elements thereof with each other, as required.
The present invention can be applied to other kinds of arrangements. For example, the whole or part of the arrangement set forth herein or in the appended claims may constitute one apparatus, or may be connected to other apparatus, or may constitute an element which forms part of another apparatus.
The present invention can also be applied to various types of cameras such as a single-lens reflex camera, a lens shutter camera or a video camera, optical apparatuses other than such cameras, apparatuses other than the optical apparatuses, apparatuses applied to the cameras or the optical or other apparatuses, or elements which constitute part of such apparatuses. | An apparatus includes a shape memory member, a deforming device which deforms the shape memory member into a predetermined state, an operating device which performs a predetermined movement in response to a movement in which the shape memory member restores itself from the predetermined state to a memorized state, and a restraining device. The restraining device restrains an operation of the deforming device at least when the shape memory member performs the movement of restoring itself from the predetermined state to the memorized state. | 6 |
BACKGROUND OF THE INVENTION
This invention relates to an activated sludge system, i.e. to the biological purification of wastewater, e.g., sewage, wherein the wastewater is treated in a reactor in the presence of sludge, optionally with the absorption of air and/or oxygen, and subsequently the mixture of treated wastewater and activated sludge is separated into purified water and sludge.
In conventional biological wastewater treatment processes, such as activation, nitrification or denitrification processes, it is necessary to separate in a downstream secondary settling tank the purified wastewater from the biomass formed by the activity of special microorganisms suspended in the wastewater as well as in the solids contained in the incoming wastewater as well as in the solids contained in the incoming wastewater. Even in the more recent wastewater treatment processes, in which the microorganisms responsible for the biological conversion are fixed on support materials, such as for example, sand, activated charcoal or polymeric foam particles, it is necessary to include a secondary settler and/or a regenerating installation for the support particles; otherwise, upon the design load being occasionally exceeded, an undesirable formation of unfixed biomass would occur, thereby detrimentally affecting the quality of the purified wastewater effluent. The installation of a downstream secondary sedimentation tank or regenerator for the support particles is, however, expensive and requires additional land, which in the case of wastewater purification is not an insignificant factor in view of the huge equipment sizes involved. In one attempt to solve this problem, a cyclically operated compressor chamber is suggested for regeneration, U.S. patent application Ser. No. 467,007, filed Feb. 16, 1983 by Uwe Fuchs, one of the co-inventors of this invention, said application being incorporated by reference herein; nevertheless, this suggested solution to the problem is less than ideal for activated sludge systems.
SUMMARY
It is thus an object of this invention to provide an improved process of the aforementioned type, together with associated apparatus, whereby a substantially complete separation of the purified wastewater and the sludge is obtained in a simple and economical manner.
Upon further study of the specification and appended claims, further objects and advantages of this invention will become apparent to those skilled in the art.
These objects are attained by providing a system comprising conducting the mixture of wastewater and activated sludge downstream of the treatment zone through a filter zone containing a bed of support particles; depositing biomass and solids from said mixture into the support particles; regenerating resultant loaded support particles within the general area of the filter zone; and withdrawing resultant purified wastewater and said biomass solids removed from the support particles from the filter zone in separate streams.
According to a preferred aspect of the invention, the filter zone and the treatment zone are contained within a single housing, e.g. the filter zone is contained within the activation basin. The creation of a filter zone containing support particles in the treatment zone reactor permits: (a) the separation of the solids present in the incoming wastewater; (b) the separation of the purified wastewater; and (c) the separation of the sludge, all taking place in the same reactor, i.e. without the necessity of a secondary settling tank. In the process, the solids and the biomass are deposited in part on the empty support particles and in part retained in the interstices of the support particles. When the filter zone becomes loaded with solids and biomass, the support particles are regenerated within the filter zone. Moreover, the regeneration may be effected continuously, as will be shown hereinbelow. The biomass obtained during the regeneration of the support particles may be removed as excess sludge or returned at least in part to the reactor as recycle sludge. It is possible thereby to entirely eliminate secondary settling following the reactor, or else, to relieve the secondary settler facility in the case of overload so as to continue to obtain a separation of purified water and sludge that is as complete as possible.
Preferably, the filter zone is maintained during normal operation as free of turbulence as possible. The proportion by volume of the support particles with respect to the volume of the filter zone is set at 40 to 80%, preferably 60 to 70%. In this manner, the disruption of the filter zone and the formation of large voids, e.g., over 5 mm in the filter bed are prevented; this would otherwise have a detrimental effect on the filter process. To achieve such flows in the filter bed which are of insufficient turbulence to disrupt the filter bed, it is preferred that space velocity of the liquid stream (assuming the influent to the filter bed to be 100% liquid and volume of filter bed to be devoid of support particles) is 0.03 to 1.2, preferably especially about 0.08 to 0.3 cm/sec. The higher the content of solids present in the wastewater, the lower must be the velocity of the liquid stream and the higher must be the intensity of the regeneration of the support particles. This may be reached in the case of a discontinuous regeneration by a high regeneration frequency or in the case of a continuous regeneration by a high mass flow of support particles to the regeneration unit.
The treatment zone of the reactor is operated advantageously as a fully mixed activation basin, optionally containing support particles for growth of the biomass, or as a column reactor definitely containing support particles for growth of the biomass. In general, the proportion by volume of the support particles in the treatment zone is set at 20 to 60%, as a function of the type of reactor used. In the case of a fully mixed activation basin the proportion by volume of the support particles is preferably 20 to 40%, and in a column reactor preferably 40 to 60%, of the total volume of the treatment zone. The choice of the appropriate type of reactor generally depends on the initial load of the wastewater. In particular, in the case of highly loaded wastewater, it is convenient to provide the reactor in the form of a column reactor, while with less loaded wastewater the employment of a fully mixed activation basin is adequate. Similarly, it is advisable to operate the reactor in the form of a column reactor to effect nitrification or denitrification processes. By highly loaded wastewater is meant a wastewater with BOD-contents greater than 1000 mg/l, COD-contents greater than 1500 mg/l and contents of suspended solids greater than 10 kg/m 3 .
Preferably and advantageously, both in the treatment zone and in the filter zone of the reactor, flexible, open cell, porous organic polymers are used as the support particles. In particular, polyurethane foam or foamed rubber or similar materials with open macropores, as provided by industry for other conventional uses, e.g., cushioning, mattresses, etc., are suitable as support materials, with the advantage that inexpensive industrial remnants or waste items may be employed. The size of the individual support particles may vary between 0.5 and 50 mm, preferably 10 to 20 mm. These ranges of dimensions of the support particles assure stable bacterial accumulations, together with the supply of oxygen and the transport of material to the interior of the support particles. If the reactor is used for the conversion of carbon compounds or as a nitrification reactor, by means of the selection of the support particles within the upper range of the values given, anoxic zones may be created inside the support particles, so that in the treatment zone of the reactor, aside from the decomposition of the carbon compounds and nitrification, denitrification processes may also be effected. However, such denitrification processes may obviously also be located in the filter zone. In principle, other supports known in the prior art can also be employed in this invention, especially in the column reactor, but such other materials do not have the advantages of the polyurethane foam. For additional details of the polyurethane foams, reference is invited to U.S. Pat. No. 4,162,216.
In addition to the filtering and precipitating function in the filtering zone, it is also possible to effect residual biological decomposition in the filter zone by aerating the filter zone slightly in normal operation. However, the aeration should generate as little turbulence as possible in the filter zone, in order to avoid the disruption of the filter bed as discussed above. Preferably the space velocity of the gas through the filter bed is maintained at about 0.2 to 3, preferably 0.5 to 1.5. m 3 gas (normal condition) per m 3 filter bed and hour.
According to a further aspect of an embodiment of the process, it is advantageous to maintain a continuous loading and regenerating process of the support particles. It is especially desirable to provide in the filter zone an upwardly directed flow of the mixture of wastewater and activated sludge and a downward migration of the support particles, and to transport the support particles for regeneration from the lower part of the filter zone, e.g. the bottom 2-20%, and possibly from the lower part of the treatment zone, to above the filter zone, in order to free the support particles of the biomass by compression and to return the support particles free of the biomass to the filter zone and possibly to the treatment zone. The downward flow of the partially empty and thus floating support particles is obtained by the weight of a pile of regenerated support particles protruding from the water. The biomass and solids freed by the compression of the support particles are collected and drawn off the system as excess sludge and/or returned to the treatment zone as recycle sludge.
The return of the recycle sludge may be eliminated, if the regeneration of the support particles, recycled for example through the wastewater inlet into the treatment zone is effected only to the extent that in the course of the compression of the support particles sufficient biomass remains in the pores of the support particles. This may be accomplished, for example, during certain intervals in the process, by conducting the compression of the support particles only to a predetermined extent of their original dimensions, e.g., 20 to 40% of original volume of the particle, and that the support particles regenerated in this manner are added to the wastewater feed, while the support particles compressed to greatest possible extent, e.g., less than 10%, preferably less than 7%, are returned to the filter zone, where they exercise a high filtering effect.
Both to support the regenerating process by means of the compression of the support particles and for the regeneration of the support particles without compression, it is further possible to effect vigorous aeration periodically in the filter zone. By means of the vigorous aeration process, the support particles are churned together in the filter zone. The result is that the solids accumulated between the support particles and the biomass adhering to the support particles are released by gas velocities of at least about 10 Nm 3 /m 3 filter bed×h.
If regeneration is performed without the subsequent compression of the support particles and only by an increased aeration in the filter zone, it is convenient to remove the biomass stripped from the support particles by the strong aeration, by means of the inflowing mixture of wastewater and activated sludge and/or an at least partial rapid emptying of the filter zone, from said filter zone. The biomass removed from the support particles and discharged from the filter zone may be transported to the primary settling tank or to a thickener.
The different possible modes of regeneration--by only the compression of the support particles or by strong aeration of the filter zone with subsequent compression of the support particles, or by vigorous aeration alone--are not restricted to certain types of reactor and may be employed, e.g., as a fully mixed basin with a filter zone, or in a column reactor with a filter zone.
The apparatus for the embodiment of the process comprises a reactor and separating means for purified wastewater and sludge. According to the invention, the reactor comprises a treatment zone, and the separating means for the deposit of the biomass from the treated wastewater comprises a filter zone containing support particles. Regenerating means for the support particles is associated with the filter zone, an activated sludge outlet, and optionally means to recycle the support particles freed of the biomass.
The sludge outlet may be equipped with a sludge return line to the treatment zone and a discharge line for excess sludge. The return line for the support particles freed of the biomass may be connected, in addition to the filter zone, also with the treatment zone, so that regenerated support particles may be returned to the filter zone and also to the treatment zone.
In view of both the effecting of the residual decomposition of organic impurities in the filter zone and of the regeneration of the support particles in the filter zone, it is appropriate to provide aeration means not only in the treatment zone, but also in the filter zone. For residual decomposition, only slight aeration may be effected without causing turbulence in the filter zone, and then vigorous aeration can be used intermittently to obtain churning of the support particles for regeneration.
Depending on the contaminant load of the wastewater, the treatment zone may be in the form of a column reactor or in the form of a fully mixed activating basin, with support particles for the biomass being optionally present in the basin.
To assure the satisfactory operation of the filter zone, the volume of the filter zone should appropriately amount to about 1/4 to 1/3 of the volume of the treatment zone.
According to an advantageous aspect of an embodiment of the apparatus of the invention, the regenerating installation for the support particles is equipped with (a) conveyor means connected with the filter zone and optionally also with the treatment zone, (b) drainage means, (c) compressing means, and (d) collecting means for the biomass released. The conveying means may advantageously comprise an air lift pump and the compressing device may comprise at least two rotating press-rolls, with the lower press-roll being preferably porous and associated with the collecting device.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a schematic illustration of a preferred embodiment of the invention comprising a substantially, if not completely, mixed activating basin with an integrated filter zone and a regenerating installation.
FIG. 2 is a schematic illustration of a preferred embodiment comprising a column reactor with an integrated filter zone.
FIG. 3 is a schematic illustration of a preferred embodiment similar to FIG. 1 for the secondary treatment of wastewater.
DETAILED DESCRIPTION
In FIG. 1, the symbol 1 designates a mixed activating basin for the biological treatment of wastewater, said basin being provided with an inlet 2 for the wastewater to be treated and an outlet 3 arranged at the upper edge of the basin for the treated wastewater. This basin is generally rectangular, but other geometric shapes can also be employed. Within the activating basin 1, a treatment zone 4 is separated by a baffle from a filter zone 6, the latter occupying approximately 1/4 of the total volume. Between the bottom of the basin and the bottom of the baffle exists a space the opening of which is in the range of about 10 to 20% of the height of the basin.
In the filter zone 6, tightly packed, porous support particles 7, preferably of a porous, open cell, porous polyurethane foam are present as the filter medium for solids and the biomass, in a volume such that 40 to 80%, preferably 60 to 70%, of the volume of the filter zone 6 are filled with support particles. To prevent the decanting of the support particles through the discharge outlet 3, a screen or grating 3a, having openings of a diameter less than the support particles, is arranged in the outlet 3. To increase the biomass concentration in the treatment zone 4, support particles for the biomass may also be arranged in this zone in amounts corresponding to a volume proportion of the treatment zone of 20 to 40%, preferably 25 to 30%. Furthermore, both in the treatment zone 4 and in the filter zone 6, aeration devices 8 are provided, whereby air and/or oxygen may be introduced. Aeration in the filter zone 6 is not absolutely necessary, but is convenient for the residual decomposition of organic compounds. For this purpose, aeration in the filter zone 6 should be such that insufficient turbulence occurs to disrupt the filter bed. The feed line to the aeration installations 8 of the filter zone 6 is equipped with a control valve 9 for this purpose. The aeration installations 8 themselves are designed so that aeration with medium to coarse bubbles will be possible, e.g., a bubble size in the range of about 5 to 20 mm. In the case of large volumetric flows of the gas, such as those potentially required for the regeneration of support particles, such aeration devices are operated in a more economical manner than with devices providing finer bubbles. Furthermore, they are substantially free of the need for maintenance, as they do not clog easily. A suitable aeration device which will be essentially non-clogable can consist of a hollow body having a gas supply pipe and a perforated top plate. The diameter of the holes in the top plate can be in the range of about 2-7 mm.
For the regeneration of the support particles 7, a regenerating apparatus 10 is arranged above the filter zone 6, said regenerating apparatus comprising conveying means 11, drainage means 12a and 12b, compression means 13a and 13b, and collecting means 14 for the biomass liberated from the supports. The conveying means 11 may comprise, for example, an air lift pump powered by compressor 17 or may be in the form of a pan or chain conveyor, and is located in the treatment zone 4, in the vicinity of the baffle 5 separating the treatment zone 4 from the filter zone 6. By virtue of this arrangement of the conveyor 11, support particles 7 may be transported from the filter zone 6 and potentially also from the treatment zone 4, to the regenerating apparatus 10, where the support particles 7 are suctioned from the filter zone 6 through the gap orifice formed between the bottom of the activating basin 1 and the baffle 5, by the conveyor means 11. At the upper end of the conveyor means 11, the support particles then drop initially onto a perforated chute 12a serving as a preliminary drainage zone and being arranged upstream and above the baffle 5, so that the water flows predominantly into the treatment zone 4. At the outlet of the chute 12a, a revolving, porous conveyor belt 12b is arranged to serve as a secondary drainage zone and for transporting the support particles to the compression device which comprises two press-rolls 13a and 13b, rotating in opposing directions. To assure the uninterrupted transport of the support particles to the press-rolls 13a, 13b, a water impermeable conveyor belt is provided for the upper press-roll 13b, said conveyor belt extending before the press-rolls 13a, 13b at an acute angle with respect to the lower perforated conveyor belt 12b. Laterally to the conveyor belts and press-rolls, a plurality of guide plates 16 are arranged.
By the opposing movement of the press-rolls 13a and 13b and the roll pressure, generated by means of springs or the like, the support particles are generally compressed to 5 to 30% of their original volume and the adhering solids, bacteria, and liquids squeezed out. The regenerated support particles are then transported, by the conveyor belt 12b passing between the press-rolls 13a and 13b, back to the filter zone 6. If support particles are present in thetreatment zone 4, part of the regenerated support particles may be drawn off and passed to the inlet 2 of the activating basin 1. The solids, bacteria and liquids squeezed from the support particles are gathered in a collector vessel 14 arranged under the two press-rolls 13a and 13b, for which reason the lower press-roll 13a is preferably also perforated. The diameter of the holes of the lower press-roll 13a, and also the hole diameter of the conveyor belt 12b, are selected so as to permit the water loaded with solids and bacteria to fall through while retaining the support particles. For example, pores of a hole diameter of 0.2 to 10 mm are used for supports of an uncompressed diameter of about 0.5 to 50 mm. The specific hole diameter will depend on the particle size of the supports and the degree of compression. The number of holes is advantageously 1-10, particularly 5-10 per square centimeter. A sludge discharge line 15 is connected from the collector vessel 14 downstream, for example, with a thickener for the further processing of the sludge.
To loosen the support particles in the packed filter zone 6 to release occluded solids and biomass, it is possible to introduce gas at a higher rate for short periods of time through the aeration spargers 8 to the filter zone 6 above. Under certain conditions such an increased introduction of gas may also be sufficient for the regeneration of the support particles, so that no special regenerating device is required. Instead, in such a case it would be necessary to provide the activation basin, at least in the vicinity of the bottom of the filter zone, with a screen or grating through which the biomass and the solids separated from the support particles during the churning of the said particles as the result of the stronger aeration may be discharged. Furthermore, the filter zone would have to be separated by a conventional overflow weir from the treating zone, in order to prevent the emptying of the treatment zone. Such a regeneration with an increased introduction of gas alone for regeneration is possible if the waste water to be treated has BOD-contents less than 50 mg/l and COD-contents less than 150 ml/l. For instance such a waste water exist in the secondary treatment of waste water for nitrification.
A suitable installation for this purpose is shown in FIG. 3. The inlet 102 of the activation basin 101 connects this with a first treatment stage (not shown) in which the major proportion of the organic pollutants is decomposed. The activation basin 101 is divided by a wall 105 in a treatment zone 104 in which the decomposition of the residual organic pollutants is conducted in conjunction with nitrification and in a filter zone 106 in which porous support particles 107 are present as the filter medium for solids and biomass. In connection with the filter zone 106 an outlet 103 is arranged at the upper edge of the basin 101 for treated waste water. To prevent the decanting of the support particles through this discharge outlet 103, a screen or grating 103a having openings of a diameter less than the support particles is provided in the outlet 103. Both zones, the treatment zone 104 and the filter zone 106, are provided with aeration devices 108. At the upper end of the wall 105 a conventional overflow weir 111 regulates the flow from the treatment zone 104 to the filter zone 106. To prevent a direct liquid flow from the overflow weir 111 to the discharge outlet 103 a baffle 117 is arranged in the middle of the filter zone 106. For the regeneration of the support particles 107 the introduction of gas through the aeration device 108 of the filter zone 106 which under normal conditions is at most such that insufficient turbulence occurs to disrupt the filter bed built by the support particles is increased for a short period of time so that the support particles are churned in order to release occluded solids and biomass. For the discharge of the separated solids and biomass after the increased aeration a sludge discharge line 115 arranged at least in the vicinity of the bottom of the filter zone 106 and provided with a screen 114 preventing the support particles to be drained is opened. After the liquid containing the released solids and biomass is leaked the discharge line 115 is closed and a new filtering step beginning with the filling of the filter zone 106 with liquid overflowing through weir 111 from the treatment zone 104 takes place. The measurement of the filter zone, the velocity of the liquid flow through the filter zone and the type of support particles in this embodiment can be the same as in the embodiment of FIG. 1.
FIG. 2 shows a column reactor 20 with an integrated filter zone 22, operating without a separate regenerating device. In this case, the liquid to be treated flows from top to bottom through the column reactor 20. For this purpose, there are provided a wastewater inlet 23 at the top and an outlet 24 for the treated liquid at the bottom. The filter zone 22, filled to 40 to 80%, preferably 60 to 70%, with support particles, is placed in the bottom area of the column reactor 20, while the treatment zone 21, filled to 20 to 60%, preferably 40 to 50%, with support particles, is located above it. An aeration installation 25 and 26 is provided for both the treatment zone 21 and the filter zone 22, with the supply of gas to the aeration installations being variable by means of control valves. As a rule, the filter zone 22 is aerated slightly or not at all, while the treatment zone 21 is aerated strongly, in keeping with the consumption of O 2 . To regenerate the loaded support particles, the outlet 24 of the column reactor 20 is closed and the concentration of particles is diluted by the accumulation of liquid. Simultaneously, the supply of gas to the aeration installations 25, 26 is increased. The subsequent churning of the support particles separates the adhering solids and biomass. After a certain regeneration period, e.g., 3 to 30 minutes, the outlet 24 is opened so that the separated substances may be discharged. To prevent the discharged substances from affecting the quality of the effluent outlet from the column reactor 20, a branch line 27 with an on-off valve is associated with the outlet 24, through which the substances discharged are conducted to the preliminary settling tank or to a thickener. Following the rinsing of the column reactor 20, the branch line 27 is closed and the purified wastewater leaving the column reactor 20 is returned to the normal outlet.
To allow for the occurrence of denitrification processes in the filter zone even without the supply of gas, a branch line 23a is associated with the inlet 23, said branch line 23a opening directly above the filter zone into the column reactor 20.
In addition to the configuration of a column reactor without a regenerating installation, it is obviously also possible to equip a column reactor in keeping with the layout shown in FIG. 1 for an activation basin with a corresponding regenerating installation.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. In the following examples, all temperatures are set forth uncorrected in degrees Celsius; unless otherwise indicated, all parts and percentages are by weight.
Specific example in connection with the embodiment of FIG. 1.
______________________________________(1) Waste water inlet BOD.sub.5 = 150 mg/l COD = 260 mg/l suspended solids = 80 mg/l waste water feed rate = 250 m.sup.3 /h(2) purified waste water BOD.sub.5 ≦20 mg/l COD ≦75 mg/l solids ≦0,2 mg/l(3) treatment zone BOD.sub.5 -volume load B.sub.R = 2 kg/m.sup.3 day BOD.sub.5 -sludge loading B.sub.TS 0,38 kg/kg · day volume 450 m.sup.3 volume of support particles 30 Vol % specific gravity of the support 60 kg/m.sup.3 particles size of the support particles 12 × 12 × 12 mm biomass in support particles 15 kg/m.sup.3 biomass not fixed at support particles about 1 kg/m.sup.3(4) filter zone volume 126 m.sup.3 = 28% of the treatment zone volume of support particles 60 Vol % velocity of the liquid 6 m/h storage capacity of solids 700 kg passage of solids to filter zone 150 mg/l running time of the filter 18 h(5) regeneration quality of support particles being 7m.sup.3 /h transported to regeneration unit quantity of support particles and 10-20 m.sup.3 /h water being transported to the press rolls intensity of pressing 75% solids content of regenerated sewage 30-50 kg/m.sup.3______________________________________
The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. | In the treatment of wastewater, the mixture of wastewater and the sludge is transported through a treatment zone, and then through a filter zone containing a bed of support particles, e.g., particles of polyurethane foam, to deposit the biomass onto the support particles. The loaded support particles are subsequently regenerated within the filter zone by means of a regenerating means in the same area as the filter zone, e.g., by strong aeration or by being compressed between press-rolls, whereby the system requires neither additional land for regeneration of the support particles nor a secondary settling tank. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to and incorporates by reference herein in its entirety the following: U.S. Provisional Patent Application Ser. No. 61/021,862, filed Jan. 17, 2008.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates generally to an adapter with a shutter, and particularly to an adapter with a shutter that protects the adapter from accumulating dust and to protect an end user from potential eye-damage if a connector is removed from the adapter.
[0004] 2. Technical Background
[0005] Fiber optic cables are widely used today to transmit a large amount of data rapidly and efficiently. Systems using fiber optic cables typically have multiple connection points, or interfaces, where the light signals must be transmitted from one set of optical fibers to another set of optical fibers. These connection points or interfaces usually involve two connectors that are mechanically and optically aligned to allow the light to traverse the connection points. These connection points typically occur within adapters that mechanically and optically align the fiber optic connectors. Usually, there are many such adapters that are used in a system and not all adapters are used when installed.
[0006] The end user of systems typically move connectors on one side of the system to connect or reconnect connectors with one another. Open adapters and the moving of connectors from one adapter to another presents at least two issues for the system and the user. First, if the adapters are open, or even if they are moved, dust may enter the adapter and interfere with the light transmission between two connectors by contaminating the adapter or the connectors. Second, when moving connectors, the connector on the opposite side of the adapter may still be connected to a light source, presenting a potential source of eye damage. There are dust caps for connectors, but they are essentially useless in this situation since the connectors are moved from one adapter to another and they cannot be used to prevent the light from exiting the connector on the back side of the system.
[0007] It would be desirable therefore to provide an adapter that has a shutter that remains in place, prevents dust from entering the adapter when a connector is not installed, and prevents eye damage by blocking the light from the connector on the back side of the system.
SUMMARY OF THE INVENTION
[0008] Disclosed herein is a fiber optic connector adapter that includes a main body having an opening for receiving a fiber optic connector, a cover for sealing the opening in the main body when a connector is not inserted into the opening, the cover being rotatedly connected to the main body, and a resilient member engaging the main body and the cover to bias the cover in a closed position, the resilient member engaging the cover only at a location that generally corresponds to a center portion of the cover.
[0009] In some embodiments, the main body has an end face with a radial projection extending around the opening.
[0010] In some embodiments, the cover has a recessed area corresponding to the readial projection.
[0011] In some embodiments, the cover has an opening in the cover to receive the resilient member.
[0012] In another aspect, a fiber optic connector adapter is disclosed that includes a main body having an opening for receiving a fiber optic connector, the main body having an end face and a radial projection on the end face extending around the opening, a cover for sealing the opening in the main body when a connector is not inserted into the opening, the cover being rotatedly connected to the main body, and a resilient member engaging the main body and the cover to bias the cover in a closed position.
[0013] In yet another aspect, a fiber optic connector adapter is disclosed that includes a main body having an opening for receiving a fiber optic connector, the main body having an end face and a radial projection on the end face extending around the opening, a cover for sealing the opening in the main body when a connector is not inserted into the opening, the cover being rotatably connected to the main body and having a recessed area corresponding to the radial projection on the end face of the main body, the recessed area having a flexible member to engage the radial projection and seal the opening, and a resilient member engaging the main body and the cover to bias the cover in a closed position, the resilient member engaging the cover only at a location that generally corresponds to a center portion of the cover.
[0014] In yet another aspect, a fiber optic connector adapter is disclosed that includes a main body having an opening for receiving a fiber optic connector, a cover for covering the opening in the main body when a connector is not inserted into the opening, the cover being rotatably connected to the main body, a flexible member engaging the main body and the cover when the connector is not inserted into the opening to thereby seal the opening, and a resilient member engaging the main body and the cover to bias the cover in a closed position.
[0015] Additional features and advantages of the invention will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the invention as described herein, including the detailed description which follows, the claims, as well as the appended drawings.
[0016] It is to be understood that both the foregoing general description and the following detailed description of the present embodiments of the invention, and are intended to provide an overview or framework for understanding the nature and character of the invention as it is claimed. The accompanying drawings are included to provide a further understanding of the invention, and are incorporated into and constitute a part of this specification. The drawings illustrate various embodiments of the invention, and together with the description serve to explain the principles and operations of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 is a front perspective view of one embodiment of an adapter according to the present invention;
[0018] FIG. 2 is a front perspective view of the adapter of FIG. 1 in a closed position;
[0019] FIG. 3 is cross section view of the adapter of FIG. 1 ;
[0020] FIG. 4 is an exploded view of the adapter of FIG. 1 ;
[0021] FIG. 5 is a perspective view of the adapter of FIG. 1 with a connector inserted therein;
[0022] FIG. 6 is a front perspective view of a second embodiment of an adapter according to the present invention;
[0023] FIG. 7 is a cross section view of the adapter of FIG. 6 ;
[0024] FIG. 8 is an exploded view of the adapter of FIG. 6 ;
[0025] FIG. 9 is a perspective view of a third embodiment of an adapter according to the present invention;
[0026] FIG. 10 is a top view of the cover and clip of the adapter of FIG. 9 ;
[0027] FIG. 11 is a side view of the cover and clip of FIG. 9 ; and
[0028] FIG. 12 is a front view of the cover and clip of FIG. 9 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0029] Reference will now be made in detail to the present preferred embodiment(s) of the invention, examples of which are illustrated in the accompanying drawings. Whenever possible, the same reference numerals will be used throughout the drawings to refer to the same or like parts.
[0030] Referring to FIGS. 1-5 , adapter 10 has a main body 12 that has a front end 14 and a rear end 16 . The main body also has an opening 18 that extends between the front end 14 and the rear end 16 to receive a connector (not illustrated). Adapter 10 is illustrated in the figures is one portion of a complete adapter. As is known in the art, a second adapter portion (not illustrated) is attached to the rear end 16 to allow another connector to be received for optical and mechanical alignment with the connector inserted into opening 18 . The second adapter portion may have any configuration or format, and may even be the same as illustrated in FIGS. 1-4 .
[0031] The adapter 10 , and particularly opening 18 , as illustrated in the figures is configured to receive an MTP type connector, but could be configured to accept any appropriate connector form.
[0032] The front end 14 of the adapter 10 has a front face 20 that has a radial projection 22 that preferably encircles the opening 18 . The radial projection 22 is illustrated as a rib that has a cross section that approximates a triangle. The radial projection 22 also preferably encircles the opening 18 in a form that approximates the opening 18 . The radial projection 22 may take any cross section shape or configuration on the front face 20 of the adapter 10 and still be within the scope of the present invention. The projection 22 may also be resilient, such as a gasket or O-ring.
[0033] The adapter 10 also includes a cover 30 , that is rotatably connected to the main body 12 by a pin 32 . The pin preferably passes through two openings 34 , 36 in the main body 12 adjacent one edge of the front end 14 . The openings 34 , 36 are preferably sized to receive the pin 32 with only minimal clearance.
[0034] The cover 30 that is preferably sized to correspond to the main body 12 , although it may be larger or smaller. The cover 30 has a recessed portion 42 that is configured to correspond to the radial projection 22 on the front face 20 of main body 12 . The recessed portion 42 also preferably includes a flexible member 44 that engages the radial projection 22 to provide a tight junction therebetween and keep out any dirt and/or debris. As best illustrated in FIG. 4 , the flexible member 44 is an O-ring seal. The flexible member 44 is preferably recessed relative to the inside surface 40 of the cover 30 so that a connector being inserted or removed from the adapter 10 will not catch on the flexible member 44 . The presence of the radial projection 22 on the front face 20 allows for a tight seal even with the flexible member 44 being recessed relative to the cover 30 . The flexible member 44 and the recessed portion 42 are preferably sized to one another such that the flexible member 44 is frictionally engaged within the recessed portion and need not be epoxied into the recessed portion 42 , although it may be.
[0035] As noted above, the projection 22 may be resilient or it may be hard. It is also possible that the cover 30 has the projection and the main body 12 has a corresponding recessed portion with a resilient member therein.
[0036] The cover 30 also has two pin openings 46 , 48 , through which the pin 32 passes to rotatably attach the cover 30 to the main body 12 . The pin openings 46 , 48 are not circular as are pin openings 34 , 36 on main body 12 . Rather, the pin openings 46 , 48 are elongated to allow the cover 30 to move relative to the pin 32 to ensure a tight fit with the main body 12 , as described in more detail below.
[0037] The adapter 10 also includes a resilient member 60 , which is illustrated as an arm spring. One end 62 of the arm spring 60 engages the main body 12 , while the other end 64 engages the cover 30 . A central portion of the resilient member 60 is wrapped around the pin 32 . As noted above, the end 64 of resilient member 60 engages a center portion 50 of the cover 30 . By contacting a center portion 50 , and in conjunction with the non-circular pin openings that allow the cover 30 to float on the pin 32 , the cover 30 maintains an even pressure on the radial projection 22 , keeping the opening 18 sealed. Preferably the resilient member 60 passes into an opening 52 that extends from a top edge 54 of cover 40 toward a bottom end 56 . While the opening 52 has a cover 58 , the opening need not have a cover and could simply be a groove or depression in the cover 30 .
[0038] The cover 30 also preferably has a rounded bottom edge 70 such that the connector will not catch on the cover 30 during insertion or removal of the connector from the opening 18 . A perspective view of a connector 90 inserted into the adapter 10 is illustrated in FIG. 5 , showing the relative placement of the cover and the connector 90 once inserted into the adapter 10 .
[0039] A second embodiment of an adapter 100 according to the present invention is illustrated in FIGS. 6-8 and has a main body 112 that has a front end 114 and a rear end 116 . The main body also has an opening 118 that extends between the front end 114 and the rear end 116 to receive a connector (not illustrated). Adapter 100 is illustrated in the figures as one portion of a complete adapter. As is known in the art, a second adapter portion (not illustrated) is attached to the rear end 116 to allow another connector to be received for optical and mechanical alignment with the connector inserted into opening 118 . The second adapter portion for adapter 100 may have any configuration or format, and may even be the same as illustrated in FIGS. 1-5 or in FIGS. 6-8 .
[0040] The adapter 100 , and particularly opening 118 , as illustrated in the figures is configured to receive an MTP type connector, but could be configured to accept any appropriate connector form.
[0041] The adapter 100 also includes a cover 130 , that is rotatably connected to the main body 112 by a pin 132 . The pin preferably passes through two openings 134 , 136 in the main body 112 adjacent one edge of the front end 114 . The openings 134 , 136 are preferably sized to receive the pin 132 with only minimal clearance.
[0042] The cover 130 that is preferably sized to correspond to the main body 112 , although it may be larger or smaller. The cover 130 has a flat front face 140 to engage a flexible member 144 , described in detail below.
[0043] The cover 130 also has two pin openings 146 , 148 , through which the pin 132 passes to rotatably attach the cover 130 to the main body 112 . The pin openings 146 , 148 are not circular as are pin openings 134 , 136 on main body 112 . Rather, the pin openings 146 , 148 are elongated to allow the cover 130 to move relative to the pin 132 to ensure a tight fit with the main body 112 , as described in more detail below.
[0044] The main body 112 has a flexible member 144 inserted therein to engage the front face 140 of cover 130 . Rather than have a flexible member in the cover 130 as in the prior embodiment, a flexible member 144 is inserted into the main body 112 of the adapter 100 . The flexible member 144 , as best seen in FIG. 7 , is configured along with the remaining interior of the main body 112 so as to accept an appropriate connector. While the flexible member 144 extends about ⅓ of the way from the front end 114 toward the rear end 116 , it need not. It could extend more or less from the front end 114 . However, the front end 145 of the flexible member 114 preferably extends above the front end 114 of the main body 112 so that it engages the front face 140 of the cover 130 when a connector is not inserted into the opening 118 .
[0045] The adapter 100 also includes a resilient member 160 , which is illustrated as an arm spring. One end 162 of the arm spring 160 engages the main body 120 , while the other end 164 engages the cover 130 in opening 152 . A central portion of the resilient member 160 is wrapped around the pin 132 . The end 164 of resilient member 160 engages cover 130 near an edge. However, the opening 152 and end 164 could both be longer so that end 164 of resilient member 160 engages the center of cover 130 as in the first embodiment. While the opening 152 has a cover 158 , the opening 152 need not have a cover and could simply be a groove or depression in the cover 130 .
[0046] An alternative embodiment of an adapter 200 is illustrated in FIGS. 9-12 . In this embodiment, the main body 202 is a standard connector adapter, but the cover 240 is connected to the main body 202 by a clip 250 . The clip 250 and the cover 240 are rotatably coupled to one another by a pin 232 , with a resilient member 260 biasing the cover 240 toward the main body 202 . In this manner, the adapter 200 may be added to already installed adapters, preventing the need to reinstall adapters and connectors in already existing systems. The adapter 200 also includes a gasket 242 that assists in maintaining a seal for the adapter 200 . The gasket 232 is preferably sized to correspond to the configuration of the main body 202 of the adapter 200 (as well as the cover 240 ).
[0047] It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit and scope of the invention. Thus it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. | An adapter with a dust shutter also provides eye protection and an even seal around the connector opening. The adapter includes a main body, a cover, and a resilient member to bias the cover in a closed position. The adapter also includes a flexible member to assist in sealing the adapter. The resilient member contacts the cover in a center portion and the cover floats relative to the main body to ensure a good seal. | 6 |
BACKGROUND OF THE INVENTION
This invention relates to novel bicyclic tetrahydroxylated pyrrolizidines and methods for their chemical synthesis. These compounds are useful inhibitors of glycosidase enzymes.
Several naturally occurring polyhydroxylated pyrrolidines, pyrrolizidines and indolizidines are powerful and specific inhibitors of glycosidases [Fellows and Fleet, Alkaloidal Glycosidase Inhibitors from Plants, in Natural Products Isolation (Ed. G. H. Wagman and R. Cooper), Elsevier, Amsterdam, 1988, pp. 540-560; Evans et al, Phytochemistry, 24 1953-1956 (1985)]. In recent years, plagiarism of plant chemistry has led to the synthesis of powerful inhibitors of other glycosidases [Fleet et al,, J. Chem. Soc., Perkin Trans. 1, 665-666, (1989); Bashyal et al, Tetrahedron 43, 3083-3093 (1987), and Fleet et al, Tetrahedron 43, 979-990 (1987)]. It is now clear that, although changes in stereochemistry of the hydroxyl groups have profound effects on the selectivity of glycosidase inhibition, it is not easy to predict the effects of such changes [Fleet et al, Tetrahedron Lett., 26 3127-3131 (1985)]. For example, 6-episcastanospermine (2) is a glucosidase inhibitor even though the stereochemistry of the four adjacent chiral centres in the piperidine is similar to those in the pyranose form of mannose [Molyneux et al, Arch. Biochem. Biophys., 251, 450-457 (1986)]. Similarly, 1,7a-diepialexine (3), structurally very similar to the powerful mannosidase inhibitor swainsonine (4), is an inhibitor of fungal glucan 1,4-α-glucosidase [Nash et al, Phytochemistry, submitted for publication]. Also, β-C-methyl deoxymannojirimycin (5) is a strong and specific α-L-fucosidase inhibitor and has no effect on human liver α-mannosidase [Fleet et al, Tetrahedron Lett., 30, In Press (1989)]. ##STR1##
With a few exceptions [Raymond and Vogel, Tetrahedron Lett., 30 705-706 (1989)], sugars have been the starting materials used in the synthesis of such compounds as castanospermines [such as (2)], Setoi et al, Tetrahedron Lett., 26 4617-4620 (1985), Hamana et al, J. Org. Chem., 52, 5492-5494 (1987) and Fleet et al, Tetrahedron Lett., 29, 3603-3606 (1988); alexines [such as (3)], Fleet et al, Tetrahedron Lett., 29, 5441-5445 (1988); and homonojirimycins [such as (4)], Anzeneno et al, J. Org. Chem. 54, 2539-2542 (1989). Invariably in the syntheses of these compounds with five adjacent chiral centres and six or seven adjacent functional groups, the strategy chosen has been to start from a hexose and to introduce the additional chiral centre late in the synthesis. An alternative is to start from derivatives of heptoses, that is by very early introduction of the additional chiral centre.
Relatively few studies have been reported on the protecting group chemistry of even readily available heptonolactones [Brimacombe and Tucker, Carbohydr. Res. 2, 341-348 (1966)]. Likewise, only a few examples of syntheses from heptose derivatives have been reported. One neat example is described by Stork et al, J. Am. Chem. Soc. 100, 8272-8273 (1978). Recently, a research group led by co-inventor Fleet herein has found that suitably protected heptonolactones can be powerful and readily manipulatable chiral pool materials. See Bruce et al, Tetrahedron 45, In press 1989, and copending application Ser. No. 07/352,068, filed May 15, 1989.
BRIEF DESCRIPTION OF THE INVENTION
In accordance with the present invention, novel bicyclic tetrahydroxylated pyrrolizidines are synthesized from the readily available heptonolactones, D-glycero-D-gulo-heptono-1,4-lactone and the analogous D-glycero-D-talo-heptono-1,4-lactone.
In a preferred embodiment of the invention, the novel 1α, 2α, 6α, 7α, 7α, β-1,2,6,7-tetrahydroxypyrrolizidine (1) is prepared from D-glycero-D-gulo-heptono-1,4-lactone by two different synthetic routes. This novel tetrahydroxylated pyrrolizidine is an effective inhibitor of human liver glycosidases. ##STR2##
The tetrahydroxyprrolizidone (1) is an analogue of 1,8-diepiswainsonine. A similar analogue of swainsonine can be made by analogous methods starting with D-glycero-D-talo-heptono-1,4-lactone to produce the novel (1S, 2R, 6R, 7S)-1,2,6,7-tetrahydroxypyrrolizidine.
DETAILED DESCRIPTION OF THE INVENTION
The invention is conveniently illustrated by the following description of the preferred embodiments in which 1α, 2α, 6α, 7α, 7αβ-1,2,6,7-tetrahydroxypyrrolizidine (1) is synthesized from D-glycero-D-gulo-heptono-1,4-lactone (6) by two different Methods A and B, in ten steps as follows in which compound numbers in parentheses correspond to compounds shown by chemical structure herein:
A.
(1) The primary hydroxyl group in heptonolactone (6) is treated with a silyl blocking agent such as tert-butyldiphenylsilyl chloride to give the protected lactone (7).
(2) The protected lactone (7) is reacted with 2,2-dimethoxypropane to provide the fully protected lactone or diacetonide (9).
(3) The diacetonide (9) is reacted with fluoride ion to cleave the silyl ether at C7 and thereby provide access to nitrogen in the ring and give the primary alcohol (10).
(4) The primary alcohol (10) is esterified with triflic anhydride to afford the triflate (11).
(5) The triflate (11) is reacted with azide ion to give the azidolactone (12).
(6) The azidolactone (12) is reduced to the azidodiol (13).
(7) The azidodiol (13) is reacted with methanesulfonyl chloride to provide the azidodimesylate (14).
(8) The azidodimesylate (14) is catalytically hydrogenated in ethanol at ambient temperature.
(9) The product from step 8 is heated in ethanol in the presence of sodium acetate to give the tetracyclic pyrrolizidine (15).
(10) The acetonide groups in the tetracyclic pyrrolizidine (15) are removed by acid hydrolysis to give the product 1α, 2α, 6α, 7α, 7αβ-1,2,6,7-tetrahydroxypyrrolizidine (1). ##STR3##
B.
Steps 1 and 2 are the same as in Method A.
(3) The fully protected lactone or diacetonide (9) is reduced to give the silyl diol (16).
(4) The silyl diol (16) is reacted with methanesulfonyl chloride to provide the dimesylate (17).
(5) Nitrogen is introduced into the ring by reaction of the dimesylate (17) with benzylamine to give the monocylic pyrrolidine (20).
(6) The silyl protecting group is removed from C7 of the monocylic pyrrolidine (20) by treatment with fluoride ion to provide the primary diol (21).
(7) The primary diol (21) is reacted with methanesulfonyl chloride to give the unstable mesylate (22) which spontaneously closes to form the second pyrrolidine ring and give the N-benzyl pyrrolizidinium salt (23).
(8) The N-benzyl group in (23) is cleaved by catalyzed hydrogenation.
(9) Neutralization of the product of step 8 gives the tetracyclic pyrrolizidine (15).
(10) The acetonide groups in the tetracyclic pyrrolizidine (15) are removed by acid hydrolysis to give the product 1α, 2α, 6α, 7α, 7αβ-1,2,6,7-tetrahydroxypyrrolizidine (1). ##STR4##
The fully protected lactone or diacetonide (9), namely 7-O-tert-butyldiphenylsilyl-2,3:5,6-di-O-isopropylidene-D-glycero-D-gulo-heptono-1,4-lactone, is a novel intermediate that can be used as a starting material for each of Methods A and B, above. Both Methods A and B result in preparation of the novel fully protected tetracyclic pyrrolizidine (15), namely 1α-2α, 7α, 7αβ-1,2,6,7-di-O-isopropylidene-1,2,6,7-tetrahydroxy pyrrolizidine, from which the protecting groups can readily be removed by acid hydrolysis.
Other such suitable reactants for use in the foregoing syntheses of Methods A and B will be apparent to the person skilled in the art after reading the present disclosure. These reactants are generally used in proportions such as to satisfy the stoichiometry of the above reaction steps. Illustrative of such other reactants are the use of t-butyldimethylsilyl chloride to introduce the silyl protecting groups; use of other ketones, e.g., acetone, 3-pentanone, dihexylketone, cyclohexanone, and the like to introduce suitable hydroxyl protecting groups; use of other azide cations to introduce the azide group, e.g. potassium, lithium and tetra-butylammonium; and use of other solvent media such as DMF, THF, DMSO, N-methylpyrrolidine, acetonitrile and the like.
The foregoing reactions in Methods A and B were illustratively carried out as follows:
SYNTHESIS OF TETRAHYDROXYPYRROLIZIDINE (1)
A. The synthesis of 1α, 2α, 6α, 7αβ-1,2,6,7-tetrahydroxypyrrolizidine (1), with five adjacent chiral centres and seven adjacent carbon atoms bearing functional groups, requires the joining of C-1, C-4 and C-7 of the heptonolactone (6) by nitrogen with inversion of configuration at C-4. The order in which the formation of the different carbon-nitrogen bonds are formed is variable, although protection of the hydroxyl groups at C-2, C-3, C-5 and C-6 is required; bis-isopropylidene protection of the hydroxyl functions assists the intramolecular cyclizations to the pyrrolidine rings, since fused five-five membered rings are formed.
The primary hydroxyl group in (6) was protected as the tert-butyldiphenylsilyl ether by reaction with tert-butyldiphenylsilyl chloride in the presence of imidazole to afford (7) in 55% yield [Hanessian and Lavallee, Can. J. Chem. 53, 2975-2977 (1975)]. Although the silyl chloride was present in only slight excess, a significant amount (18%) of a disilyl derivative was also formed; the structure of this by-product was tentatively assigned as the 2,7-disilylether (8), since hydroxyl groups α- to lactone carbonyl groups show enhanced reactivity in silylation reactions [Mark and Zbiral, Monatsch. Chem. 112, 215-239 (1981)]. Reaction with 2,2-dimethoxypropane in the presence of a catalyst of dl-camphor sulphonic acid gave the diacetonide (9) [68% yield], in which the presence of two 5-ring ketals is clearly indicated by two singlets for the quaternary isopropylidene carbons at about δ110 in the 13 C NMR spectrum; the quaternary carbon of a six ring ketal generally appears below δ100. If the acetonation reaction was stopped before completion, both 5- and 6-ring monoacetonides could be isolated from the reaction mixture, indicating that (9) is the thermodynamic product.
One approach to the synthesis of (1) from the divergent intermediate (9) requires initial introduction of nitrogen at C-7. Access was gained to C-7 by cleavage of the silyl ether with fluoride ion to give the primary alcohol (10) in 86% yield. Esterification of (10) with trifluoromethane sulphonic anhydride afforded the triflate (11) which with sodium azide in dimethylformamide at room temperature gave the azide (12) [77% yield from (10)]. The lactone (12) was reduced by sodium borohydride in ethanol to the azidodiol (13) [93% yield] which was reacted with excess methanesulphonyl chloride in pyridine in the presence of 4-dimethylaminopyridine to give the dimesylate (14) [94% yield]. Hydrogenation of the azidodimesylate (14) in ethanol in the presence of a catalyst of palladium black, followed by heating in ethanol in the presence of sodium acetate, lead directly to the tetracyclic pyrrolizidine (15) in 76% yield. In (15), C-1 is equivalent with C-7, C-2 with C-6 and C-3 with C-5 giving only five signals in the δ2.5-5.0 region of the 1 H NMR sprectrum, and only four signals in the δ55-85 region of the 13 C NMR spectrum; additionally in the .sup. 13 C NMR spectrum, the quaternary isopropylidene carbons are equivalent and there are two pairs of equivalent isopropylidene methyl carbons. Removal of the acetonide groups from (15) by treatment with aqueous trifluoroacetic acid gave the desired tetrahydroxypyrrolizidine (1) in 90% yield [15% overall yield for the ten steps from heptonolactone (6)]. It is clear that removal of the two cyclic ketals in (15) has resulted in a change of the torsion angles within the structure, since there are significant changes in the coupling constants between (1) and (15).
B. An alternative synthesis of (1) from the fully protected lactone (9) involves initial formation of a pyrrolidine ring between C-1 and C-4. Reduction of the lactone (9) with lithium aluminum hydride in tetrahydrofuran gave the diol (16) in the 77% yield, providing access to the C-1 and C-4 hydroxyl groups while all the other oxygen functions are protected. The silyl diol (16) was then converted into the dimesylate (17) [66% yield] by treatment with methanesulphonyl chloride in pyridine in the presence of 4-dimethylaminopyridine; the anhydrosugar (19) [32% yield] was also obtained in this reaction, presumably arising from intramolecular cyclization of the monomesylate (18). Nitrogen was introduced by reaction of the dimesylate (17) with benzylamine giving the monocyclic pyrrolidine (20) in 72% yield; efficient cyclization of 1,4-dimesylates to pyrrolidines on treatment with benzylamine has been reported by Fleet et al., Tetrahedron44, 2469-2655 (1988); Fleet and Son, Ibid. 44, 2637-2647 (1988). The formation of the second pyrrolidine ring was achieved by first removing the silyl protecting group from C-7 of (20) by treatment with fluoride ion (84% yield). Subsequent mesylation of the primary alcohol (21) gave the unstable mesylate (22) which spontaneously closed to give the N-benzyl pyrrolizidinium salt (23). Cleavage of the N-benzyl group by hydrogenation of (23) in ethanol in the presence of palladium black, followed by neutralization with sodium bicarbonate gave the pyrrolizidine diacetonide (15) [31% yield from (21)], identical in all respects to the sample of (15) prepared by the alternative Method A, above.
GLYCOSIDASE INHIBITION
The effect of 1α,2α,6α,7α,7αβ-1,2,6,7-tetrahydroxypyrrolizidine (1) on the activity of 12 human liver glycosidases was tested by assay methods described by Daher et al., Biochem. J.258, 613-615 (1989). The compound (1) is a weak inhibitor of all human lysosomal, Golgi II and neutral α-mannosidases (I 50 approximately 1 mM); in addition it is also a weak inhibitor of α-fucosidase, α-and β-galactosidase, and the broad specificity β-galactosidase/β-glucosidase. The pyrrolizidine (1) is structurally related to 1,4-dideoxy-1,4-imino-L-allitol (DIA) (24) which is also a relatively weak inhibitor of lysosomal α-mannosidase (K i 1.2×10 -4 M). DIA (24) is comparable to the pyrrolizidine (1) in its inhibition of the neutral and Golgi II α-mannosidases [Cenci di Bello et al., Biochem. J.259, 855-861 (1989)]; both DIA and (1) have a relatively broad specificity of inhibition of glycosidases [Daher et al., supra.]. In contrast, the closely related indolizidine 8,8a-diepiswainsonine (25) is a very effective inhibitor of lysosomal (K i 2×10 -6 M) and Golgi processing α-mannosidase, both in vivo and in vitro, and the indolizidine (25) fits the active site of the α-mannosidases more closely than (1) or (24).
The following examples will further illustrate the invention in greater detail although it will be appreciated that the invention is not limited to these specific examples.
METHODS
Melting points were recorded on a Kofler block and are corrected. Infrared spectra were recorded on either a Perkin-Elmer 781 spectrophotomer or a Perkin-Elmer 1750 IR FT spectrometer. Optical rotations were measured on a Perkin-Elmer 241 polarimeter with a path-length of 10 cm; concentrations are given in g/100 ml. 1 H NMR spectra were run either at 200 MHz on a Varian Gemini 200 spectrometer, or at 300 MHz on a Bruker WH 300 spectrometer. Chemical shifts are quoted on the scale using residual solvent as an internal standard. 13 C NMR spectra were recorded at 50 MHz on a Varian Gemini 200 spectrometer; for samples in D 2 O, dioxan (δ67.2) was added as a reference. Mass spectra were recorded on either a VG Micromass ZAB 1F, a VG Mass 1ab 20-250 or a TRIO 1 spectrometer using chemical ionization (CI) or desorption chemical ionization (DCI) techniques. Microanalyses were performed by the microanalytical service of the Dyson Perrins Laboratory, Oxford, U.K. T.l.c. was performed on glass plates coated with silica gel Blend 41 (80% silica gel HF 254 and 20% silica gel G) or on aluminum plates coated with Merck silica gel 60F 254 . Compounds were visualized with a spray of 0.2% w/v ceric sulphate and 5% ammonium molybdate in 2 M sulphuric acid, or 0.5% ninhydrin in methanol (for amines). Flash chromatography was carried out using Sorbsil C60 40/60 flash silica gel. Dry column chromatography was carried out using Merck Kieselgel 60H. Ion exchange columns were packed with Aldrich 50X, 8-100 resin in the H + form. Pyridine and benzylamine were distilled (and stored) over potassium hydroxide. Hexane was distilled to remove involatile fractions. Immediately prior to use, dimethylformamide (DMF) and dichloromethane were distilled from calcium hydride, and tetrahydrofurane (THF) was distilled from sodium benzophenone ketyl. D-glycero-D-gulo-Heptono-1,4-lactone (6) was obtained from Sigma.
EXAMPLE 1
7-O-tert-Butyldiphenylsilyl-D-glycero-D-gulo-heptono-1,4-lactone (7) and 2,7-di-O-tert-Butyldiphenylsilyl-D-glycero-D-gulo-heptono-1,4-lactone (8)
D-glycero-D-gulo-Heptono-1,4-lactone (6) (10 g, 48.08 mmol) and imidazole (4.98 g, 1.5 equiv) were added to dry DMF (25 ml) and the mixture stirred at 0° C. under nitrogen. tert-Butylchlorodiphenylsilane (13.74 ml, 1.1 equiv) was added slowly, after which the reaction mixture was allowed to warm up to room temperature over three hours. After 22 hours, t.l.c. (eluant ethyl acetate) indicated that the mixture contained the desired monosilyl derivative (R f 0.65) and a smaller amount of another carbohydrate derivative (R f 0.9). The crude reaction mixture was shaken with water (50 ml), causing a white precipitate to form. Ethyl acetate (90 ml) was added and the layers separated after shaking. The aqueous layer was back-extracted with more ethyl acetate (25 ml). The combined organic extracts were washed with saturated aqueous sodium chloride (4×25 ml) and dried (magnesium sulphate). Evaporation of the solvent followed by dry column chromatography (eluant hexane:ethyl acetate, 2:1, increasing the eluant polarity with each fraction), yielding 7 -O-tert-butyldiphenylsilyl-D-glycero-D-gulo-heptono-1,4-lactone (7) (11.02 g, 55%) as a white solid, m.p. 54°-57° C. (Found: C, 61.58; H, 6.86%. C 23 H 30 O 7 Si requires: C, 61.87; H, 6.77%); [α] d 20 -10.56° (c, 0.99 in CHCl 3 ); v max (CHCl 3 ) 3410 (broad, OH) and 1790 cm -1 (γ-lactone); and 2,7-di-O-tert-butyldiphenylsilyl-D-glycero-D-gulo-heptono-1,4-lactone (8) (5.94 g, 18%) as a colorless, viscous oil [α] D 20 -4.08° (c, 1.20 in CHCl 3 ); v max (CHCl 3 ) 3440 (broad, OH) and 1790 cm -1 (γ-lactone).
EXAMPLE 2
7-O-tert-Butyldiphenylsilyl-2,3:5,6-di-O-isopropylidene-D-glycero-D-gulo-heptono-1,4-lactone (9)
7-O-tert-Butyldiphenylsilyl-d-glycero-D-gulo-heptono-1,4-lactone (7) (3.00 g, 6.73 mmol) and d1-camphor sulphonic acid (0.15 g, 5%) were dissolved in dry acetone (60 ml). 2,2-Dimethoxypropane (3.50 g, 5 equiv) was added and the mixture was stirred at 50° C. under reflux for 22 hours. The reaction was quenched by addition of excess sodium hydrogen carbonate, at which stage t.l.c. (eluant hexane:ethyl acetate, 6:1) indicated that the reaction mixture contained three compounds, one major product (R f 0.6) together with two minor products (R f 0.8 and 0.1). After filtration and evaporation of the solvent, the residue was purified by flash chromatography (eluant hexane:ethyl acetate, 8:1), yielding 7-O-tert-butyldiphenylsilyl-2,3:5,6-di-O-isopropylidene-D-glycero-D-gulo-heptono-1,4-lactone (9) (2.40 g, 68%) as a white, crystalline solid, m.p. 104°-106° C. (Found: C, 66.19; H, 7.58%. C 29 H 38 O 7 Si requires: C, 66.13; H, 7.27%); [α] D 20 -21.64° (c, 0.98 in CHCl 3 ); v max (CHCl 3 ) 1790 (γ-lactone), 1386 and 1377 cm -1 (CMe 2 ).
EXAMPLE 3
2,3:5,6-Di-O-isopropylidene-D-glycero-D-gulo-heptono-1,4-lactone (10)
7-O-tert-Butyldiphenylsilyl-2,3:5,6-di-O-isopropylidene-D-glycero-D-gulo-heptono-1,4-lactone (9) (4.11 g, 7.81 mmol) was dissolved in dry THF (200 ml) and the solution was stirred under nitrogen. Tetra-n-butylammonium fluoride (11.7 ml of a 1M solution in THF, 1.5 equiv) was added dropwise. After one and a half hours t.l.c. (eluant hexane:ethyl acetate, 6:1) indicated one product at the baseline but no starting material (R f 0.6). Evaporation of the solvent gave a pale yellow oil which was purified by flash chromatography (eluant ethyl acetate:hexane, 3:2) yielding 2,3:5,6-di-O-isopropylidene-D-glycero-D-gulo-heptono-1,4-lactone (10) (1.93 g, 86%) as a white, crystalline solid, m.p. 115°-120° C. (Found: C, 54.46; H, 6.99%. C 13 H 20 O 7 requires: C, 54.16; H, 6.99%); [α] D 20 -53.40° (c, 1.05 in CHCl 3 ); v max (CHCl 3 ) 3560 (OH), 1790 (γ-lactone), 1388 and 1379 cm -1 (CMe 2 ).
EXAMPLE 4
7-Azido-7-deoxy-2,3:5,6-di-O-isopropylidene-D-glycero-D-gulo-heptono-1,4-lactone (12)
2,3:5,6-Di-O-isopropylidene-D-glycero-D-gulo-heptono-1,4-lactone (10) (0.50 g, 1.74 mmol) was dissolved in dry dichloromethane (50 ml) and dry pyridine (0.28 ml, 2 equiv) was added and the solution was stirred at -30° C. under nitrogen. Trifluoromethanesulphonic anhydride (0.44 ml, 1.5 equiv) was added slowly, and after 30 minutes, t.l.c. (eluant ethyl acetate:hexane, 2:1) indicated complete conversion to product (R f 0.9). The reaction mixture was worked up as quickly as possible by washing with ice cold saturated aqueous sodium chloride (35 ml) followed by drying over sodium sulphate. The solvent was evaporated leaving an orange residue which was dissolved in dry DMF (20 ml). Without further purification, sodium azide (0.226 g, 2 equiv based on quantitative triflation) was added and the mixture stirred at room temperature under nitrogen. After 30 minutes, t.l.c. (eluant hexane:ethyl acetate, 2:1) indicated that a product had formed (R f 0.4). The solvent was evaporated, leaving a residue which was dissolved in dichloromethane (30 ml) and washed with water (3×15 ml). After drying (magnesium sulphate) and evaporation of the solvent, flash chromatography (eluant hexane:ethyl acetate, 2:1) yielded 7-azido-7-deoxy-2,3:5,6-di-O-isopropylidene-D-glycero-D-gulo-heptono-1,4-lactone (12) (0.42 g, 77% over two steps) as a white, crystalline solid, m.p. 89°-91° C. (Found: C, 50.10; H, 6.29; N, 13.18%. C 13 H 19 N 3 O 6 requires: C, 49.84; H, 6.11; N, 13.41%); [α].sub. d 20 +34.57° (c, 1.00 in CHCl 3 ); v max (CHCl 3 ) 2110 (N 3 ), 1795 (γ-lactone), 1386 and 1378 cm -1 (CMe 2 ).
EXAMPLE 5
7-Azido-7-deoxy-2,3:5,6-di-O-isopropylidene-D-glycero-D-gulo-heptitol (13)
7-Azido-7-deoxy-2,3:5,6-di-O-isopropylidene-D-glycero-D-gulo-heptono-1,4-lactone (12) (1.84 g, 5.88 mmol) was dissolved in ethanol (100 ml) and stirred at 0° C. under nitrogen. Sodium borohydride (0.445 g, 2 equiv) was added and the reaction mixture allowed to warm up to room temperature. After 18 hours, t.l.c. (eluant hexane:ethyl acetate, 2:1) indicated that all starting material had been converted to product (R f 0.2). The reaction was quenched by addition of excess solid ammonium chloride, with effervescence. Filtration and evaporation of the solvent gave a residue which was purified by flash chromatography (eluant hexane:ethyl acetate, 2:1) yielding 7-azido-7-deoxy-2,3:5,6-di-O-isopropylidene-D-glycero-D-gulo-heptitol (13) (1.74 g, 93%) as a colorless, viscous oil (Found: C, 49.26; H, 7.30; N, 13.26%. C 13 H 23 N 3 O 6 requires: C, 49.20; H, 7.30; N, 13.24%); [α] D 20 +2.87° (c, 0.94 in CHCl 3 ); v max 3553 (broad, OH), 2107 (N 3 ), 1384 and 1375 cm -1 (CMe 2 ).
EXAMPLE 6
7-Azido-7-deoxy-2,3:5,6-di-O-isopropylidene-1,4-di-O-methanesulphonyl-D-glycero-D-gulo-heptitol (14)
7-Azido-7-deoxy-2,3:5,6-di-O-isopropylidene-D-glycero-D-gulo-heptitol (13) (0.95 g, 3.00 mmol) and 4-dimethylaminopyridine (DMAP) (1 mg) were dissolved in dry pyridine (15 ml) and stirred at 0° C. under nitrogen. Methanesulphonyl chloride (1.39 ml, 6 equiv) was added slowly and after 4 hours the reaction mixture was allowed to warm up to room temperature. After 18 hours, t.l.c. (eluant hexane:ethyl acetate, 2:1) indicated that no starting material remained (R f 0.2) while a major product had formed (R f 0.25). The solvent was evaporated, leaving a red oil which was dissolved in ethyl acetate (150 ml) and washed with water (75 ml). After drying (magnesium sulphate) the crude mixture was purified by flash chromatography (eluant hexane:ethyl acetate, 2:1) yielding 7-azido-7-deoxy-2,3:5,6-di-O-isopropylidene-1,4-di-O-methanesulphonyl-D-glycero-D-gulo-heptitol (14) (1.33 g, 94%) as a colorless, viscous oil, [α] D 20 +8.22° (c, 1.07 in CHCl 3 ); v.sub. max (CHCl 3 ) 2109 cm -1 (N 3 ).
EXAMPLE 7
1α,2α,6α,7α,7αβ-1,2:6,7-Di-O-isopropylidene-1,2,6-7-tetrahydroxy pyrrolizidine (15)
7-Azido-7-deoxy-2,3:5,6-di-O-isopropylidene-1,4-di-O-methanesulphonyl-D-glycero-D-gulo-heptitol (14) (0.64 g, 1.35 mmol) was dissolved in ethanol (50 ml) and palladium black (10%) was added. After degassing the solution, the reaction mixture was stirred vigorously under hydrogen at room temperature for two hours. At this stage, t.l.c. (eluant hexane:ethyl acetate, 2:1) indicated that all starting material (R f 0.25) had reacted to give a product which remained at the baseline. The reaction mixture was filtered through celite to remove the catalyst, sodium acetate (0.33 g, 3 equiv based on quantitative reduction) added and the mixture stirred at 50° C. under nitrogen. After 12 hours, t.l.c. (eluant ethyl acetate:methanol, 9:1) showed that the reaction mixture was predominantly one compound (R f 0.5). After evaporating the solvent, the crude mixture was purified by flash chromatography (eluant ethyl acetate, increasing polarity to ethyl acetate:methanol, 9:1) giving 1α,2α,6α,7α,7αβ-1,2:6,7-di-O-isopropylidene-1,2,6,7-tetrahydroxy pyrrolizidine (15) (0.26 g, 76% over two steps) as a pale brown solid, m.p. 66°-69° C. (diethyl ether) (Found: C, 60.81; H, 8.44; N, 5.23%. C 13 H 21 NO 4 requires: C, 61.16; H, 8.29; N, 5.49%); [α] D 20 +1.06° (c, 1.14 in CHCl 3 ).
EXAMPLE 8
1α,2α,6α,7α,7αβ-1,2,6,7-Tetrahydroxy Pyrrolizidine (1)
1α,2α,6α,7α,7αβ-1,2,6,7-Di-O-isopropylidene-1,2,6,7-tetrahydroxy pyrrolizidine (15) (112 mg, 0.44 mmol) was dissolved in 50% aqueous trifluoroacetic acid (20 ml) and stirred at room temperature for six hours. After evaporation of the solvent, the residue was dissolved in water and purified on an ion exchange column (H + form), eluting with 0.5M aqueous ammonia. Freeze drying yielded 1α,2α,6α,7α,7αβ-1,2,6,7-tetrahydroxy pyrrolizidine (1) (69 mg, 90%) as a pale brown solid, m.p. 170°-175° C. (dec.) (Found: C, 47.62; H, 7.65; N, 7.77%. C 7 H 13 NO 4 requires: C, 47.99; H, 7.48; N, 8.00%); [α] D 20 0° (c, 1.06 in H 2 O); v max (KBr disc) 3400 cm -1 (very broad, OH).
EXAMPLE 9
7-O-tert-Butyldiphenylsilyl-2,3:5,6-di-O-isopropylidene-D-glycero-D-gulo-heptitol (16)
7-O-tert-Butyldiphenylsilyl-1,2:5,6-di-O-isopropylidene-D-glycero-D-gulo-heptono-1,4-lactone (9) (116 mg, 0.22 mmol) was dissolved in dry THF (10 ml) and stirred at 0° C. under nitrogen. Lithium aluminum hydride (25 mg, 3 equiv) was added and the reaction mixture allowed to warm up slowly to room temperature. After 9 hours, t.l.c. (eluant hexane:ethyl acetate, 2:1) indicated that no starting material remained (R f 0.9) while a major product had formed (R f 0.1). The reaction was quenched by the addition of excess solid ammonium chloride, the mixture filtered and the solvent evaporated. Purification by flash chromatography (eluant hexane:ethyl acetate, 3:1) yielded 7-O-tert-butyldiphenylsilyl-2,3:5,6-di-O-isopropylidene-D-glycero-D-gulo-heptitol (16) (78 mg, 77%) as a colorless, viscous oil, [α] D 20 -2.39° (c, 1.05 in CHCl 3 ); v max (CHCl 3 ) 3561 (broad, OH), 1383 and 1374 cm -1 (CMe 2 ).
EXAMPLE 10
7-O-tert-Butyldiphenylsilyl-2,3:5,6-di-O-isopropylidene-1,4-di-O-methanesulphonyl-D-glycero-D-gulo-heptitol (17) and 1,4-anhydro-7-O-tert-butyldiphenylsilyl-1-deoxy-2,3:5,6-di-O-isopropylidene-D-glycero-D-gulo-heptitol (19)
7-O-tert-Butyldiphenylsilyl-2,3:5,6-di-O-isopropylidene-D-glycero-D-gulo-heptitol (16) (260 mg, 0.49 mmol) and DMAP (1 mg) were dissolved in dry pyridine (10 ml) and stirred at 0° C. under nitrogen. Methanesulphonyl chloride (0.15 ml, 4 equiv) was added slowly and after 3 hours the reaction mixture was allowed to warm up to room temperature. After 20 hours, t.l.c. (eluant hexane:ethyl acetate, 3:2) indicated that two products had formed (R f 0.5 and 0.8) while no starting material remained (R f 0.4). After evaporation of the solvent, the residue was shaken with ethyl acetate (60 ml), leaving an insoluble brown solid. The filtrate was washed with water (70 ml) and dried (magnesium sulphate). After filtration and evaporation of the solvent, flash chromatography (eluant hexane:ethyl acetate, 3:1) yielded 7-O-tert-butyldiphenylsilyl-2,3:5,6-di-O-isopropylidene-1,4-di-O-methanesulphonyl-D-glycero-D-gulo-heptitol (17) (224 mg, 67%) as a colorless, viscous oil, [α] D 20 -9.40° (c, 1.08 in CHCl 3 ); and 1,4-anhydro-7-O-tert-butyldiphenylsilyl-1-deoxy-2,3:5,6-di-O-isopropylidene-D-glycero-D-gulo-heptitol (19) (81 mg, 32%) as a colorless, viscous oil, [α] D 20 +34.71° (c, 1.02 in CHCl 3 ); v max (CHCl 3 ) 1382 and 1375 cm -1 (CMe 2 ).
EXAMPLE 11
N-Benzyl-7-O-tert-butylphenylsilyl-1,4-dideoxy-2,3:5,6-di-O-isopropylidene-1,4-imino-D-glycero-D-allo-heptitol (20)
7-O-tert-Butyldiphenylsilyl-2,3:5,6-di-O-isopropylidene-1,4-di-O-methanesulphonyl-D-glycero-D-gulo-heptitol (17) (147 mg, 0.21 mmol) was dissolved in benzylamine (10 ml) and stirred at 50° C. under nitrogen for 72 hours. At this stage, t.l.c. (eluant hexane:ethyl acetate, 3:1) indicated that no starting material remained (R f 0.2) while a major product had formed (R f 0.8). The benzylamine was evaporated, leaving a dark red oil which was dissolved in ethyl acetate (20 ml). Silica gel was added and the solvent evaporated to pre-absorb the compound. Flash chromatography (eluant hexane, increasing polarity to hexane:ethyl acetate, 6:1) yielded N-benzyl-7-O-tert-butyldiphenylsilyl-1,4-dideoxy-2,3:5,6-di-O-isopropylidene-1,4-imino-D-glycero-D-allo-heptitol (20) (94 mg, 72%) as a pale yellow, viscous oil, [α] D 20 -14.08° (c, 1.20 in CHCl 3 ); v max (CHCl 3 ) 1383 and 1375 cm -1 (CMe 2 ).
EXAMPLE 12
N-Benzyl-1,4-dideoxy-2,3:5,6-di-O-isopropylidene-1,4-imino-D-glycero-D-allo-heptitol (21)
N-Benzyl-7-O-tert-butyldiphenylsilyl-1,4-dideoxy-2,3:5,6-di-O-isopropylidene-1,4-imino-D-glycero-D-allo-heptitol (20) (94 mg, 0.16 mmol) was dissolved in dry THF (10 ml) and stirred at room temperature under nitrogen. Tetra-n-butylammonium fluoride (0.23 ml of a 1M solution in THF, 1.5 equiv) was added and after 3 hours, t.l.c. (eluant hexane:ethyl acetate, 3:1) indicated that no starting material remained (R f 0.8) while a major product had formed (R f 0.25). Evaporation of the solvent followed by flash chromatography (eluant hexane:ethyl acetate, 3:1) yielding N-benzyl-1,4-dideoxy-2,3:5,6-di-O-isopropylidene-1,4-imino-D-glycero-D-allo-heptitol (21) (48 mg, 84%) as a colorless, viscous oil, [α] D 20 -58.44° (c, 1.03 in CHCl 3 ); v max (CHCl 3 ) 3670 (OH), 1386 and 1377 cm -1 (CMe 2 ).
EXAMPLE 13
1α,2α,6α,7α,7αβ-1,2:6,7-Di-O-isopropylidene-1,2,6,7-tetrahydroxy pyrrolizidine (15)
N-Benzyl-1,4-dideoxy-2,3:5,6-di-O-isopropylidene-1,4-imino-D-glycero-D-allo-heptitol (21) (91 mg, 0.25 mmol) was dissolved in dry dichloromethane (15 ml). Dry pyridine (0.04 ml, 2 equiv) was added and the solution stirred at 0° C. under nitrogen. Methanesulphonyl chloride (0.03 ml, 1.5 equiv) was added slowly, and after 4 hours the reaction mixture was allowed to warm up to room temperature. After 24 hours, t.l.c. (eluant hexane:ethyl acetate, 3:1) indicated a product at the baseline but no starting material (R f 0.25). Evaporation of the solvent and trituration with diethyl ether (2×5 ml) gave a white solid residue which was dissolved in ethanol (5 ml) and added to a mixture of pre-reduced palladium black (10%) in degassed ethanol (10 ml). The resultant mixture was stirred vigorously at room temperature under hydrogen for 24 hours and then filtered through celite. Evaporation of the solvent gave a white solid residue which was dissolved in ethyl acetate (20 ml), washed with saturated aqueous sodium hydrogen carbonate (10 ml) and dried (magnesium sulphate). Flash chromatography (eluant ethyl acetate, increasing polarity to ethyl acetate:methanol, 9:1) yielded 1α,2α,6α,7α,7αβ-1,2:6,7-di-O-isopropylidene-1,2,6,7-tetrahydroxy pyrrolizidine (15) (20 mg, 31%) as a pale yellow oil with spectroscopic data identical to those in Example 7, above.
Various other examples will be apparent to the person skilled in the art after reading the present disclosure without departing from the spirit and scope of the invention. It is intended that all such other examples be included within the scope of the appended claims. | Novel bicyclic tetrahydroxylated pyrrolizidines are disclosed which are inhibitors of glycosidase enzymes. A preferred inhibitor is 1α, 2α, 6α, 7α, 7αβ-1,2,6,7-tetrahydroxypyrrolizidine. It is synthesized from D-glycero-D-gulo-heptono-1,4-lactone.
Novel Intermediate compounds prepared during this synthesis are 7-O-tert-butyldiphenylsilyl-2,3:5,6-di-O-isopropylidene-D-glycero-D-gulo-hept ono-1,4-lactone and 1α, 2α, 6α, 7α, 7αβ-1,2:6,7-di-O-isopropylidene-1,2,6,7-tetrahydroxypyrrolizidine. | 2 |
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